Mxene filler oriented modified anti-corrosion carbon fabric liner and preparation method thereof

Abstract

The invention discloses an Mxene filler oriented modification anti-corrosion carbon fabric liner and a preparation method thereof, and belongs to the technical field of fabric liner composite material preparation, Ti3AlC2 is added into an etching reagent, constant-temperature water bath stirring is performed, after an Al layer is removed through etching, repeated water washing centrifugation is performed until Ti3C2Tx begins to be spontaneously layered and oscillated, the mixture is placed in an ice-water bath for ultrasonic treatment and centrifugation, supernate is collected, and the Mxene filler oriented modification anti-corrosion carbon fabric liner is obtained. After freeze drying, the MXene nanosheet is obtained; adding the Mxene modified phenolic resin and phenolic resin into a solvent, and ultrasonically dispersing uniformly to obtain an Mxene modified phenolic resin solution; the preparation method comprises the following steps: pretreating carbon cloth, immersing the pretreated carbon cloth in an Mxene modified phenolic resin solution, carrying out pulling dipping for multiple times, and carrying out drying treatment to obtain a prepreg; and then hot-pressing and curing to obtain the anti-corrosion carbon fabric liner directionally modified by the Mxene filler. The Mxene nanosheets are directionally arranged in a phenolic resin matrix to construct a labyrinth structure to slow down the infiltration speed of a corrosive medium, and meanwhile, the Mxene nanosheets serve as a lubricating phase to improve the lubricating performance, and the protection effect and the tribological performance of the liner are synchronously improved.

Description

Technical Field

[0001] The present invention belongs to the technical field of preparing composite materials of fabric liner, and in particular relates to a MXene filler directionally modified anti-corrosion carbon fabric liner and a preparation method thereof. Background Art

[0002] Spherical plain bearings, as the "joints" of machinery, connect and support two components while reducing friction between rotating parts. They are widely used in fields such as aerospace and high-speed rail. However, the friction coefficient and wear rate between the metal mating components remain high, and their adaptability to harsh environments is poor, limiting the bearing's service life and leading to high maintenance costs. Fabric liners are commonly used in sliding components such as alloy spherical plain bearings, imparting these bearing structures with flexible rotation and maintenance-free features, meeting the need for liquid-free lubrication and becoming a core component of spherical plain bearings. Fabric-reinforced resin-based composites are made by weaving various reinforcing fiber monofilaments into a fabric, then impregnating them with a resin matrix, drying them, and finally curing them into a composite material. The fabric provides load-bearing and anti-wear properties, while the resin matrix acts as a continuous phase, connecting and securing the reinforcing fibers and transferring loads to the fibers through the interface. This not only maximizes the fiber's excellent performance but also protects them from damage. However, with increasing equipment power and operating conditions, the widely used lubricated fabric (polytetrafluoroethylene) liners are no longer able to meet the demands of heavy-duty operating conditions. In addition, in harsh environments such as high humidity and salt spray, the protection of the fabric gasket to the bearing is limited, and the existence of its gap defects makes it difficult to meet the long-term protection requirements of the gasket for the alloy bearing.

[0003] Document 1, Chinese patent number "ZL 1115807330 B," provides a method for preparing a self-lubricating lining fabric composite material. This method utilizes a reinforced fiber / polytetrafluoroethylene fiber blended fabric as a reinforcement, while simultaneously introducing metal hydroxides and copolymers as toughening components on the reinforcement surface to construct a strong-tough integrated interface phase, thereby increasing the service life of the composite material. However, the fabric blending process employed in this method is complex, and the reinforcement modification methods are complicated, making it unsuitable for large-scale production and application of the composite material. Furthermore, the lubricating fibers have weak corrosion resistance, limiting the practicality of the fabric lining in harsh environments. Document 2, Chinese patent number "ZL 117429095 B," provides a highly thermally conductive, wear-resistant self-lubricating lining and a method for preparing the same. A metal coating is formed by chemically plating the surface of aramid fibers, which is then impregnated with resin and hot-pressed to form a composite material. This method utilizes the high thermal conductivity of the metal coating to effectively channel heat generated during friction, and the composite material exhibits improved wear resistance. However, the friction coefficient of the pad prepared by this method is relatively large, which affects the rotational flexibility of the spherical bearing; at the same time, only the interface is optimized, and the adverse effects of the void defects inside the resin on the protective performance of the pad cannot be taken into account.

[0004] In view of the poor wear resistance of existing polytetrafluoroethylene-based lubricating fabrics under heavy load conditions and their inability to meet high load requirements, the problem of rapid penetration of corrosive media due to void defects in traditional fabric liners in high-humidity salt spray environments, and the problem that the resin matrix and fiber interface in traditional composite materials easily become stress concentration points and penetration channels for corrosive media, it is urgent to find a new modified anti-corrosion carbon fabric liner and its preparation method to solve key technical problems such as heavy-load lubrication, long-term corrosion protection, process simplification and multi-performance synergy, and provide high-performance, long-life, maintenance-free joint bearing liner solutions for high-end equipment fields such as aerospace and high-speed railways. 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 Mxene filler directionally modified anti-corrosion carbon fabric liner and a preparation method thereof, so as to solve the technical problems of insufficient wear resistance, poor corrosion resistance and complex preparation process of spherical bearing liners under heavy load and harsh environment.

