ZrO2 / MXene / HBPSi-EP composite material and preparation method

Abstract

The present invention discloses a ZrO2 / MXene / HBPSi-EP composite material and a preparation method, specifically comprising the following steps: mixing ZrOCl2·8H2O and a MXene dispersion, ultrasonicating, hydrothermally reacting, washing, adding deionized water, ultrasonically stirring, and freeze-drying to obtain ZrO2 / MXene powder; placing diethylene glycol and KH-560 in a reactor for polycondensation to obtain HBPSi with epoxy end groups; adding HBPSi to an epoxy resin EP-51 stirred in an oil bath and heating for prepolymerization; adding ZrO2 / MXene powder dispersed in acetone, stirring, adding a curing agent, injecting the composite material into a glass mold coated with a release agent to remove bubbles, performing a curing reaction, and demolding. The composite material prepared by the present invention has both excellent mechanical properties and friction properties, and can meet the friction application requirements of the electronics industry, automobile manufacturing, aerospace and other fields.

Description

Technical Field

[0001] The present invention belongs to the technical field of composite material preparation, and in particular relates to a ZrO2 / MXene / HBPSi-EP composite material, and also relates to a preparation method of the composite material. Background Art

[0002] Friction and wear can lead to energy loss on mechanical surfaces, causing serious energy loss, shortening the service life of equipment, and increasing mechanical accidents. Therefore, with the development of science and technology, the requirements for high wear resistance and low friction performance of mechanical parts have become increasingly urgent.

[0003] Epoxy resin (EP) is widely used in the automotive, aerospace, and packaging industries due to its excellent mechanical properties, low shrinkage, superior adhesion, and chemical stability. However, EP's inherent brittleness, high coefficient of friction, and high wear severely limit its application in advanced friction and wear applications. To improve the wear resistance of traditional epoxy resins, lubricating fillers or nanofillers are used to modify them. EP composites, prepared by mixing various reinforcing fillers with an EP matrix, possess excellent mechanical and anti-friction properties and therefore have broad potential for application in tribology.

[0004] Graphene-like layered materials MXene (a family of transition metal carbides and carbonitrides) have a larger interlayer spacing than graphene and weak van der Waals forces between layers, making them easy to slip during friction. They have high mechanical strength, excellent friction performance and self-lubricating properties. He et al. prepared amino-modified Ti3C2T x The results show that MXene can be used as a high-potential lubricant filler and reinforcing additive in polymer matrices to enhance their friction properties.

[0005] In recent years, inorganic oxide particles have garnered widespread attention in the lubrication field due to their excellent friction-reducing and anti-wear properties. Zirconium dioxide (ZrO2), with its high strength and load-bearing capacity, is a popular lubricant additive in composite materials. Therefore, combining MXene with ZrO2 can yield a high-hardness, highly wear-resistant, self-lubricating composite filler.

[0006] Hyperbranched polysiloxanes (HBPSi) are organic-inorganic hybrid polymers with a Si-OC backbone and organic groups as side chains. HBPSi not only exhibits high reactivity but also possesses a unique dendritic structure that contains numerous internal voids. HBPSi reacts with a variety of resins, and its void structure reduces crosslink density, forming a uniform and stable blend system, thereby enhancing the toughness of resin-based composites. Summary of the Invention

[0007] The purpose of the present invention is to provide a method for preparing a ZrO2 / MXene / HBPSi-EP composite material, which solves the problems of low mechanical strength, high friction coefficient and high wear rate of existing composite materials.

