Fiber fabric composite and method for producing the same, and self-lubricating solid material and joint bearing liner

Abstract

The application relates to the technical field of self-lubricating composite materials, and provides a fiber fabric composite material, a preparation method thereof, a self-lubricating solid material and a joint bearing pad. The fiber fabric composite material comprises a fiber fabric and an impregnated resin loaded on the fiber fabric, and the impregnated resin comprises sulfonated polyarylene ether ketone. The fiber fabric composite material has excellent lubricating performance under low-temperature heavy-load conditions, and the preparation method is simple.

Description

Technical Field

[0001] This application relates to the field of self-lubricating composite materials technology, and in particular to a fiber fabric composite material, a method for preparing the same, a self-lubricating solid material, and a spherical bearing liner. Background Technology

[0002] Wind tunnels are the cradle of aerospace engine development, and their experimental testing capabilities are a crucial indicator of aircraft development levels. In large cryogenic wind tunnels, the spherical plain bearings and sliding supports used in the nozzle section flexible plate support and internal section support are subjected to heavy loads and low temperatures for extended periods. Spherical plain bearings are a type of spherical sliding bearing, characterized by high load capacity, impact resistance, corrosion resistance, wear resistance, self-aligning properties, and good lubrication.

[0003] For self-lubricating spherical plain bearings, the realization of their self-lubricating and friction-reducing function is determined by the tribological properties of the gaskets made of fiber-woven composite materials. To improve the accuracy of low-temperature Reynolds number wind tunnel tests and the service life and safety of key components, the gasket material is required to have a low coefficient of friction and excellent wear resistance under extreme environments such as low temperature / large temperature change (110K-323K) nitrogen, normal temperature air, and heavy loads. As a key component of the bearing, the self-lubricating fiber-woven composite material plays a crucial role in the bearing's performance.

[0004] Currently, self-lubricating fabric composites are mainly formed by combining fabric fibers with lubricating properties with impregnating resins and then curing them. The impregnating resin can improve the bonding force between fibers, making the fibers more rigid from a soft and easily deformable state, thus improving the mechanical strength and load-bearing capacity of the fabric. The impregnating liquids currently used are mainly of two categories: thermosetting polymers (such as phenolic resins or epoxy resins) and thermoplastic polymers (such as polyetherimide). The frictional properties of the fiber fabrics obtained after curing with the two types of impregnating liquids do not differ significantly at room temperature. However, at low temperatures, the lubrication properties of fiber fabrics prepared with thermosetting resins are poor, while those prepared with thermoplastic resins are superior. However, the coefficients of friction of commonly used phenolic resin-reinforced fabrics and polyetherimide-reinforced fabrics both show a significant increase with decreasing temperature, indicating that their lubrication performance needs further improvement. Summary of the Invention

[0005] Based on this, this application provides a fiber fabric composite material, its preparation method, a self-lubricating solid material, and a spherical bearing gasket. The fiber fabric composite material of this application exhibits excellent lubrication performance under low-temperature heavy-load conditions, and its preparation method is simple.

[0006] In a first aspect, this application provides a fiber fabric composite material comprising a fiber fabric and an impregnation resin loaded on the fiber fabric, the impregnation resin comprising sulfonated polyarylether ketone.

[0007] In a second aspect, this application provides a method for preparing the fiber fabric composite material described in the first aspect of this application, comprising: impregnating the fiber fabric with an impregnation solution containing an impregnation resin, thereby loading the impregnation resin onto the fiber fabric.

[0008] Thirdly, this application provides a self-lubricating solid material, including a supporting substrate and a fiber fabric composite material bonded to the surface of the supporting substrate, wherein the fiber fabric composite material is the fiber fabric composite material of this application.

[0009] Fourthly, this application provides a spherical bearing gasket made of the self-lubricating solid material.

[0010] The fiber-fabric composite material provided in this application incorporates sulfonated polyaryletherketone (PAEK) as an impregnation resin. The polar sulfonate groups in PAEK bond with the fiber fabric via van der Waals bonds, enhancing the bonding ability between the resin and the fabric. Furthermore, due to the linear polymer structure of PAEK, it not only avoids the low-temperature brittleness and lack of lubricity of traditional thermosetting phenolic resins during friction but also effectively blends with lubricating fibers. This synergistic effect improves the low-temperature lubricity of the composite material, making it suitable for low-temperature heavy-load environments. Additionally, the preparation method of this application modifies PAEK, which is insoluble at room temperature, by introducing polar sulfonate groups to improve its solubility. This allows for the direct loading of high-performance polymers onto the fiber fabric in the form of a PAEK impregnation solution. This method is characterized by its simplicity, low cost, and high practicality.