[0006] In order to achieve the above object, the present invention adopts the following technical solutions: The present invention discloses a method for preparing a MXene filler directionally modified anti-corrosion carbon fabric liner, comprising: Ti3AlC2 was added to the etching reagent and stirred in a constant temperature water bath. After etching to remove the Al layer, the Ti3C2T x The mixture began to spontaneously separate and, after shaking, was placed in an ice-water bath for ultrasonic treatment, centrifuged and the supernatant was collected and freeze-dried to obtain MXene nanosheets. Adding MXene nanosheets and phenolic resin into a solvent and uniformly dispersing them by ultrasonication to obtain a MXene-modified phenolic resin solution; After pretreatment, the carbon cloth is immersed in a MXene-modified phenolic resin solution, pulled and impregnated multiple times, and dried to obtain a prepreg; and then hot-pressed and cured to obtain a MXene filler-directed modified anti-corrosion carbon fabric liner.

[0007] Preferably, the etching reagent is prepared by mixing an HCl solution and LiF, and stirring the mixture in an ice-water bath for 10-20 minutes. The concentration of the HCl solution is 8-10 mol / L. The usage ratio of Ti3AlC2, HCl solution, and LiF is (0.99-3.96) g: (20-60) mL: (0.99-3.96) g.

[0008] Preferably, the stirring conditions in the constant temperature water bath include: a rotation speed of 200-600 rpm / min, a water bath temperature of 30-40° C., and a stirring time of 40-56 h.

[0009] Preferably, the conditions for water washing and centrifugation include: water washing and centrifugation for 7-10 times, a rotation speed of 3000-5000 rpm, and each centrifugation for 3-5 minutes, until the pH value of the upper layer liquid is neutral.

[0010] Preferably, the shaking time is 15-60 min; the ultrasonic treatment time in the ice water bath is 0.5-1.5 h; the centrifugation time is 3-5 min at a speed of 3000-5000 rpm; and the freeze drying time is 36-48 h.

[0011] Preferably, in the MXene-modified phenolic resin solution, the mass fraction of MXene nanosheets is 0-0.20%; the solvent is acetone, and the mass ratio of acetone to phenolic resin is (4-7): (1-3); and the ultrasonic dispersion time is 10-15 min.

[0012] Preferably, the carbon cloth pretreatment method comprises: completely immersing the carbon cloth in acetone, sealing it, soaking it at room temperature for 42-54 hours, washing it with deionized water, and drying it at 60-80°C.

[0013] Preferably, the pulling and impregnation method comprises: pulling and impregnation in the same direction, impregnating for 8-10 seconds each time and drying, and repeating 2-3 times; and the drying treatment temperature is 50-70° C. and the time is 6-8 hours.

[0014] Preferably, the conditions for hot pressing curing include: a temperature of 165-175° C., a pressure of 4-6 MPa, and a time of 10-15 min.

[0015] The present invention also discloses a MXene filler directionally modified anti-corrosion carbon fabric liner, which is prepared by the above-mentioned preparation method. Compared with the unmodified carbon fabric liner, the MXene filler directionally modified anti-corrosion carbon fabric liner has a tensile strength increased by 12.10%, a corrosion current density reduced by 84.03%, an average friction coefficient reduced by 26.41%, and a wear rate reduced by 68.27%.

[0016] Compared with the prior art, the present invention has the following beneficial effects: This invention discloses a method for preparing an anti-corrosion carbon fabric liner with MXene filler modified in a directional manner. First, a single or few layers of MXene nanosheet filler are produced by etching. The filler is then evenly dispersed in a phenolic resin solution, effectively dispersing it within the phenolic resin to form a multifunctional composite phase characterized by "nano-enhancement, lubrication, and corrosion protection." Spontaneous delamination is combined with ultrasonic treatment to improve the efficiency of MXene flake exfoliation, prevent uneven performance caused by agglomeration, and ensure that the MXene flakes form a uniform "maze" barrier within the phenolic resin. Multiple pull-up and impregnation methods are used to parallelize the filler on the carbon fabric surface. This not only blocks microcrack propagation and improves mechanical properties, but also acts as a solid lubricating phase, enhancing the material's wear resistance and service life. Furthermore, the "maze effect" created by the multi-layered MXene arrangement prolongs the penetration rate of corrosive media into the material, reducing the liner's corrosion current density and enhancing the carbon fabric liner's corrosion resistance and protective effect on alloy bearings. High temperature and high pressure fully crosslink the phenolic resin while simultaneously fixing the MXene's directional structure. Carbon fabric reinforcement is used to withstand harsh operating conditions such as high temperatures and heavy loads. Two-dimensional MXene nanosheets are directionally arranged in a phenolic resin matrix, slowing the infiltration of corrosive media while simultaneously acting as a lubricating phase to improve lubrication performance, thereby simultaneously enhancing the protective and tribological properties of the liner. While carbon fabric reinforcement effectively improves the mechanical properties of the liner, the introduction of MXene filler enhances the liner's wear resistance and corrosion protection, providing important guidance for further expanding the application of self-lubricating liners.