[0008] The technical solution adopted by the present invention is a method for preparing a ZrO2 / MXene / HBPSi-EP composite material, which is specifically implemented according to the following steps:

[0009] Step 1: Ti3AlC2 is etched and layered using HCl / LiF to prepare a MXene dispersion;

[0010] Step 2: ZrOCl2·8H2O and MXene dispersion are mixed and stirred, ultrasonically treated, placed in a high-pressure reactor for hydrothermal reaction, cooled, filtered and washed, deionized water is added to the obtained product, ultrasonically stirred, and freeze-dried to obtain ZrO2 / MXene powder;

[0011] Step 3, placing diethylene glycol and KH-560 in a reactor for polycondensation reaction, and gradually increasing the temperature under nitrogen atmosphere protection and condensation reflux, so that the temperature of the distillate is maintained at 40-65° C., until the temperature of the distillate drops below 40° C. and the reaction is completed, to obtain a hyperbranched polysiloxane HBPSi with an epoxy end group;

[0012] In step 4, the epoxy resin EP-51 is stirred in an oil bath, and then HBPSi is slowly added to the EP-51 and heated for prepolymerization. ZrO2 / MXene powder dispersed in acetone is added and stirred. Then, the curing agent DDS is added and the colloid is injected into a glass mold coated with a release agent. The mold is placed in a vacuum drying oven and a vacuum pump is used to remove bubbles. Finally, the curing reaction is carried out, cooled, and demolded to obtain the ZrO2 / MXene / HBPSi-EP composite material.

[0013] The present invention is also characterized in that:

[0014] In step 1, specifically: after LiF and HCl are mixed and reacted for 20-30 minutes, Ti3AlC2 powder is slowly added to the uniform mixture of LiF and HCl, and stirred at 25-45°C for 12-36 hours to obtain a fully reacted mixed dispersion; then the mixed dispersion is washed with deionized water at a centrifugal speed of 3500 rpm until the pH of the supernatant reaches 6.0, and ultrasonically treated at 150-210W for 15-20 minutes, centrifuged to obtain a MXene dispersion.

[0015] In step 2, the hydrothermal reaction temperature is 180-220°C, the hydrothermal reaction time is 20-36 hours, the freeze-drying time is 2 days, and the freeze-drying temperature is -55°C to -45°C.

[0016] In step 2, the mass ratio of ZrOCl2·8H2O to MXene is 1:0.5~2.

[0017] In step 3, the molar ratio of diethylene glycol to KH-560 is 3:2 to 2.4.

[0018] In step 3, the polycondensation reaction process is specifically as follows: rising from 100°C to 170-175°C and keeping the reaction warm for 8-11 hours; when the reaction temperature is 100-120°C, the heating rate is 15-20°C / h, and the keeping reaction time is 2-3 hours; when the reaction temperature is 120-150°C, the heating rate is 10-15°C / h, and the keeping reaction time is 4-5 hours; when the reaction temperature is 150-175°C, the heating rate is 5-10°C / h, and the keeping reaction time is 2-3 hours.

[0019] In step 4, the prepolymerization temperature is 130-150° C., and the prepolymerization time is 20-30 min.

[0020] In step 4, the mass ratio of epoxy resin EP-51 to curing agent DDS is 16:9; the mass of HBPSi is 2-10 wt% of the total mass of epoxy resin EP-51 and curing agent DDS; and the mass of ZrO2 / MXene powder is 0.2-1 wt% of the total mass of epoxy resin EP-51 and curing agent DDS.

[0021] In step 4, the curing reaction process is: first, heating from room temperature to 160-180°C at a heating rate of 1-2°C / min, and keeping warm for 3-5 hours; then heating to 220-240°C at a heating rate of 1-2°C / min, and keeping warm for 2-3 hours.

[0022] The present invention first combines ZrO2 with a layered material, MXene, to form ZrO2 / MXene. The high strength and load-bearing capacity of ZrO2, combined with the excellent friction and self-lubricating properties of MXene, enable the composite to achieve superior performance compared to adding a single lubricating reinforcing phase, resulting in a synergistic lubrication effect. Furthermore, the prepared dendritic HBPSi contains numerous cavities, which can reduce the crosslink density, thereby enhancing the toughness of the epoxy resin-based composite. Furthermore, the epoxy-terminated HBPSi facilitates incorporation into the network during the early stages of curing. As the curing reaction proceeds, the hyperbranched molecules form a permeating scaffold in the early stages of curing. Each hyperbranched crosslink and its directly connected region can be treated as an "effective sphere." Once the effective spheres penetrate the epoxy network, toughness and other properties are significantly enhanced. Thanks to these advantages, the resulting ZrO2 / MXene / HBPSi-EP composite exhibits both excellent mechanical and frictional properties. BRIEF DESCRIPTION OF THE DRAWINGS

