Wear-resistant PEEK composite material and preparation method thereof

Abstract

The invention relates to the technical field of high polymer materials, in particular to a wear-resistant PEEK composite material and a preparation method thereof.The preparation method comprises the steps that phenylethynyl phthalic anhydride is added into polyether-ether-ketone powder for evaporation end-capping treatment, end-capped polyether-ether-ketone with an alkynylated large end and a small end is formed, and end-capped polyether-ether-ketone with the alkynylated large end and the small end is prepared; dispersing the mixed filler particles in a mixed solution containing a silane coupling agent, stirring, and carrying out melt mixing treatment on the stirred composite filler and terminated polyether-ether-ketone to obtain a composite melt; carrying out hot pressing on the composite melt to form a crystal structure, and carrying out thermal cycle diffusion treatment on the crystal structure to obtain a heat treatment product comprising an interface diffusion layer; and performing scanning treatment on the heat treatment product based on pulse laser to melt the polyether-ether-ketone on the surface layer and activate the interface diffusion layer to form the wear-resistant composite material comprising the wear-resistant coating. The technical problems that in the prior art, a wear-resistant coating is weak in interface bonding force with a base body and prone to being stripped too early are solved, and the wear rate is greatly reduced compared with the prior art.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of high polymer materials, in particular to a wear-resistant PEEK composite material and a preparation method thereof. BACKGROUND

[0002] Polyether ether ketone (PEEK) has excellent high-temperature resistance, corrosion resistance and high strength characteristics, and is applied to high-wear scenarios such as aircraft engine components, automobile transmission systems and medical implant devices. To meet the long-life requirements under frictional conditions, the existing technology generally adds hard particles or fiber fillers to the PEEK matrix and assists with surface coating to improve overall wear resistance. Common processes include direct injection molding after melt blending, or spraying polytetrafluoroethylene, MoS2 and other solid lubricating coatings on the surface of the molded part.

[0003] However, in complex service environments such as high temperature, high load or dry friction, the existing PEEK composite material has the problem of weak interfacial bonding force between the wear-resistant coating and the matrix, which leads to premature peeling of the coating. The coating and the matrix are mainly bonded by van der Waals force or mechanical embedding effect, lack of chemical bond bridging and transition layer, under the action of cyclic shear stress, microcracks at the interface rapidly expand, causing large-area peeling of the coating, making the material quickly lose low friction characteristics, and the actual service life is only 30% to 50% of the expected value, which seriously restricts the large-scale application of PEEK composite materials in high-end equipment.

[0004] Therefore, a new preparation method is needed to solve the above problems. SUMMARY

[0005] The main purpose of the present application is to provide a preparation method of a wear-resistant PEEK composite material, which aims to overcome the technical problem of weak interfacial bonding force between the wear-resistant coating and the matrix of the existing PEEK composite material, which leads to premature peeling of the coating.

[0006] In order to solve the above problems, the present application provides a preparation method of a wear-resistant PEEK composite material, which comprises: A preparation method of a wear-resistant PEEK composite material, characterized in that the method comprises: Preparation of end-capped polyether ether ketone with alkyne group large end and small end, mixing filler particles are dispersed in a mixed solution containing silane coupling agent for stirring to form a composite filler, and the composite filler and the end-capped polyether ether ketone are melt mixed to obtain a composite melt; The composite melt is hot-pressed to obtain a crystal structure of the composite melt surface layer forming a crystallization zone, and the crystal structure is subjected to thermal cycle diffusion treatment to diffuse the small end of the end-capped polyether ether ketone into the crystal structure to form an interfacial diffusion layer, thereby obtaining a heat-treated product; scanning the surface of the heat treated product with pulsed laser and passing in silane vapor to form covalent anchoring of the acetylenic large end in the crystalline zone, and to form micro-protrusion structure of the small end of the interfacial diffusion layer by polycondensation reaction with the silane vapor, to obtain the wear-resistant composite material; stirring the mixed filler particles dispersed in the mixed solution containing silane coupling agent, and then melt mixing the stirred composite filler with the end-capped polyether ether ketone to obtain a composite melt; hot-pressing the composite melt to form a crystal structure, and heat cycle diffusion treatment of the crystal structure to obtain a heat treated product comprising an interfacial diffusion layer; scanning the heat treated product with pulsed laser to melt the surface layer of polyether ether ketone and activate the interfacial diffusion layer, to form a wear-resistant composite material comprising a wear-resistant coating; wherein the large chain segment end of the wear-resistant coating forms a covalent bond with the surface layer crystalline zone, and the small chain segment end extends to the interfacial diffusion layer to form a micro-protrusion structure.