[0017] Furthermore, HCl provides a strong acidic environment, and LiF slowly releases F - ions, to achieve gentle exfoliation of the Al layer and avoid violent reaction that may damage the MXene structure. Stir in a sealed container for 10-20 minutes to allow F - The ions are evenly distributed to avoid local over-etching, and the resulting MXene sheets have small size deviations, ensuring the consistency of subsequent directional arrangement.

[0018] Furthermore, the low temperature environment of 30-40℃ inhibits the oxidation of Mxene, and the rotation speed of 200-600rpm provides moderate mechanical shear force to promote Al 3+ Diffusion, long-term stirring for 40-56h improves Al exfoliation and Mxene purity.

[0019] Furthermore, 7-10 water washes thoroughly remove corrosive residues such as AlCl3 and HF, stabilizing the pH of the supernatant to neutral, thus preventing acidic catalytic degradation during subsequent resin curing. A gentle centrifugation rate prevents excessive sedimentation and agglomeration of the MXene, improving the efficiency of exfoliation during subsequent ultrasonic treatment.

[0020] Furthermore, a 15-60 minute oscillation process initially disperses the flakes through mechanical collision, reducing the ultrasonic processing load and improving overall exfoliation efficiency. A 0.5-1.5 hour low-temperature ultrasound process achieves secondary exfoliation, while also reducing the loss of -OH groups caused by thermal damage and enhancing hydrogen bonding with the phenolic resin. A 36-48 hour freeze-drying process forms a porous structure, preventing the stacking of flakes caused by traditional drying and ensuring a monodispersed state within the phenolic resin, enhancing the effectiveness of the "maze effect."

[0021] Furthermore, 0-0.20% by mass fraction of MXene avoids brittle fracture caused by high filling. The capillary force generated by solvent evaporation guides the MXene sheets to align, while increasing the gap filling rate of the carbon cloth fibers and avoiding dry spot defects.

[0022] Furthermore, slow drying at 60-80°C avoids sudden thermal cracking of the fibers, maintains the mechanical properties of the carbon cloth, and provides a reliable base for composite reinforcement.

[0023] Furthermore, 2-3 simultaneous pulls induce the MXene sheets to orient along the pull direction, resulting in anisotropic reinforcement of the liner. Low-temperature drying at 50-70°C initially fixes the MXene orientation structure, preventing sheet displacement during subsequent transfer and providing a stable substrate for hot pressing.

[0024] Furthermore, a temperature of 165-175°C promotes the condensation of the hydroxymethyl group of the phenolic resin, forming a three-dimensional network structure, while a pressure of 4-6 MPa densifies the liner. The high pressure inhibits the displacement of the MXene sheets, and the oriented structure is highly retained.

[0025] The present invention also discloses a corrosion-resistant carbon fabric liner modified with MXene filler. Compared to an unmodified carbon fabric liner, its tensile strength is increased by 12.10%. This is due to the reinforced network formed by the oriented arrangement of MXene nanosheets in the phenolic resin. These nanosheets act as physical crosslinks, effectively dispersing stress and inhibiting crack propagation, enabling the liner to withstand greater external forces and maintain structural integrity under harsh operating conditions such as high temperature and heavy loads. The corrosion current density is reduced by 84.03%, significantly slowing the corrosion rate of the material. The multi-layered, oriented MXene creates a "maze effect," significantly extending the penetration path of the corrosive medium within the material and reducing its diffusion rate. Furthermore, the active groups on the MXene surface adsorb the corrosive medium, further reducing its attack on the liner and alloy bearing, effectively enhancing the liner's corrosion resistance and extending its service life in corrosive environments. The average friction coefficient is reduced by 26.41%, and the wear rate is reduced by 68.27%. This indicates that the liner generates less resistance during friction and significantly reduces wear. MXene nanosheets, acting as a solid lubricant, provide sliding lubrication at the friction interface, reducing direct contact between the friction pairs. Furthermore, MXene debris generated by wear can fill surface pits, forming a lubricating transfer film, thereby reducing the coefficient of friction, improving wear resistance, reducing maintenance frequency, and lowering operating costs. This achieves a synergistic improvement in mechanical, corrosion resistance, and tribological properties, overcoming the single-performance limitations of traditional carbon fabric liners and broadening the application range of self-lubricating liners. They are particularly suitable for applications requiring extremely high material performance, such as aerospace and chemical equipment, providing a more reliable solution for sealing and protecting high-end equipment. BRIEF DESCRIPTION OF THE DRAWINGS

[0026] Figure 1 The scanning electron microscope morphology of the MXene nanosheets and the MXene filler directionally modified anti-corrosion carbon fabric liner prepared in Example 2 of the present invention; wherein (a) is a MXene nanosheet; (b) is a MXene filler directionally modified anti-corrosion carbon fabric liner; Figure 2 This is a comparison chart of the mechanical properties of the unmodified carbon fabric liner prepared in Comparative Example 1 of the present invention and the Mxene filler directionally modified anti-corrosion carbon fabric liner prepared in Example 2, wherein P-CF / PF is a carbon fabric liner and M-CF / PF is a Mxene filler directionally modified anti-corrosion carbon fabric liner; Figure 3 This is a comparison chart of polarization curves of the unmodified carbon fabric liner prepared in Comparative Example 1 of the present invention and the Mxene filler directionally modified anti-corrosion carbon fabric liner prepared in Example 2, wherein P-CF / PF is a carbon fabric liner and M-CF / PF is a Mxene filler directionally modified anti-corrosion carbon fabric liner; Figure 4This is a comparison chart of the tribological properties of the unmodified carbon fabric liner prepared in Comparative Example 1 of the present invention and the Mxene filler directionally modified anti-corrosion carbon fabric liner prepared in Example 2; wherein (a) is the friction coefficient, and (b) is a comparison of the average friction coefficient and wear rate. DETAILED DESCRIPTION

[0027] 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.