[0023] Figure 1 is a scanning electron microscope image of ZrO2 / MXene-1:1 prepared in Example 1 of the present invention;

[0024] Figure 2 is a scanning electron microscope image of ZrO2 / MXene-2:1 prepared in Example 2 of the present invention;

[0025] Figure 3 is a scanning electron microscope image of ZrO2 / MXene-1:2 prepared in Example 3 of the present invention;

[0026] Figure 4 Schematic diagram of the synthesis process of HBPSi with an epoxy end group in the method of the present invention;

[0027] Figure 5 The bending strength diagram of the ZrO2 / MXene / HBPSi-EP composite material system with 6 wt% HBPSi and different addition amounts of ZrO2 / MXene nanofillers;

[0028] Figure 6 Impact strength diagram of ZrO2 / MXene / HBPSi-EP composite material system with 6wt% HBPSi and different addition amounts of ZrO2 / MXene nanofillers;

[0029] Figure 7 This is a curve showing the change of friction coefficient of pure EP resin and ZrO2 / MXene / 6wt% HBPSi-EP composite material with an addition amount of 0.4wt.% as a function of friction time. DETAILED DESCRIPTION

[0030] The present invention will be described in detail below with reference to the accompanying drawings and specific embodiments.

[0031] The preparation method of the ZrO2 / MXene / HBPSi-EP composite material of the present invention is specifically implemented according to the following steps:

[0032] Step 1: Ti3AlC2 is etched and layered using HCl / LiF to prepare a MXene dispersion;

[0033] Specifically, LiF and HCl were mixed and reacted for 20-30 minutes, and then Ti3AlC2 powder was slowly added to the uniform mixture of LiF and HCl, and stirred at 25-45°C for 12-36 hours to obtain a fully reacted mixed dispersion. The mixed dispersion was then washed with deionized water at a centrifugal speed of 3500 rpm until the pH of the supernatant reached 6.0, and then ultrasonicated at 150-210 W for 15-20 minutes. Finally, the mixture was centrifuged at 3500 rpm for 1 hour to obtain a MXene dispersion. The concentration of the MXene dispersion was 5 mg / mL.

[0034] Step 2: zirconium oxychloride octahydrate ZrOCl2·8H2O and MXene dispersion are mixed and stirred in a mass ratio of 1:0.5-2, and ultrasonically treated for 30 minutes. The mixed solution is transferred to a polytetrafluoroethylene-lined high-pressure reactor for hydrothermal reaction. After the reaction is completed, it is cooled to room temperature, filtered, and washed several times with anhydrous ethanol. Deionized water is added to the obtained product, ultrasonically stirred, and freeze-dried to obtain ZrO2 / MXene powder;

[0035] The hydrothermal reaction temperature is 180-220°C, the hydrothermal reaction time is 20-36 hours, the freeze-drying time is 2 days, and the freeze-drying temperature is -55°C to -45°C;

[0036] Step 3, diethylene glycol and γ-(2,3-epoxypropoxy)propyltrimethoxysilane (KH-560) are placed in a reactor equipped with a stirrer, a thermometer, a nitrogen inlet and a condenser in a molar ratio of 3:2 to 2.4 for polycondensation reaction. Under the protection of nitrogen atmosphere and condensation reflux, the reaction is carried out by a "one-pot polycondensation method" with gradient temperature increase and controlled heating rate, and the temperature of the distillate is maintained at 40-65°C. During this process, liquid is distilled out of the round-bottom flask where the distillate is collected until the temperature of the distillate drops below 40°C, and the reaction is completed to obtain a hyperbranched polysiloxane (HBPSi) with an epoxy end group; the purpose of using gradient temperature increase is to completely distill off the by-product methanol. The synthesis process of HBPSi is as follows Figure 4 As shown;