[0011] Other features and advantages of this application will be described in detail in the following detailed description section. Attached Figure Description

[0012] Figure 1 This is a flowchart illustrating the preparation process of sulfonated polyether ether ketone, sulfonated polyether ether ketone impregnation liquid, and sulfonated polyether ether ketone reinforced fiber fabric composite material in one embodiment of this application.

[0013] Figure 2 This is a SEM image of the original lubricated surface of the fiber fabric according to one embodiment of this application;

[0014] Figure 3 The photograph shows a comparison of the solubility of polyether ether ketone in Preparation Example 1 before and after sulfonation modification.

[0015] Figure 4 Infrared spectra of polyether ether ketone (PEEEK) and sulfonated PEEK in Preparation Example 1. Detailed Implementation

[0016] To facilitate understanding of this application, a more complete description will be provided below with reference to the accompanying drawings. This application can be implemented in many different forms and is not limited to the embodiments described herein. Rather, these embodiments are provided to provide a more thorough and complete understanding of the disclosure of this application.

[0017] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. The terminology used herein, in the specification of this application, is for the purpose of describing particular embodiments only and is not intended to be limiting of the application. The term "and / or" as used herein includes any and all combinations of one or more of the associated listed items.

[0018] Currently, the friction of commonly used phenolic resin-reinforced and polyetherimide-reinforced fabrics increases significantly with decreasing temperature, limiting their application in spherical bearings. Polyaryletherketones (PAGEs) are thermoplastic polymers with chemically reactive functional groups (C=O and CO bonds). Compared to thermosetting phenolic resins, PAGEs exhibit interlaminar slippage during shearing, forming a homogeneous blend structure with the fibrous fabric and thus reducing friction. However, unlike phenolic and polyetherimide resins, PAGEs are insoluble in any organic solvent, preventing their use as impregnation solutions. They can only be introduced through methods such as blending with fibers, for example, using PAGEs as co-spun fibers in fabrics and introducing other nanoscale particles into impregnation solutions primarily composed of phenolic or polyetherimide resins. This method involves complex preparation processes, expensive raw materials, and limited practicality. To address this issue, the inventors of this application propose a sulfonated polyaryletherketone (PAEK) impregnation solution. This solution involves sulfonating and grafting PAEK, which solves the problem that PAEK is insoluble in any organic solvent and therefore cannot be used as an impregnation solution. This novel impregnation solution, upon contact with the fiber fabric, utilizes the sulfonate group to bind with polar groups such as hydroxyl groups on the fiber fabric, successfully introducing sulfonated PAEK onto the fabric. Based on this, this application is filed.

[0019] In a first aspect, this application provides a fiber fabric composite material comprising a fiber fabric and an impregnation resin loaded on the fiber fabric, the impregnation resin comprising sulfonated polyarylether ketone.

[0020] In this application, the sulfonated polyarylether ketone is prepared by sulfonation modification (reaction) of polyarylether ketone. It should be understood that polyarylether ketone (PAEK) is a class of crystalline polymers formed by the connection of phenylene rings via oxygen bridges (ether bonds) and carbonyl groups (ketones). Depending on the order and ratio of the ether bonds, ketone groups, and benzene rings in the molecular chain, many different polymers can be formed, such as polyether ether ketone (PEEK), polyether ketone (PEK), polyether ketone ketone (PEKK), polyether ether ketone ketone (PEEKK), and polyether ketone ether ketone ketone (PEKEKK), etc. The sulfonation modification method can be as described in the second aspect below for preparing sulfonated polyarylether ketone.

[0021] In some embodiments, the polyaryletherketone includes one or more of polyetheretherketone, polyetherketone, polyetherketoneketone, and polyetheretherketoneketone. Optionally, the sulfonated polyaryletherketone is sulfonated polyetheretherketone (SPEEK).

[0022] In this application, the fiber fabric can be a self-lubricating fiber fabric, such as a woven fabric including one or more fibers, including polytetrafluoroethylene (PTFE) fibers. In some embodiments, the fiber fabric is a blend of PTFE fibers and aramid fibers (e.g., Nomex), wherein the mass ratio of PTFE fibers to aramid fibers is (1.5–2.5):1, for example, 1.5:1, 1.8:1, 2:1, 2.1:1, 2.2:1, or 2.5:1. The blended fabric is, for example, woven using a twill weave with PTFE fibers as the weft yarn and aramid fibers as the warp yarn, with the surface enriched with PTFE fibers serving as the lubricating surface.