[0028] 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.

[0029] 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.

[0030] In the present invention, unless otherwise specified, percentages (%) or parts refer to percentages by weight or parts by weight relative to the composition.

[0031] 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.

[0032] 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.

[0033] 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.

[0034] 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.

[0035] In the present invention, unless otherwise specified, each reaction or operation step can be carried out sequentially or in accordance with the order. Preferably, the reaction method herein is carried out sequentially.

[0036] 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.

[0037] The present invention discloses a method for preparing a corrosion-resistant carbon fabric liner with a directionally modified MXene filler. The method includes: preparing MXene nanosheets by etching and uniformly dispersing them in a phenolic resin. The sheets are then impregnated into a resin matrix through pulling to create a multi-layered stacked structure. This creates a "maze effect" that mitigates internal defects in the matrix, effectively extending the dispersion path of the corrosive medium in the coating, and imparting excellent corrosion resistance to the carbon fabric liner. Furthermore, the MXene forms a tribofilm at the friction interface, significantly reducing the friction coefficient and wear rate, thereby extending the service life of the self-lubricating liner.

[0038] The present invention discloses a method for preparing a MXene filler directionally modified anti-corrosion carbon fabric liner, which comprises the following specific steps: Step 1: Pre-treat the carbon cloth to remove surface impurities and sizing agents before use; The carbon cloth specification is 6-12 K.

[0039] The carbon cloth is pretreated by completely immersing it in acetone, sealing it, and soaking it at room temperature for 42-54 hours. After soaking, it is rinsed with deionized water and dried in an oven at 60-80°C to obtain a clean pretreated carbon cloth.

[0040] Step 2: Preparation of MXene filler by etching: Add a mixture of HCl solution and LiF as an etchant to a polytetrafluoroethylene reagent bottle, seal and stir until completely cooled. Slowly add Ti3AlC2 to the etching reagent to prevent the material from oxidizing, and stir in a constant temperature water bath to remove the Al layer. After etching, the crude product is repeatedly centrifuged in deionized water to Ti3C2T x Spontaneous delamination begins. After shaking, the mixture is placed in an ice-water bath for sonication and then centrifuged to collect the uniform dark green supernatant. Finally, the resulting dark green supernatant is freeze-dried to yield single-layer or few-layer MXene nanosheets.

[0041] The concentration of HCl solution is 8-10 mol / L, and the amount used is 20-60 mL.

[0042] The amount of LiF added is 0.99-3.96 g.

[0043] The sealed stirring was carried out in an ice water bath for 10-20 min.

[0044] The amount of Ti3AlC2 added to the etching reagent was 0.99-3.96 g, and the duration was 15-25 min.

[0045] The water bath temperature for removing the Al layer is 30-40 °C, the magnetic stirring speed is 200-600 rpm / min, and the stirring time is 40-56 h.

[0046] The crude product is centrifuged 7-10 times at a centrifuge speed of 3000-5000 rpm, each time for 3-5 minutes, until the pH of the upper liquid is neutral.

[0047] The shaking time is 15-60 min, the ultrasonic time in an ice water bath is 0.5-1.5 h, the centrifugation time is 3-5 min, and the speed is 3000-5000 rpm.

[0048] The freeze-drying time is 36-48 h.

[0049] Step 3: Add MXene nanosheets and phenolic resin to a solvent and ultrasonically disperse them until uniformly dispersed to form a MXene-modified phenolic resin solution. The carbon cloth is completely immersed in the modified phenolic resin and impregnated multiple times in the same direction, followed by drying to obtain a prepreg.

[0050] The mass fraction of Mxene nanosheets dispersed in phenolic resin was 0-0.20%, and the ultrasonic time was 10-15 min.

[0051] The solvent is acetone, and the mass ratio of acetone to phenolic resin is 4:1-7:3.

[0052] The pull-up impregnation method is to impregnate for 8-10 seconds each time, followed by oven drying for 10-15 minutes, for 2-3 cycles. The drying temperature is then 50-70°C for 6-8 hours.

[0053] Step 4: The prepreg is hot-pressed and cured in a vulcanizer, and then naturally cooled to room temperature to obtain a MXene filler directionally modified anti-corrosion carbon fabric liner.

[0054] Hot pressing curing is carried out using a vulcanizing machine, and the hot pressing parameters are: temperature 165-175 °C, pressure 4-6 MPa, and hot pressing time 10-15 min.