[0037] The specific reaction process is as follows: the temperature is raised from 100°C to 170-175°C and kept warm for 8-11 hours; when the reaction temperature is 100-120°C, the heating rate is 15-20°C / h, and the heat preservation reaction time is 2-3 hours; when the reaction temperature is 120-150°C, the heating rate is 10-15°C / h, and the heat preservation reaction time is 4-5 hours; when the reaction temperature is 150-175°C, the heating rate is 5-10°C / h, and the heat preservation reaction time is 2-3 hours;

[0038] Step 4: Stir the epoxy resin EP-51 in an oil bath at 130-150°C for 10-60 minutes, then slowly add HBPSi to EP-51 and heat prepolymerize at 130-150°C for 20-30 minutes. Then, add ZrO2 / MXene powder dispersed in acetone and continue stirring for 5-10 minutes. Then, add the curing agent DDS and inject the colloid into a glass mold coated with a release agent. Then, place it in a vacuum drying oven at 130-150°C and use a vacuum pump to remove bubbles for 20-30 minutes. Finally, transfer the mold to a blast drying oven to perform a curing reaction by programmed temperature increase, cool naturally, and demold to obtain a ZrO2 / MXene / HBPSi-EP composite material.

[0039] The mass ratio of epoxy resin to curing agent is 16:9; the mass of HBPSi is 2-10wt% of the total mass of epoxy resin EP-51 and curing agent DDS; the mass of ZrO2 / MXene powder is 0.2-1wt% of the total mass of epoxy resin EP-51 and curing agent DDS;

[0040] The curing reaction process is: first, heating from room temperature to 160-180°C at a heating rate of 1-2°C / min, and keeping warm for 3-5 hours; then heating to 220-240°C at a heating rate of 1-2°C / min, and keeping warm for 2-3 hours.

[0041] The present invention discloses a method for preparing a ZrO2 / MXene / HBPSi-EP composite material. First, ZrO2 / MXene fillers in different proportions are prepared using a hydrothermal method. A novel epoxy-terminated HBPSi is synthesized via a polycondensation reaction using γ-glycidyloxypropyltrimethoxysilane and diethylene glycol. A resin is modified with HBPSi to serve as a matrix. The HBPSi is then added to a molten resin matrix and heated for prepolymerization. ZrO2 / MXene fillers are then incorporated into the matrix as a solid lubricant, and a curing agent, 4,4-diaminophenylsulfone (DDS), is added. The composite material is then cured and molded using a casting method to produce a ZrO2 / MXene / HBPSi-EP composite material with excellent interfacial bonding strength, high mechanical strength, low friction, and high wear resistance. This allows the resin-based composite material to reduce friction coefficients and minimize friction and wear failures when used in aerospace applications, thereby improving component precision and extending its overall service life.

[0042] Example 1

[0043] The preparation method of the ZrO2 / MXene / HBPSi-EP composite material of the present invention is specifically as follows:

[0044] Step 1, using HCl / LiF to etch and layer Ti3AlC2 to prepare a MXene dispersion;

[0045] Specifically, after LiF and HCl were mixed and reacted for 30 minutes, Ti3AlC2 powder was slowly added to the uniform mixture of LiF and HCl, and stirred at 35°C for 24 hours to obtain a fully reacted mixed dispersion; then the mixed dispersion was washed with deionized water at a centrifugal speed of 3500 rpm until the pH of the supernatant reached 6.0, and then ultrasonically treated at 180W for 20 minutes, and finally centrifuged at a rate of 3500 rpm for 1 hour to obtain a MXene dispersion.

[0046] Step 2: octahydrate zirconium oxychloride ZrOCl2·8H2O and 70 mL MXene dispersion (mass ratio of the two is 1:1) are ultrasonically treated for 30 minutes to mix evenly, and the mixed solution is transferred to a polytetrafluoroethylene-lined autoclave for reaction at a temperature of 180°C and a reaction time of 20 hours. After the reaction is completed, the mixed solution in the autoclave is cooled to room temperature, filtered and washed several times with anhydrous ethanol, deionized water is added to the obtained product, ultrasonically stirred, and freeze-dried for 2 days at a freeze-drying temperature of -50°C to obtain ZrO2 / MXene powder; marked as ZrO2 / MXene-1:1; Figure 1 As shown in the figure, it can be seen that when the filler ratio is evenly distributed, there are a lot of wrinkles and stratification phenomena, it has a high specific surface area and good dispersion.