[0023] Furthermore, the areal density of the fiber fabric is 180 g / m³. 2 ~220g / m 2 The diameter of PTFE fiber is 14μm to 18μm, and the diameter of aramid fiber is 15μm to 25μm.

[0024] Optionally, the thickness of the fiber fabric is 0.2 mm to 0.25 mm.

[0025] In some embodiments, the impregnating resin content in the fiber fabric composite material is 8% to 35% by mass, for example, 8%, 10%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 20%, 25%, 30%, and 35%. Preferably, the impregnating resin content in the fiber fabric composite material is 15% to 30% by mass, which can further improve lubricity while ensuring low wear.

[0026] Secondly, this application provides a method for preparing the fiber fabric composite material, comprising: impregnating the fiber fabric with an impregnation solution containing an impregnation resin, thereby loading the impregnation resin onto the fiber fabric.

[0027] In some embodiments, the preparation method further includes: preparing the sulfonated polyarylether ketone.

[0028] In one specific embodiment, the method for preparing the sulfonated polyarylether ketone includes the following steps:

[0029] S1: The polyarylether ketone is subjected to a sulfonation reaction with a sulfonating agent to prepare a solution containing sulfonated polyarylether ketone;

[0030] S2: Mix the sulfonated polyaryletherketone solution with water to precipitate a crude product containing sulfonated polyaryletherketone;

[0031] S3: The crude product is washed sequentially with an alkaline aqueous solution and water, and then dried to obtain the sulfonated polyarylether ketone.

[0032] In step S1, optionally, the sulfonating agent includes one or more of concentrated sulfuric acid, fuming sulfuric acid, and chlorosulfuric acid.

[0033] Optionally, the amount of the sulfonating agent used relative to 1g of the polyarylether ketone is 5mL to 50mL; for example, 5mL, 10mL, 12mL, 15mL, 20mL, 25mL, 30mL, 40mL, 45mL or 50mL.

[0034] Optionally, the sulfonation reaction is carried out at a temperature of 50°C to 90°C for 3 hours to 10 hours. The sulfonation reaction can be carried out under stirring conditions, with a stirring speed of 200 rpm to 500 rpm.

[0035] In step S2, ultrapure water can be used to gradually precipitate the crude product from the solution containing sulfonated polyarylether ketone. The temperature of the ultrapure water is, for example, 0°C to 5°C.

[0036] In step S3, washing with the alkaline aqueous solution can remove hydrogen ions from the crude product. Optionally, the method of washing the crude product with the alkaline aqueous solution includes: placing the crude product in the alkaline aqueous solution and stirring at 60°C to 90°C for 3 to 8 hours.

[0037] Optionally, the alkaline aqueous solution includes an aqueous solution of sodium hydroxide and / or an aqueous solution of potassium hydroxide.

[0038] Furthermore, the alkali concentration in the alkaline aqueous solution is 1 g / L to 10 g / L.

[0039] In step S3, during the water washing process, ultrapure water can be used for multiple washes until the washing solution is neutral.

[0040] In step S3, the drying is vacuum drying, the drying temperature is 60℃~80℃, and the drying time is 24h~48h.

[0041] In some embodiments, the impregnation solution containing the impregnation resin has a mass concentration of 8% to 20%, for example, 8%, 8.5%, 9%, 9.5%, 10%, 12%, 15%, or 18%.

[0042] In this application, the impregnation solution containing the impregnation resin may be selected from various organic solvents capable of dissolving the impregnation resin, depending on the degree of sulfonation of the sulfonated polyarylether ketone. In some embodiments, the solvent in the impregnation solution includes one or more of N,N-dimethylformamide (DMF), N-methylpyrrolidone (NMP), and dichloromethane (CH2Cl2).

[0043] In this application, the impregnation solution can be prepared by mixing the impregnation resin and the solvent and then stirring to dissolve them. The stirring speed can be 100 rpm to 300 rpm.

[0044] To improve the loading rate of the impregnating resin on the fiber fabric, preferably, the impregnation process includes placing the fiber fabric in the impregnation liquid for ultrasonic treatment, re-drying, and repeating the operation multiple times, wherein ultrasonic treatment helps the fiber fabric to combine with the impregnation liquid, so that the liquid molecules are within the fibers.