[0055] The present invention also discloses a MXene filler directionally modified anti-corrosion carbon fabric liner. Compared with the unmodified carbon fabric liner, the tensile strength is increased by 12.10%, the corrosion current density is reduced by 84.03%, the average friction coefficient is reduced by 26.41%, and the wear rate is reduced by 68.27%.

[0056] This invention utilizes MXene nanosheets in a phenolic resin matrix to create a "maze effect." By extending the permeation path of corrosive media and reducing corrosion current density, this carbon fabric liner provides long-term protection for alloy bearings. This addresses the limitations of existing technologies that only optimize the interface but fail to address internal defects within the resin matrix. Addressing the technical bottleneck of existing polytetrafluoroethylene-based lubricated fabrics, which suffer from poor wear resistance under heavy loads and are unable to meet high load requirements, this invention proposes replacing traditional fibers with carbon fabric as a reinforcement, leveraging its superior mechanical properties and thermal stability to address high-temperature and heavy-load conditions. Simultaneously, by incorporating two-dimensional MXene nanosheets as a solid lubricating phase, a composite structure combining load-bearing capacity and lubrication properties is constructed, significantly improving the wear resistance and service life of the liner. A simple pull-and-impregnation method achieves parallel alignment of the MXene nanosheets on the carbon fabric surface, simplifying the preparation process. The MXene two-dimensional sheet structure simultaneously achieves a multifunctional synergistic effect of mechanical reinforcement, lubrication and wear reduction, and corrosion protection, transcending a single performance optimization model to achieve simultaneous improvements in tribological and protective properties. By creating a strong interphase through the oriented arrangement of MXene nanosheets, this not only enhances interfacial bonding strength but also leverages its metallic conductivity to provide active protection against electrochemical corrosion, reversing the passive protection model of existing technologies that rely solely on physical barriers or chemical plating. Through innovative material systems (combining carbon fabric, MXene, and phenolic resin) and structural innovations (a directional "maze" structure), this system addresses key technical challenges such as heavy-duty lubrication, long-term corrosion protection, process simplification, and multi-performance synergy, providing a high-performance, long-life, maintenance-free spherical plain bearing liner solution for high-end equipment such as aerospace and high-speed rail.

[0057] 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.

[0058] Example 1 A method for preparing a MXene filler directionally modified anti-corrosion carbon fabric liner, comprising: Step 1: Completely immerse the 6K carbon cloth in acetone, seal it, and soak it at room temperature for 54 hours. After soaking, rinse it with deionized water and dry it in an oven at 80°C to obtain a clean carbon cloth.

[0059] Step 2: Preparation of Mxene filler by etching: Add 20 mL of 9M HCI and 0.99 g of LiF as an etchant mixture to a polytetrafluoroethylene reagent bottle, seal and stir in an ice-water bath for 10 min until completely cooled. Slowly add 0.99 g of Ti3AlC2 to the etching reagent within 15 min to prevent oxidation of the material, and magnetically stir at 200 rpm / min in a 30 ° C constant temperature water bath for 40 h to remove the Al layer. After etching, the crude product is centrifuged in deionized water at 3000 rpm / min for 5 min, and repeated 7 times until the pH of the upper liquid is 7. At this time, Ti3C2T x Spontaneous demixing began. After 20 minutes of shaking, the mixture was sonicated in an ice-water bath for 0.5 hours. Centrifugation was then performed at 3000 rpm / min for 5 minutes, and the homogeneous dark green supernatant was collected. Finally, the resulting dark green supernatant was freeze-dried for 36 hours to yield minority-layer and monolayer MXene nanosheets.

[0060] Step 3: Add the MXene nanosheets to a 20% by mass phenolic resin and sonicate for 10 minutes until uniformly dispersed, creating a 0.05% by mass MXene-modified phenolic resin solution. The carbon cloth was completely immersed in the modified phenolic resin for 8 seconds, lifted vertically, and placed in an oven for 10 minutes. This was repeated twice, followed by drying at 50°C for 6 hours to obtain a prepreg.

[0061] Step 4: The prepreg is hot-pressed and cured at a temperature of 170 °C and a pressure of 6 MPa for 10 min in a vulcanizer. After naturally cooling to room temperature, a MXene filler-directionally modified anti-corrosion carbon fabric liner is obtained.

[0062] Example 2 A method for preparing a MXene filler directionally modified anti-corrosion carbon fabric liner, comprising: Step 1: Completely immerse the 6K carbon cloth in acetone, seal it, and soak it at room temperature for 48 hours. After soaking, rinse it with deionized water and dry it in an oven at 60°C to obtain a clean carbon cloth.

[0063] Step 2: Preparation of Mxene filler by etching: Add 40 mL of 9M HCI and 1.98 g of LiF as an etchant mixture to a polytetrafluoroethylene reagent bottle, seal and stir in an ice-water bath for 15 min until completely cooled. Slowly add 1.98 g of Ti3AlC2 to the etching reagent within 20 min to prevent oxidation of the material, and magnetically stir at 400 rpm / min in a 35 ° C constant temperature water bath for 48 h to remove the Al layer. After etching, the crude product is centrifuged in deionized water at 3500 rpm / min for 3 min, and repeated 8 times until the pH of the upper liquid is 7. At this time, Ti3C2T x Spontaneous demixing began. After 15 minutes of shaking, the mixture was sonicated in an ice-water bath for 1 hour. Centrifugation was then performed at 3500 rpm / min for 3 minutes, and the homogeneous dark green supernatant was collected. Finally, the resulting dark green supernatant was freeze-dried for 36 hours to yield few-layer and single-layer MXene nanosheets.