[0047] Step 3, 0.6 mol of diethylene glycol and 0.44 mol of KH-560 are added to a 250 mL four-necked flask equipped with a stirrer, a thermometer, a nitrogen inlet and a condenser, and under nitrogen atmosphere protection and condensation reflux, a "one-pot polycondensation method" of gradient heating and controlling the heating rate is used, specifically, from 100 ° C to 170 ° C for 8 hours, when the reaction temperature is 100-120 ° C, the heating rate is 15 ° C / h, and the insulation reaction time is 2 hours; when the reaction temperature is 120-150 ° C, the heating rate is 10 ° C / h, and the insulation reaction time is 4 hours; when the reaction temperature is 150-170 ° C, the heating rate is 5 ° C / h, and the insulation reaction time is 2 hours; and the temperature of the distillate is maintained at 40-65 ° C until the temperature of the distillate drops below 40 ° C, to obtain a hyperbranched polysiloxane with an epoxy end group, recorded as HBPSi;

[0048] In step 4, 86.40 g of epoxy EP resin was stirred at 130°C for 10 minutes. Then, 6 wt% HBPSi was slowly added to the molten EP while stirring and mixed for 15 minutes. 0.2 wt% of the filler ZrO2 / MXene was dispersed in acetone and poured into a beaker. Stirring continued for 5 minutes, followed by the addition of 64.60 g of the curing agent DDS. The colloid was then carefully poured into a glass mold coated with a release agent and placed in a vacuum drying oven at 130°C. Air bubbles were removed using a vacuum pump for 30 minutes. Finally, the mold was transferred to a forced-air drying oven and cured by a programmed temperature ramp (170°C for 4 hours followed by 230°C for 2 hours). After curing was complete and the mixture was allowed to cool naturally, the ZrO2 / MXene / HBPSi-EP composite was removed from the mold.

[0049] Example 2

[0050] The preparation method of the ZrO2 / MXene / HBPSi-EP composite material of the present invention is specifically as follows:

[0051] Step 1, using HCl / LiF to etch and layer Ti3AlC2 to prepare a MXene dispersion;

[0052] Specifically, after LiF and HCl were mixed and reacted for 30 minutes, Ti3AlC2 powder was slowly added to the uniform mixture of LiF and HCl, and stirred at 35°C for 24 hours to obtain a fully reacted mixed dispersion; then, the mixed dispersion was washed with deionized water at a centrifugal speed of 3500 rpm until the pH of the supernatant reached 6.0, and then ultrasonically treated at 180W for 20 minutes, and finally centrifuged at a speed of 3500 rpm for 1 hour to obtain a MXene dispersion;

[0053] Step 2: octahydrate zirconium oxychloride ZrOCl2·8H2O and 80 mL MXene dispersion (mass ratio of the two is 2:1) are ultrasonically treated for 30 min to mix evenly, and the mixed solution is transferred to a polytetrafluoroethylene-lined autoclave for reaction at a temperature of 180 ° C and a reaction time of 20 h. After the reaction is completed, the mixed solution in the autoclave is cooled to room temperature, filtered and washed several times with anhydrous ethanol, deionized water is added to the obtained product, ultrasonically stirred, and freeze-dried for 2 days at a freeze-drying temperature of -50 ° C to obtain ZrO2 / MXene powder; marked as ZrO2 / MXene-2:1; Figure 2 As shown in the figure, it can be concluded that when there is too much ZrO2, a large number of nanoparticles gather on the surface of MXene nanosheets and the dispersion decreases.