[0045] According to a preferred embodiment, the impregnation process includes the following steps:

[0046] a) The fiber fabric is placed in the impregnation solution containing the impregnation resin and subjected to ultrasonic treatment;

[0047] b) Dry the ultrasonically treated fiber fabric;

[0048] c) Repeat the ultrasonic treatment and drying process as a cycle 2 to 4 times;

[0049] Optionally, the duration of each ultrasound treatment is 10 to 30 minutes, for example, 10 minutes, 15 minutes or 20 minutes.

[0050] Optionally, the drying temperature for each drying cycle is 50°C to 70°C, for example, 50°C, 60°C or 70°C; and the drying time for each drying cycle is 5 min to 20 min, for example, 10 min, 15 min or 20 min.

[0051] In some embodiments, before impregnating the fiber fabric with an impregnation solution containing an impregnation resin, the preparation method further includes: sequentially cleaning and plasma surface treatment of the fiber fabric.

[0052] Optionally, the cleaning process includes: ultrasonically cleaning the fibrous fabric in acetone for 3 to 7 hours (e.g., 5 hours), then ultrasonically cleaning it in ethanol for 3 to 7 hours (e.g., 5 hours), and then drying it in a forced-air drying oven.

[0053] Optionally, in the plasma surface treatment, the gas used is an oxygen-containing gas with a power of 80W to 120W and a treatment time of 5min to 20min. The plasma surface treatment can create fine, rough peaks on the fabric surface, increasing its specific surface area. This facilitates greater contact between the fabric and the impregnation liquid, allowing for wetting. Furthermore, it introduces hydroxyl groups into the fiber fabric, improving the bonding strength between the fabric and the impregnation resin.

[0054] In some embodiments, after impregnating the fiber fabric with an impregnation solution containing an impregnation resin, the preparation method further includes:

[0055] d) The resin-impregnated fiber fabric is cured and molded by hot pressing. This curing process ensures full contact between the resin and the fabric, resulting in a tightly packed composite material. The applied pressure is 0.5 MPa to 2 MPa, the hot pressing temperature is 80°C to 200°C, and the hot pressing time is 1 hour to 3 hours.

[0056] Optionally, the hot pressing is performed in two stages:

[0057] In the first stage, the temperature is increased to 80℃ to 120℃ at a heating rate of 3℃ / min to 5℃ / min, and maintained for 50min to 70min.

[0058] In the second stage, the temperature is increased to 160℃ to 200℃ at a rate of 3℃ / min to 5℃ / min, and maintained for 50min to 70min.

[0059] According to one embodiment, the fiber fabric composite material is a sulfonated polyetheretherketone reinforced fiber fabric composite material, such as... Figure 1 As shown, the preparation method of this composite material includes:

[0060] (1) Preparation of sulfonated polyether ether ketone

[0061] After mixing polyether ether ketone powder with a sulfonating agent, the mixture is heated to carry out a sulfonation reaction, resulting in a solution containing sulfonated polyether ether ketone.

[0062] The solution was washed with water to precipitate the crude product, which was then filtered to obtain the precipitated sulfonated polyether ether ketone (crude product).

[0063] The crude product was mixed with an alkaline aqueous solution, heated to dissolve, and then subjected to solid-liquid separation. After washing with water and drying, dried sulfonated polyether ether ketone was obtained.

[0064] (2) Dissolve sulfonated polyether ether ketone in a solvent to prepare sulfonated polyether ether ketone impregnation solution.

[0065] (3) The fiber fabric is impregnated with sulfonated polyether ether ketone impregnation liquid, and then hot-pressed and dried to cure and shape, thus obtaining the cured fabric, i.e. fiber fabric composite material.

[0066] Thirdly, this application provides a self-lubricating solid material, comprising a supporting substrate and a fiber fabric composite material bonded to the surface of the supporting substrate, wherein the fiber fabric composite material is the fiber fabric composite material provided in this application. In some embodiments, the fiber fabric composite material is bonded to one surface of the supporting substrate.

[0067] In some embodiments, the support substrate is made of metal, such as various metal materials used in spherical bearings. Optionally, the metal material includes 9Cr18, GCr15, or 304 stainless steel, preferably 9Cr18. By introducing the fiber fabric composite material onto the surface of the support substrate, the self-lubricating solid material retains high self-lubricating properties even under low-temperature, heavy-load conditions.

[0068] According to this application, the supporting substrate and the fiber fabric composite material can be bonded together using various adhesives, such as epoxy resin AB adhesive. The amount of adhesive used is not limited, as long as it is sufficient to bond the adhesive surfaces of the supporting substrate and the fiber fabric composite material together; the adhesive surface is the back side of the fabric's lubricated surface.

[0069] Fourthly, this application provides a spherical bearing gasket made of the self-lubricating solid material.