[0064] Step 3: Add the MXene nanosheets to a 25% by mass phenolic resin and ultrasonicate for 10 minutes until uniformly dispersed, creating a 0.15% by mass MXene-modified phenolic resin solution. The carbon cloth was completely immersed in the modified phenolic resin for 10 seconds, lifted vertically, and placed in an oven for 15 minutes. This was repeated three times, followed by drying at 60°C for 8 hours to obtain a prepreg.

[0065] Step 4: The prepreg is hot-pressed and cured at a temperature of 170 °C and a pressure of 5 MPa for 10 min in a vulcanizer. After naturally cooling to room temperature, a MXene filler-directionally modified anti-corrosion carbon fabric liner is obtained.

[0066] Example 3 A method for preparing a MXene filler directionally modified anti-corrosion carbon fabric liner, comprising: Step 1: Completely immerse the 12K carbon cloth in acetone, seal it, and soak it at room temperature for 42 hours. After soaking, rinse it with deionized water and dry it in an oven at 60°C to obtain a clean carbon cloth.

[0067] Step 2: Preparation of Mxene filler by etching: Add 60 mL of 9M HCI and 3.96 g of LiF as an etchant mixture to a polytetrafluoroethylene reagent bottle, seal and stir in an ice-water bath for 20 min until completely cooled. Slowly add 3.96 g of Ti3AlC2 to the etching reagent within 20 min to prevent oxidation of the material, and magnetically stir at 600 rpm / min in a 40 ° C constant temperature water bath for 56 h to remove the Al layer. After etching, the crude product is centrifuged in deionized water at 5000 rpm / min for 3 min, and repeated 10 times until the pH of the upper liquid is 7. At this time, Ti3C2T x Spontaneous demixing began. After 60 minutes of shaking, the mixture was sonicated in an ice-water bath for 1.5 hours. Centrifugation was then performed at 5000 rpm / min for 3 minutes, and the homogeneous dark green supernatant was collected. Finally, the resulting dark green supernatant was freeze-dried for 48 hours to yield few-layer and single-layer MXene nanosheets.

[0068] Step 3: Add MXene nanosheets to 30% by mass phenolic resin and ultrasonicate for 15 minutes until uniformly dispersed, creating a 0.20% by mass MXene-modified phenolic resin solution. The carbon cloth was completely immersed in the modified phenolic resin for 10 seconds, lifted vertically, and placed in an oven for 15 minutes. This was repeated three times, followed by drying at 70°C for 8 hours to obtain a prepreg.

[0069] Step 4: The prepreg is hot-pressed and cured at a temperature of 170 °C and a pressure of 4 MPa for 15 min in a vulcanizer. After naturally cooling to room temperature, a MXene filler-directionally modified anti-corrosion carbon fabric liner is obtained.

[0070] Example 4 A method for preparing a MXene filler directionally modified anti-corrosion carbon fabric liner, comprising: Step 1: Completely immerse the 6K carbon cloth in acetone, seal it, and soak it at room temperature for 50 hours. After soaking, rinse it with deionized water and dry it in an oven at 70°C to obtain a clean carbon cloth.

[0071] Step 2: Preparation of Mxene filler by etching: Add 30 mL of 8M HCI and 1.98 g of LiF as an etchant mixture to a polytetrafluoroethylene reagent bottle, seal and stir in an ice-water bath for 12 minutes until completely cooled. Slowly add 1.98 g of Ti3AlC2 to the etching reagent within 20 minutes to prevent oxidation of the material, and magnetically stir at 300 rpm / min in a 32 ° C constant temperature water bath for 46 hours to remove the Al layer. After etching, the crude product is centrifuged in deionized water at 4000 rpm / min for 4 minutes, and repeated 9 times until the pH of the upper liquid is 7. At this time, Ti3C2T x Spontaneous demixing began. After oscillation for 30 minutes, the mixture was sonicated in an ice-water bath for 1 hour. Centrifugation was then performed at 4000 rpm / min for 4 minutes, and the homogeneous dark green supernatant was collected. Finally, the resulting dark green supernatant was freeze-dried for 40 hours to yield few-layer and single-layer MXene nanosheets.

[0072] Step 3: Add MXene nanosheets to 25% by mass phenolic resin and sonicate for 12 minutes until uniformly dispersed, creating a 0.01% by mass MXene-modified phenolic resin solution. The carbon cloth was completely immersed in the modified phenolic resin for 9 seconds, lifted vertically, and placed in an oven for 15 minutes. This was repeated twice, followed by drying at 55°C for 7 hours to obtain a prepreg.

[0073] Step 4: The prepreg is hot-pressed and cured at a temperature of 165 °C and a pressure of 4 MPa for 12 min in a vulcanizer. After naturally cooling to room temperature, a MXene filler-directionally modified anti-corrosion carbon fabric liner is obtained.