[0054] Step 3, 0.6 mol of diethylene glycol and 0.44 mol of KH-560 are added to a 250 mL four-necked flask equipped with a stirrer, a thermometer, a nitrogen inlet and a condenser, and under nitrogen atmosphere protection and condensation reflux, a "one-pot polycondensation method" of gradient heating and controlling the heating rate is used, specifically, the reaction is continuously carried out from 100 ° C to 175 ° C for 9 hours, when the reaction temperature is 100-120 ° C, the heating rate is 20 ° C / h, and the insulation reaction time is 3 hours; when the reaction temperature is 120-150 ° C, the heating rate is 15 ° C / h, and the insulation reaction time is 4 hours; when the reaction temperature is 150-175 ° C, the heating rate is 10 ° C / h, and the insulation reaction time is 2 hours; and the temperature of the distillate is maintained at 40-65 ° C until the temperature of the distillate drops below 40 ° C, to obtain a hyperbranched polysiloxane with an epoxy end group, recorded as HBPSi;

[0055] In step 4, the epoxy EP resin was stirred at 130°C for 10 minutes. Then, 4 wt% HBPSi was slowly added to the molten EP while stirring and stirred for 15 minutes until uniformly mixed. Next, 0.4 wt% of the filler ZrO2 / MXene-2:1 was dispersed in acetone, poured into a beaker, and stirred for 5 minutes. The curing agent DDS was then added. The colloid was then carefully poured into a glass mold coated with a release agent and placed in a vacuum drying oven at 130°C. Air bubbles were removed using a vacuum pump for approximately 30 minutes. Finally, the mold was transferred to a forced air drying oven and cured by a programmed temperature increase (170°C for 4 hours followed by 230°C for 2 hours). After curing was complete and the mixture was allowed to cool naturally, the ZrO2 / MXene / HBPSi-EP composite was obtained.

[0056] Example 3

[0057] The preparation method of the ZrO2 / MXene / HBPSi-EP composite material of the present invention is specifically as follows:

[0058] Step 1, using HCl / LiF to etch and layer Ti3AlC2 to prepare a MXene dispersion;

[0059] Specifically, after LiF and HCl were mixed and reacted for 30 minutes, Ti3AlC2 powder was slowly added to the uniform mixture of LiF and HCl, and stirred at 35°C for 24 hours to obtain a fully reacted mixed dispersion; then, the mixed dispersion was washed with deionized water at a centrifugal speed of 3500 rpm until the pH of the supernatant reached 6.0, and then ultrasonically treated at 180W for 20 minutes, and finally centrifuged at a speed of 3500 rpm for 1 hour to obtain a MXene dispersion;

[0060] Step 2: octahydrate zirconium oxychloride ZrOCl2·8H2O and 70 mL MXene dispersion (mass ratio of the two is 1:2) are ultrasonically treated for 30 minutes to mix evenly, and the mixed solution is transferred to a polytetrafluoroethylene-lined autoclave for reaction at a temperature of 180°C and a reaction time of 20 hours. After the reaction is completed, the mixed solution in the autoclave is cooled to room temperature, filtered and washed several times with anhydrous ethanol. Deionized water is added to the obtained product, ultrasonically stirred, and freeze-dried for 2 days at a freeze-drying temperature of -50°C to obtain ZrO2 / MXene powder; marked as ZrO2 / MXene-1:2; Figure 3 As shown in the figure, it can be concluded that when too much MXene is added, a multilayer structure stacked on top of each other will appear, limiting its dispersibility.

[0061] Step 3, 0.6 mol of diethylene glycol and 0.44 mol of KH-560 are added to a 250 mL four-necked flask equipped with a stirrer, a thermometer, a nitrogen inlet and a condenser, and under nitrogen atmosphere protection and condensation reflux, a "one-pot polycondensation method" of gradient heating and controlling the heating rate is used, specifically, the reaction is continuously carried out from 100 ° C to 175 ° C for 10 hours, when the reaction temperature is 100-120 ° C, the heating rate is 20 ° C / h, and the insulation reaction time is 2 hours; when the reaction temperature is 120-150 ° C, the heating rate is 10 ° C / h, and the insulation reaction time is 6 hours; when the reaction temperature is 150-175 ° C, the heating rate is 5 ° C / h, and the insulation reaction time is 3 hours; and the temperature of the distillate is maintained at 40-65 ° C until the temperature of the distillate drops below 40 ° C, to obtain a hyperbranched polysiloxane with an epoxy end group, recorded as HBPSi;