[0007] Further, the mixed filler particles are particles formed by mixing boron nitride with at least one of silicon oxide, aluminum oxide or silicon carbide, and the boron nitride accounts for 60-70% of the total mass of the mixed filler particles.

[0008] Further, the mixed solution comprises γ-glycidoxypropyltrimethoxysilane, polyether amine and isopropanol solution, and the γ-glycidoxypropyltrimethoxysilane accounts for 0.9-1% of the total mass of the mixed filler particles, and the polyether amine accounts for 0.6-0.7% of the total mass of the mixed filler particles.

[0009] Further, the evaporation end-capping treatment of the polyether ether ketone powder with phenylacetylenyl phthalic anhydride to form the end-capped polyether ether ketone comprising acetylenic large end and small end comprises: vacuum rotary evaporation pretreatment of the polyether ether ketone powder in a rotary evaporator, and then adding phenylacetylenyl phthalic anhydride to the pretreated ether ether ketone powder under argon atmosphere to obtain an end-capping reaction system; single-sided esterification treatment of the end-capping reaction system by slowly heating and stirring at 330-335℃ to obtain the end-capped polyether ether ketone powder with single-sided acetylenic large end and free hydroxyl small end.

[0010] Further, the step of dispersing the mixed filler particles in isopropanol solution and stirring comprises the step of dispersing the mixed filler particles in the mixed solution containing silane coupling agent to form a composite filler after stirring. Disperse the mixed filler particles in an isopropyl alcohol solution for dispersion treatment to obtain a filler dispersion liquid; Under the conditions of pH 8-9 and temperature 70-75℃, magnetically stir the filler dispersion liquid to obtain a double-shell filler including an epoxy inner shell layer and an outer shell layer; Cool the double-shell filler to 50-55℃ for interfacial ring-opening reaction treatment to obtain a gradient core-shell structure composite filler.

[0011] Further, the step of melt-mixing the stirred composite filler with the capped polyether ether ketone to obtain a composite melt includes: Add the gradient core-shell structure composite filler and capped polyether ether ketone powder according to a mass ratio of 100:20-22 into a mixer, and perform shear melt dispersion treatment at a temperature of 360-365℃ to make the acetylenic group large end undergo click chemistry reaction with the outer shell layer and the free hydroxyl group small end embedded into the epoxy inner shell layer, thereby obtaining a composite melt.

[0012] Further, the step of hot-pressing the composite melt to form a crystal structure includes: Place the composite melt in a hot press mold, and set the upper mold temperature to 380-190℃ and the lower mold temperature to 340-350℃. Set the pressure of the hot press mold to 90-95MPa, and perform hot-pressing treatment on the composite melt to obtain a nascent crystal melt. Unload the pressure on the nascent crystal melt to set the shape, and make the polyether ether ketone molecular chain form a high-orientation crystal region on the surface layer to obtain a crystal structure.

[0013] Further, the step of performing thermal cycle diffusion treatment on the crystal structure to obtain a heat-treated product including an interfacial diffusion layer includes: Under a nitrogen protective atmosphere, heat the crystal structure at 150-155℃ for 60-65 minutes to obtain a slightly rearranged crystal structure. Heat the slightly rearranged crystal structure to 200-210℃ for 40-45 minutes to make the free hydroxyl group small end diffuse to the epoxy inner shell layer to obtain an intermediate product containing an inner interfacial diffusion layer. Heat the intermediate product to 270-280℃ for 25-30 minutes to make the acetylenic group large end undergo thermal-induced click crosslinking in the outer shell layer to obtain a transition product. After heating the transition product to 170-180℃ for 45-50 minutes, further heat it to 50-60℃ for 70-80 minutes to obtain a heat-treated product.