[0074] Example 5 A method for preparing a MXene filler directionally modified anti-corrosion carbon fabric liner, comprising: Step 1: Completely immerse the 12K carbon cloth in acetone, seal it, and soak it at room temperature for 48 hours. After soaking, rinse it with deionized water and dry it in an oven at 65°C to obtain a clean carbon cloth.

[0075] Step 2: Preparation of Mxene filler by etching: Add 50 mL of 10M HCI and 3.96 g of LiF as an etchant mixture to a polytetrafluoroethylene reagent bottle, seal and stir in an ice-water bath for 18 minutes until completely cooled. Slowly add 3.96 g of Ti3AlC2 to the etching reagent within 20 minutes to prevent oxidation of the material, and magnetically stir at 500 rpm / min in a 36 ° C constant temperature water bath for 52 hours to remove the Al layer. After etching, the crude product is centrifuged in deionized water at 4500 rpm / min for 3 minutes, and repeated 8 times until the pH of the upper liquid is 7. At this time, Ti3C2T x Spontaneous demixing began. After oscillation for 40 minutes, the mixture was sonicated in an ice-water bath for 1.5 hours. Centrifugation was then performed at 4500 rpm / min for 3 minutes, and the homogeneous dark green supernatant was collected. Finally, the resulting dark green supernatant was freeze-dried for 44 hours to yield minority-layer and monolayer MXene nanosheets.

[0076] Step 3: MXene nanosheets were added to a 30% by mass phenolic resin and ultrasonicated for 14 minutes until uniformly dispersed, creating a 0.10% by mass MXene-modified phenolic resin solution. The carbon cloth was completely immersed in the modified phenolic resin for 8 seconds, lifted vertically, and placed in an oven for 15 minutes. This was repeated three times, followed by drying at 65°C for 7.5 hours to obtain a prepreg.

[0077] Step 4: The prepreg is hot-pressed and cured at a temperature of 175 °C and a pressure of 5 MPa for 14 min in a vulcanizer. After naturally cooling to room temperature, a MXene filler-directionally modified anti-corrosion carbon fabric liner is obtained.

[0078] Comparative Example 1 A method for preparing an unmodified carbon fabric liner comprises: Step 1: Completely immerse the 6K carbon cloth in acetone, seal it, and soak it at room temperature for 48 hours. After soaking, rinse it with deionized water and dry it in an oven at 60°C to obtain a clean carbon cloth.

[0079] Step 2: The carbon cloth was completely immersed in the phenolic resin for 10 seconds, lifted vertically and placed in an oven for 15 minutes. The pulling and dipping were repeated three times, and then dried at 60 °C for 8 hours to obtain the prepreg.

[0080] Step 3: The prepreg was hot-pressed and cured at 170 °C and 5 MPa for 10 min in a vulcanizer. After naturally cooling to room temperature, an unmodified carbon fabric liner was obtained.

[0081] Figure 1Scanning electron microscopy images of MXene nanosheets and a MXene filler-directed modified anti-corrosion carbon fabric liner prepared in Example 2 of the present invention. (a) shows a MXene nanosheet; (b) shows a MXene filler-directed modified anti-corrosion carbon fabric liner. As can be seen from the images, the MXene nanosheets prepared by the etching method exhibit a clear 2D layered structure, with a size of approximately 2-5 μm and a thickness of approximately 2.74 nm. In the MXene filler-directed modified anti-corrosion carbon fabric liner, the filler is clearly visible spread out on the surface.

[0082] Figure 2 This is a comparison chart of the mechanical properties of the unmodified carbon fabric liner prepared in Comparative Example 1 of the present invention and the Mxene filler directionally modified anti-corrosion carbon fabric liner prepared in Example 2, wherein P-CF / PF is a carbon fabric liner and M-CF / PF is a Mxene filler directionally modified anti-corrosion carbon fabric liner. It can be seen from the figure that the tensile strength of the Mxene filler directionally modified anti-corrosion carbon fabric liner is increased by 12.10% compared with the carbon fabric liner.

[0083] Figure 3 This is a comparison of the polarization curves of the unmodified carbon fabric liner prepared in Comparative Example 1 of the present invention and the Mxene filler directionally modified anti-corrosion carbon fabric liner prepared in Example 2, wherein P-CF / PF is a carbon fabric liner and M-CF / PF is a Mxene filler directionally modified anti-corrosion carbon fabric liner. As can be seen from the figure, the corrosion current density increases from 9.15 × 10 -6 A / cm 2 Reduced to 1.46 × 10 of MXene filler directional modified anti-corrosion carbon fabric liner -6 A / cm 2 , a decrease of 84.03%.

[0084] Figure 4 This is a comparison chart of the tribological properties of the unmodified carbon fabric liner prepared in Comparative Example 1 of the present invention and the anti-corrosion carbon fabric liner with MXene filler directionally modified prepared in Example 2; wherein (a) is the friction coefficient, and (b) is a comparison of the average friction coefficient and wear rate; it can be seen from the figure that compared with the carbon fabric liner, the average friction coefficient of the anti-corrosion carbon fabric liner with MXene filler directionally modified is reduced by 26.41%, and the wear rate is reduced by 68.27%.