[0070] The present application is illustrated below through specific embodiments, but should not be construed as limiting the present application.

[0071] In the following examples and comparative examples,

[0072] The PTFE / Nomex blended fiber fabric is woven using a twill weave method, with PTFE fibers in the weft and Nomex fibers in the warp interlaced. One side of the fabric is the lubricating side (PTFE occupies 3 / 4 of the lubricating surface area), and the other side is the bonding side (Nomex occupies 3 / 4 of the bonding surface area). The areal density of the fiber fabric is 200 g / m³. 2 The diameter of PTFE fiber is 14μm-18μm, the diameter of Nomex fiber is 15μm-25μm, the mass ratio of PTFE fiber to Nomex fiber is 2:1, and the thickness of the fiber fabric is 0.2mm. Figure 2 This is a surface morphology diagram of the lubricated surface of the fabric, where the warp is Nomex fiber and the weft is PTFE fiber.

[0073] The polyetheretherketone powder is model 450G manufactured by Wiesger, and it is ground to 1000 mesh before use.

[0074] The concentrated sulfuric acid is 98 wt.% concentrated sulfuric acid.

[0075] Preparation Example 1

[0076] This preparation example illustrates the preparation method of sulfonated polyether ether ketone.

[0077] 1) Add 10g of polyether ether ketone powder to 100mL of concentrated sulfuric acid and stir. Control the dissolution (reaction) temperature at 60℃, the stirring rate at 350rpm, and the dissolution time at 3h to prepare a sulfonated polyether ether ketone solution.

[0078] 2) Slowly add the sulfonated polyether ether ketone solution to 2L of ultrapure water at 0℃ to precipitate sulfonated polyether ether ketone solid.

[0079] 2) Add 10g of sodium hydroxide to 2L of ultrapure water to obtain an alkaline solution. Place the precipitated sulfonated polyether ether ketone solid in the alkaline solution and stir at 100rpm at 80℃. Neutralize and wash for 8h to obtain a mixture containing flocculent solids.

[0080] 4) Filter the mixture containing flocculent solids and wash the remaining flocculent solids with ultrapure water until the pH of the washing solution is 7. Filter the mixture and finally dry the moistened sulfonated polyether ether ketone (SPEEK) particles in a vacuum drying oven at 60°C for 24 hours to obtain sulfonated polyether ether ketone (SPEEK) particles.

[0081] Figure 4 To obtain the infrared absorption spectra of the polyether ether ketone powder before and after sulfonation treatment in Example 1, the following methods were used: Figure 4 As can be seen, after sulfonation modification, the infrared spectrum of SPEEK shows the addition of a unique absorption peak of the sulfonic acid group (-SO3H), at 1252 cm⁻¹. -1 and 1080cm -1 These peaks correspond to the antisymmetric and symmetric O=S=O stretching vibrations in the sulfonic acid group, respectively, at 1024 cm⁻¹. -1 and 710cm -1 The stretching peaks of S=O and SO, respectively, indicate that the sulfonic acid group was successfully introduced into the molecular structure, while retaining the original carbonyl group (-Ar-C(=O)-Ar-, 1647 cm⁻¹). -1 The absorption peaks of Ar (representing benzene) and ether bonds (-Ar-O-, 1221 cm⁻¹) are observed. -1 This indicates that the introduction of sulfonate groups did not change the main chain structure of the polymer.

[0082] Figure 3To test the solubility of polyether ether ketone powder before and after sulfonation treatment in Example 1, the same mass of sulfonated polyether ether ketone and polyether ether ketone (0.1 g / mL) were added to the same volume of DMF, and stirred at the same stirring speed (200 rpm) for 2 hours. Figure 3 As can be seen, sulfonated polyether ether ketone can be dissolved in DMF, successfully obtaining a sulfonated polyether ether ketone impregnation solution (left beaker). However, unmodified polyether ether ketone cannot be dissolved, and the powder precipitates (right beaker), making it unusable as an impregnation solution.

[0083] Example 1

[0084] 1. Preparation of sulfonated polyetheretherketone impregnation solution

[0085] Mix 2g of sulfonated polyether ether ketone with 18g of N,N-dimethylformamide and stir at 200rpm until dissolved to obtain sulfonated polyether ether ketone impregnation solution.

[0086] 2. Preparation of composite materials

[0087] 1) Take a piece of PTFE / Nomex blended fiber fabric, ultrasonically clean the fabric in acetone for 5 hours, ultrasonically clean it in ethanol for 5 hours, and then dry it in a forced-air drying oven. Place the dried fabric in a plasma surface treatment instrument, using air as the plasma treatment source, with a power of 100W and a treatment time of 10 minutes.