[0062] In step 4, the epoxy resin (EP) was stirred at 130°C for 10 minutes. Then, 8 wt% HBPSi was slowly added to the molten EP while stirring and mixed thoroughly for 15 minutes. 0.6 wt% of the filler ZrO2 / MXene (1:2) was dispersed in acetone, poured into a beaker, and stirred for 5 minutes. The curing agent, DDS, was then added. The colloid was then carefully poured into a glass mold coated with a release agent and placed in a vacuum drying oven at 130°C. Air bubbles were removed using a vacuum pump for approximately 30 minutes. Finally, the mold was transferred to a forced-air drying oven and cured by a programmed temperature ramp (170°C for 4 hours followed by 230°C for 2 hours). After curing was complete and the mixture was allowed to cool naturally, the ZrO2 / MXene / HBPSi-EP composite was obtained.

[0063] Depend on Figure 5 and Figure 6 It can be concluded that the addition of 6wt.% of HBPSi with epoxy end groups to modify EP as a matrix showed even better flexural strength of 148.94MPa and impact strength of 26.41kJ / m 2 .

[0064] Depend on Figure 5 It can be concluded that the flexural strength of the composite material is further improved after adding different amounts of ZrO2 / MXene nanofillers with 6wt.% HBPSi-EP as the matrix. At the same time, the flexural strength of the composite material with an addition amount of 0.4wt.% ZrO2 / MXene filler reaches a maximum of 167.452MPa.

[0065] Depend on Figure 6 It can be concluded that the impact strength of the composite material is further improved after adding different amounts of ZrO2 / MXene nanofillers with 6wt.% HBPSi-EP as the matrix. At the same time, the impact strength of the composite material with an addition amount of 0.4wt.% ZrO2 / MXene filler reaches a maximum of 36.23kJ / m 2 .

[0066] Depend on Figure 7 The average friction coefficient of the 0.4 wt.% ZrO2 / MXene / 6 wt.% HBPSi-EP composite was 0.32, a 45.8% decrease compared to the 0.59 friction coefficient of the unfilled EP resin, indicating that the presence of ZrO2 / MXene has a friction-reducing effect on the EP resin.

[0067] The preparation method of the ZrO2 / MXene / HBPSi-EP composite material of the present invention comprises modifying ZrO2 / MXene nanocomposite particles by using hyperbranched polysiloxane, and then incorporating the modified particles into EP resin to prepare a composite material with excellent mechanical and friction properties. The preparation process has broad practicality and promotion value. The ZrO2 / MXene / HBPSi-EP composite material prepared by the method of the present invention has both excellent mechanical and friction properties, and can meet the friction application requirements of the electronics industry, automobile manufacturing, aerospace and other fields.

[0068] The mechanism of action of the present method is as follows: First, ZrO2 is compounded with the layered material MXene to form ZrO2 / MXene. The high strength and load-bearing capacity of ZrO2 and the superior friction and self-lubricating properties of MXene enable the composite to achieve superior performance compared to adding a single lubricating reinforcing phase, resulting in a synergistic lubrication effect. Furthermore, the prepared dendritic HBPSi contains numerous cavities, which reduce the crosslink density, thereby enhancing the toughness of the epoxy resin-based composite. Furthermore, the epoxy-terminated HBPSi facilitates incorporation into the network during the early stages of curing. As the curing reaction proceeds, the hyperbranched molecules form a permeating scaffold in the early stages of curing. Each hyperbranched crosslink and its directly connected region can be treated as an "effective sphere." Once the effective spheres penetrate the epoxy network, toughness and other properties are significantly enhanced. Thanks to these advantages, the resulting ZrO2 / MXene / HBPSi-EP composite exhibits both excellent mechanical and frictional properties.