[0085] In summary, the present invention provides a method for preparing a MXene filler-directed modified anti-corrosion carbon fabric liner. First, a single or few-layer MXene nanosheets are prepared by etching. The MXene nanosheets are then uniformly dispersed in a phenolic resin solution. A prepreg is prepared by multiple unidirectional pulling and impregnation of carbon fabric. Finally, the MXene filler-directed modified anti-corrosion carbon fabric liner is obtained by hot pressing and curing. The MXene filler-directed modified anti-corrosion carbon fabric liner prepared by the present invention has excellent load-bearing performance. The MXene nanosheets are oriented and multi-leveled in the resin matrix. On the basis of improving the interfacial bonding between the carbon fibers and the phenolic resin, a three-dimensional "maze" structure is constructed to effectively block the infiltration of corrosive media, thereby improving the liner's protective ability for alloy bearings. In addition, the two-dimensional MXene nanosheets act on the friction interface during friction to form a self-lubricating film, significantly reducing the friction coefficient and wear rate of the MXene filler-directed modified anti-corrosion carbon fabric liner. In particular, the corrosion current density is 9.15 × 10 compared to the unmodified carbon fabric liner. -6 A / cm 2 1.46 × 10 MXene filler directional modified anti-corrosion carbon fabric liner -6 A / cm 2 It was reduced by 84.03% and the wear rate was significantly reduced by 68.27%.

[0086] 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 MXene filler directionally modified anti-corrosion carbon fabric liner, characterized in that: include: Ti3AlC2 was added to the etching reagent and stirred in a constant temperature water bath. After etching to remove the Al layer, the Ti3C2T x The mixture began to spontaneously separate and, after shaking, was placed in an ice-water bath for ultrasonic treatment, centrifuged and the supernatant was collected and freeze-dried to obtain MXene nanosheets. Adding MXene nanosheets and phenolic resin into a solvent and uniformly dispersing them by ultrasonication to obtain a MXene-modified phenolic resin solution; After pretreatment, the carbon cloth is immersed in a MXene-modified phenolic resin solution, pulled and impregnated multiple times, and dried to obtain a prepreg; and then hot-pressed and cured to obtain a MXene filler-directed modified anti-corrosion carbon fabric liner.

2. The method for preparing the MXene filler directionally modified anti-corrosion carbon fabric liner according to claim 1, characterized in that: The etching reagent is prepared by mixing an HCl solution and LiF, and sealing and stirring in an ice-water bath for 10-20 minutes; the concentration of the HCl solution is 8-10 mol / L; and the usage ratio of the Ti3AlC2, HCl solution, and LiF is (0.99-3.96) g: (20-60) mL: (0.99-3.96) g.

3. The method for preparing the MXene filler directionally modified anti-corrosion carbon fabric liner according to claim 1, characterized in that: The stirring conditions of the constant temperature water bath include: a rotation speed of 200-600 rpm / min, a water bath temperature of 30-40° C., and a stirring time of 40-56 h.

4. The method for preparing the MXene filler directionally modified anti-corrosion carbon fabric liner according to claim 1, characterized in that: The conditions for the water washing centrifugation include: 7-10 water washing centrifugations, a rotation speed of 3000-5000 rpm, and each centrifugation for 3-5 minutes, until the pH value of the upper layer liquid is neutral.

5. The method for preparing the MXene filler directionally modified anti-corrosion carbon fabric liner according to claim 1, characterized in that: The oscillation time is 15-60 min; the ultrasonic treatment time in the ice-water bath is 0.5-1.5 h; the centrifugation time is 3-5 min, and the rotation speed is 3000-5000 rpm; and the freeze-drying time is 36-48 h.

6. The method for preparing the MXene filler directionally modified anti-corrosion carbon fabric liner according to claim 1, characterized in that: In the MXene-modified phenolic resin solution, the mass fraction of MXene nanosheets is 0-0.20%; the solvent is acetone, and the mass ratio of acetone to phenolic resin is (4-7): (1-3); and the ultrasonic dispersion time is 10-15 min.

7. The method for preparing the MXene filler directionally modified anti-corrosion carbon fabric liner according to claim 1, characterized in that: The carbon cloth pretreatment method comprises: completely immersing the carbon cloth in acetone, sealing it, soaking it at room temperature for 42-54 hours, washing it with deionized water, and drying it at 60-80°C.

8. The method for preparing the MXene filler directionally modified anti-corrosion carbon fabric liner according to claim 1, characterized in that: The pulling and impregnation method comprises: pulling and impregnation in the same direction, impregnating for 8-10 seconds each time and drying, and repeating the cycle 2-3 times; and drying at a temperature of 50-70° C. for 6-8 hours.

9. The method for preparing the MXene filler directionally modified anti-corrosion carbon fabric liner according to claim 1, characterized in that: The conditions for the hot pressing curing include: a temperature of 165-175° C., a pressure of 4-6 MPa, and a time of 10-15 min.

10. A MXene filler directional modified anti-corrosion carbon fabric liner, characterized in that: The MXene filler directionally modified anti-corrosion carbon fabric liner is prepared by the preparation method according to any one of claims 1 to 9. Compared with the unmodified carbon fabric liner, the tensile strength is increased by 12.10%, the corrosion current density is reduced by 84.03%, the average friction coefficient is reduced by 26.41%, and the wear rate is reduced by 68.27%.

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