[0088] 2) Place the plasma-treated fabric in a polyetheretherketone (PEEK) impregnation solution, sonicate for 15 minutes, and then place it in a forced-air drying oven to dry at 60°C for 10 minutes. Repeat this sonication and drying process twice more as one cycle.

[0089] 3) Curing the fabric by hot pressing: Apply a pressure of 1 MPa, heat to 100°C at a rate of 5°C / min, and maintain for 60 min. Continue heating to 160°C at a rate of 5°C / min and maintain for 60 min.

[0090] 4) The hot-pressed and cured product was allowed to cool naturally to obtain a fiber fabric composite material, denoted as M1. The mass content of the impregnating resin in this composite material was calculated to be 18%.

[0091] Example 2

[0092] 1) Take a piece of PTFE / Nomex blended fiber fabric, ultrasonically clean the fabric in acetone for 5 hours, ultrasonically clean it in ethanol for 5 hours, and then dry it in a forced-air drying oven. Place the dried fabric in a plasma surface treatment instrument, using air as the plasma treatment source, with a power of 100W and a treatment time of 10 minutes.

[0093] 2) Place the plasma-treated fabric in a polyetheretherketone (PEEK) impregnation solution (same as in Example 1), sonicate for 15 min, and then place it in a forced-air drying oven to dry at 60°C for 10 min. Repeat this sonication and drying process three times as one cycle.

[0094] 3) Curing the fabric by hot pressing: Apply a pressure of 1 MPa, heat to 110°C at a rate of 5°C / min, and maintain for 50 min. Continue heating to 160°C at a rate of 5°C / min and maintain for 60 min.

[0095] 4) The hot-pressed and cured product was allowed to cool naturally to obtain a fiber fabric composite material, denoted as M2. The mass content of the impregnating resin in this composite material was calculated to be 25%.

[0096] Comparative Example 1

[0097] The Iron Anchor brand 204 phenolic resin adhesive produced by Shanghai Xinguang Chemical Co., Ltd. was used as the impregnation liquid.

[0098] Take a piece of PTFE / Nomex blended fiber fabric, ultrasonically clean it in acetone for 5 hours, ultrasonically clean it in ethanol for 5 hours, and then dry it in a forced-air drying oven. Place the dried fabric in a plasma surface treatment instrument, using air as the plasma source, with a power of 100W and a treatment time of 10 minutes.

[0099] The plasma-treated fabric was placed in a phenolic resin impregnation solution and ultrasonically treated for 15 minutes. It was then dried in a forced-air drying oven at 70°C for 15 minutes. This process was repeated twice. The fabric was then cured by hot pressing. A pressure of 1 MPa was applied, and the temperature was increased to 100°C at a rate of 5°C / min and maintained for 60 minutes. The temperature was then increased to 160°C at a rate of 5°C / min and maintained for 60 minutes. After the heating process was completed, the fabric was allowed to cool naturally, yielding a phenolic resin-reinforced fiber fabric, denoted as D-M1.

[0100] Comparative Example 2

[0101] Polyetherimide resin (manufactured by SABIC, brand name ULTEM 1000) was used as the impregnation liquid, N,N-dimethylformamide was used as the solvent, and the resin content was 20% by mass.

[0102] Take a piece of PTFE / Nomex blended fiber fabric, ultrasonically clean it in acetone for 5 hours, ultrasonically clean it in ethanol for 5 hours, and then dry it in a forced-air drying oven. Place the dried fabric in a plasma surface treatment instrument, using air as the plasma source, with a power of 100W and a treatment time of 10 minutes.

[0103] The plasma-treated dried fabric was placed in polyetherimide and ultrasonically treated for 15 minutes. It was then dried in a forced-air drying oven at 80°C for 20 minutes. This process was repeated twice. The fabric was then cured by hot pressing. A pressure of 1 MPa was applied, and the temperature was increased to 100°C at a rate of 5°C / min and maintained for 60 minutes. The temperature was then increased to 160°C at a rate of 5°C / min and maintained for 60 minutes. After the heating process was completed, the fabric was allowed to cool naturally to obtain the polyetherimide-reinforced fiber fabric, denoted as D-M2.

[0104] Application Example 1-2

[0105] The application examples illustrate the preparation method of self-lubricating solid materials.

[0106] An adhesive is prepared by mixing two components of commercial epoxy resin AB glue.