[0069] The ZrO2 / MXene / HBPSi-EP composite material prepared by the present invention, the high strength and high load-bearing capacity of ZrO2 and the superior friction and self-lubricating properties of MXene, facilitate a synergistic lubrication effect on EP when friction occurs, thereby achieving excellent friction performance. In addition, the presence of HBPSi can effectively improve the mechanical properties of the EP composite material. This allows the prepared epoxy composite material to better meet the performance requirements of friction materials in fields such as aerospace. HBPSi with epoxy end groups is obtained by polycondensation reaction using diethylene glycol and KH560. The HBPSi-modified ZrO2 / MXene / EP composite material exhibits high toughness, low friction, and high wear resistance. This provides a feasible solution for the preparation of resin-based composite materials with both excellent mechanical and friction properties.

Claims

1. A method for preparing a ZrO2 / MXene / HBPSi-EP composite material, characterized in that: Please follow the steps below to implement it: Step 1: Ti3AlC2 is etched and layered using HCl / LiF to prepare a MXene dispersion; Step 2: ZrOCl2·8H2O and MXene dispersion are mixed and stirred, ultrasonically treated, placed in a high-pressure reactor for hydrothermal reaction, cooled, filtered and washed, deionized water is added to the obtained product, ultrasonically stirred, and freeze-dried to obtain ZrO2 / MXene powder; Step 3, placing diethylene glycol and KH-560 in a reactor for polycondensation reaction, and gradually increasing the temperature under nitrogen atmosphere protection and condensation reflux, so that the temperature of the distillate is maintained at 40-65° C., until the temperature of the distillate drops below 40° C. and the reaction is completed, to obtain a hyperbranched polysiloxane HBPSi with an epoxy end group; The molar ratio of diethylene glycol to KH-560 is 3:2~2.4; The polycondensation reaction process is as follows: the temperature is raised from 100°C to 170-175°C and kept warm for 8-11 hours; when the reaction temperature is 100-120°C, the heating rate is 15-20°C / h and the heat preservation time is 2-3 hours; when the reaction temperature is 120-150°C, the heating rate is 10-15°C / h and the heat preservation time is 4-5 hours; when the reaction temperature is 150-175°C, the heating rate is 5-10°C / h and the heat preservation time is 2-3 hours; Step 4: Stir the epoxy resin EP-51 in an oil bath, then slowly add HBPSi to the EP-51 and heat for prepolymerization. Add ZrO2 / MXene powder dispersed in acetone and stir. Then add the curing agent DDS. Pour the colloid into a glass mold coated with a release agent, place it in a vacuum drying oven, and use a vacuum pump to remove bubbles. Finally, allow the curing reaction to proceed, cool, and demold to obtain the ZrO2 / MXene / HBPSi-EP composite material. The mass ratio of epoxy resin EP-51 and curing agent DDS is 16:9; the mass of HBPSi is 2-10wt% of the total mass of epoxy resin EP-51 and curing agent DDS; the mass of ZrO2 / MXene powder is 0.2-1wt% of the total mass of epoxy resin EP-51 and curing agent DDS.

2. The method for preparing the ZrO2 / MXene / HBPSi-EP composite material according to claim 1, characterized in that: In the step 2, the hydrothermal reaction temperature is 180-220° C., the hydrothermal reaction time is 20-36 hours, the freeze-drying time is 2 days, and the freeze-drying temperature is -55° C. to -45° C.

3. The method for preparing the ZrO2 / MXene / HBPSi-EP composite material according to claim 1, characterized in that: In step 2, the mass ratio of ZrOCl2·8H2O to MXene is 1:0.5~2.

4. The method for preparing the ZrO2 / MXene / HBPSi-EP composite material according to claim 1, characterized in that: In the step 4, the prepolymerization temperature is 130-150° C., and the prepolymerization time is 20-30 minutes.

5. The method for preparing the ZrO2 / MXene / HBPSi-EP composite material according to claim 1, characterized in that: In step 4, the curing reaction process is: first, heating from room temperature to 160-180°C at a heating rate of 1-2°C / min, and keeping warm for 3-5 hours; then heating to 220-240°C at a heating rate of 1-2°C / min, and keeping warm for 2-3 hours.

6. A ZrO2 / MXene / HBPSi-EP composite material prepared by the method according to any one of claims 1 to 5.

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