[0107] Prepare 9Cr18 as the support substrate, sand the bonding surface with sandpaper to make its roughness about 300-500nm, and then use acetone and ethanol for ultrasonic cleaning and drying.

[0108] After cutting the composite materials M1 to M2 prepared in Examples 1-2 to the same size as the bonding surface of the support substrate, the adhesive is applied to the bonding surface of the support substrate and bonded to the bonding surface of each composite material. The materials are then placed naturally to cure the epoxy resin and bond the fabric and support material to obtain a self-lubricating solid material.

[0109] Application Comparative Example 1-2

[0110] Self-lubricating solid materials were prepared according to the method of Application Example 1, except that composite material M1 was replaced with composite materials D-M1 and D-M2 of Comparative Examples 1 and 2, respectively, to obtain self-lubricating solid materials.

[0111] Performance testing

[0112] Tribological properties of self-lubricating solid materials prepared according to Examples 1-2 and Comparative Examples 1-2 were tested using a low-temperature friction and wear testing machine (model MDZ-01GL). The test conditions were as follows: the fabric composite material (lubricated surface) of the sample was rubbed against a quenched GCr15 sample; the GCr15 roughness was 130 nm ± 10 nm; the experimental loading force was 700 N (nominal contact stress was 18.2 MPa); the linear velocity was 12 mm / s; the sample was rubbed at room temperature for 1 hour, and then rubbed at -10℃, -40℃, -70℃, -100℃, -130℃, and -160℃ for 10 minutes each. The coefficients of friction were calculated according to Formula 1. Finally, after drying, the wear rate was calculated by weighing according to Formula 2.

[0113] μ=F / P Formula 1

[0114] Where μ represents the coefficient of friction, F is the frictional force (N), and P is the applied force (N);

[0115] ω=Δm / (ρ·P·L) Formula 2

[0116] Where ω is the wear rate (m 3 (N·m) -1 ); Δm is the mass difference before and after wear (g); ρ is the density of the fabric composite material (g·m³). -3 P is the applied force (N); L is the sliding distance (m).

[0117] The test results are shown in Table 1.

[0118] Table 1

[0119]

[0120] According to the data in Table 1, the friction coefficient and wear rate of the sulfonated polyetheretherketone (PEEK) reinforced fabric of this application are lower than those of the phenolic resin reinforced fiber fabric and the polyetherimide resin reinforced fiber fabric at low temperatures. As shown in Comparative Example 1, the friction coefficient of the reinforced fabric impregnated with thermosetting phenolic resin increases rapidly with decreasing temperature, exceeding 0.2 after the temperature drops below -100°C. As shown in Comparative Example 2, the friction coefficient of the reinforced fabric impregnated with thermoplastic polyetherimide resin increases with decreasing temperature, and while the overall friction coefficient is lower than that of the thermosetting phenolic resin reinforced fabric, the wear rate is too high. However, the reinforced fabric cured using the impregnation solution prepared in this application, as shown in Examples 1 and 2, exhibits a slow increase in friction coefficient with decreasing temperature, followed by a slow decrease below -100°C. Within a wide low-temperature range, the variation in friction coefficient with temperature is reduced, significantly lower than that of Comparative Example 1 and Comparative Example 2, and the low-temperature friction performance is stable. Furthermore, the wear rate of the reinforced fiber composite material prepared in this application is also lower than that of the comparative example, indicating that the polyaryletherketone impregnation liquid containing active sites can effectively prevent stress concentration and reduce wear after curing, and achieve a synergistic effect with PTFE to reduce friction.

[0121] The technical features of the above embodiments can be combined in any way. For the sake of brevity, not all possible combinations of the technical features in the above embodiments are described. However, as long as there is no contradiction in the combination of these technical features, they should be considered to be within the scope of this specification.

[0122] The embodiments described above are merely illustrative of several implementation methods of this application, and while the descriptions are specific and detailed, they should not be construed as limiting the scope of the invention patent. It should be noted that those skilled in the art can make various modifications and improvements without departing from the concept of this application, and these all fall within the protection scope of this application. Therefore, the protection scope of this application should be determined by the appended claims.

Claims

1. A fiber fabric composite material, characterized in that, The invention comprises a fibrous fabric and an impregnation resin loaded on the fibrous fabric, the impregnation resin comprising sulfonated polyaryletherketone; The fiber fabric is a blend of polytetrafluoroethylene (PTFE) fiber and aramid fiber, with a mass ratio of PTFE fiber to aramid fiber of (1.5-2.5):

1. In the fiber fabric composite material, the impregnation resin has a mass content of 8% to 35%.

2. The fiber fabric composite material according to claim 1, characterized in that, The sulfonated polyaryletherketone is prepared by sulfonating polyaryletherketone, and the polyaryletherketone includes one or more of polyether etherketone, polyether ketone, polyether ketone ketone, and polyether ether ketone ketone.

3. The fiber fabric composite material according to claim 1, characterized in that, The areal density of the fiber fabric is 180 g / m³. 2 ~220g / m 2 The diameter of polytetrafluoroethylene fiber is 14μm to 18μm, and the diameter of aramid fiber is 15μm to 25μm.

4. The fiber fabric composite material according to claim 3, characterized in that, The thickness of the fiber fabric is 0.2 mm to 0.25 mm.

5. The fiber fabric composite material according to any one of claims 1-4, characterized in that, The sulfonated polyaryletherketone is a sulfonated polyether etherketone.

6. A method for preparing the fiber fabric composite material according to any one of claims 1-5, characterized in that, include: The fiber fabric is impregnated with an impregnation solution containing an impregnation resin, thereby loading the impregnation resin onto the fiber fabric.

7. The preparation method according to claim 6, characterized in that, Also includes: The method for preparing the sulfonated polyarylether ketone includes: The polyarylene ether ketone is subjected to a sulfonation reaction with a sulfonating agent to prepare a solution containing sulfonated polyarylene ether ketone; The solution containing sulfonated polyarylether ketone was mixed with water to precipitate a crude product containing sulfonated polyarylether ketone. The crude product was washed sequentially with an alkaline aqueous solution and water, and then dried to obtain the sulfonated polyarylether ketone.

8. The preparation method according to claim 7, characterized in that, The method for preparing the sulfonated polyarylether ketone satisfies at least one of the following conditions: (1) The sulfonating agent includes one or more of concentrated sulfuric acid, fuming sulfuric acid, and chlorosulfuric acid; (2) The amount of the sulfonating agent used is 5 mL to 50 mL relative to 1 g of the polyarylether ketone; (3) The sulfonation reaction temperature is 50℃~90℃, and the reaction time is 3h~10h; (4) The method of washing the crude product with the alkaline aqueous solution includes: placing the crude product in the alkaline aqueous solution and stirring at 60℃~90℃ for 3h~8h; (5) The alkaline aqueous solution includes sodium hydroxide aqueous solution and / or potassium hydroxide aqueous solution; (6) The drying is vacuum drying, the drying temperature is 60℃~80℃, and the drying time is 24h~48h.

9. The preparation method according to claim 6 or 7, characterized in that, The impregnation process includes the following steps: The fiber fabric is placed in the impregnation solution containing the impregnation resin and subjected to ultrasonic treatment; Dry the ultrasonically treated fiber fabric; The ultrasonic treatment and drying process is repeated 2 to 4 times as a cycle.

10. The preparation method according to claim 9, characterized in that, Each ultrasound treatment lasts for 10 to 30 minutes.

11. The preparation method according to claim 9, characterized in that, The drying temperature is 50℃~70℃ for each drying cycle, and the drying time is 5min~20min.

12. The preparation method according to claim 6 or 7, characterized in that, Before impregnating the fiber fabric with an impregnation solution containing an impregnation resin, the following steps are also included: The fiber fabric is sequentially cleaned and subjected to plasma surface treatment. In the plasma surface treatment, the gas used is oxygen-containing gas, the power is 80W to 120W, and the treatment time is 5min to 20min. And / or, after impregnating the fiber fabric with an impregnation solution containing an impregnation resin, it further includes: The fiber fabric loaded with impregnated resin is cured and molded by hot pressing, wherein the applied pressure is 0.5MPa to 2MPa, the hot pressing temperature is 80℃ to 200℃, and the hot pressing time is 1h to 3h.

13. The preparation method according to claim 12, characterized in that, The hot pressing is carried out in two stages: In the first stage, the temperature is increased to 80℃ to 120℃ at a heating rate of 3℃ / min to 5℃ / min, and maintained for 50min to 70min. In the second stage, the temperature is increased to 160℃ to 200℃ at a rate of 3℃ / min to 5℃ / min, and maintained for 50min to 70min.

14. A self-lubricating solid material, characterized in that, The invention comprises a support substrate and a fiber fabric composite material bonded to the surface of the support substrate, wherein the fiber fabric composite material is the fiber fabric composite material according to any one of claims 1-5.

15. A spherical plain bearing liner, characterized in that, Made from the self-lubricating solid material as described in claim 14.

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