[0014] Further, the step of scanning the heat-treated product with a pulsed laser to melt the surface polyether ether ketone and activate the interfacial diffusion layer to form a wear-resistant composite material including a wear-resistant coating, and then scanning the surface of the heat-treated product with a pulsed laser and introducing silane vapor to covalently anchor the large end of the acetylation in the crystalline region, and having the small end of the interfacial diffusion layer undergo a polycondensation reaction with the silane vapor to form a micro-protrusion structure, thereby obtaining the wear-resistant composite material, includes: The heat-treated product is subjected to a first-stage scanning process using pulsed laser light, with a scanning speed and power density of 28~30W / cm². 2 This yields a surface-melted activated product. Trimethylchlorosilane vapor, accounting for 0.3% of the volume of the laser processing chamber, is introduced into the chamber, and laser scanning is continued for 10-15 minutes to obtain an intermediate composite material containing a siloxane prepolymer layer. The intermediate composite material was subjected to a second-stage scanning process, with the scanning speed and power density reduced to 20-22 W / cm². 2 The siloxane prepolymer layer is cured to form a wear-resistant coating, resulting in a wear-resistant composite material including the wear-resistant coating.

[0015] This application also discloses a wear-resistant PEEK composite material, which is prepared by the method for preparing wear-resistant PEEK composite materials as described in any of the above claims.

[0016] Beneficial effects: This application proposes a method for preparing a wear-resistant PEEK composite material. During friction, the large chain segments of the wear-resistant coating are firmly anchored to the crystalline region through covalent bonds to avoid stress concentration and delamination. The micro-protrusion structure formed by the small chain segments, together with the interface diffusion layer, enables the continuous and controllable release of lubricating components and dynamic adaptive adjustment of surface morphology. The laser-induced high-density microstructure surface and low-density internal gradient further enhance thermal conductivity and fatigue resistance. The surface roughness Ra of the treated composite material is stably controlled within 0.6 μm, and the wear rate is significantly reduced compared with the existing technology benchmark. This forms a tough and wear-resistant long-life interface system, improving the operational stability and maintenance economy of high-end equipment. Attached Figure Description

[0017] Figure 1 This is a schematic diagram of the preparation method steps of a wear-resistant PEEK composite material in one embodiment of the present invention.

[0018] Figure 2 This is a schematic diagram of the preparation method steps of a wear-resistant PEEK composite material in another embodiment of the present invention.

[0019] The realization of the objective, functional features and advantages of the present invention will be further explained in conjunction with the embodiments and with reference to the accompanying drawings. Detailed Implementation

[0020] To make the objectives, technical solutions, and advantages of this application clearer, the following detailed description is provided in conjunction with the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative and not intended to limit the scope of this application.

[0021] Those skilled in the art will understand that, unless specifically stated otherwise, the singular forms “a,” “an,” “the,” and “the” used herein may also include the plural forms. It should be further understood that the term “comprising” as used in this specification means the presence of features, integers, steps, operations, elements, modules, and / or components, but does not exclude the presence or addition of one or more other features, integers, steps, operations, elements, modules, components, and / or groups thereof. It should be understood that when an element is referred to as “connected” or “coupled” to another element, it may be directly connected or coupled to the other element, or there may be intermediate elements. Furthermore, “connected” or “coupled” as used herein may include wireless connection or wireless coupling. The term “and / or” as used herein includes all or any modules and all combinations of one or more associated listed items.

[0022] It will be understood by those skilled in the art that, unless otherwise defined, all terms used herein (including technical and scientific terms) have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains. It should also be understood that terms such as those defined in general dictionaries should be understood to have the same meaning as in the context of the prior art, and should not be interpreted in an idealized or overly formal sense unless specifically defined as herein.

[0023] Reference Figure 1 This invention provides a method for preparing a wear-resistant PEEK composite material, the method comprising: S1: Phenylacetyl phthalic anhydride is added to polyether ether ketone powder for evaporation and end-capping treatment to form end-capped polyether ether ketone including alkynylated large and small ends. End-capped polyether ether ketone with alkynylated large and small ends is prepared. Mixed filler particles are dispersed in a mixed solution containing silane coupling agent and stirred to form a composite filler. The composite filler is melt-mixed with the end-capped polyether ether ketone to obtain a composite melt. In step S1, polyetheretherketone (PEEK) powder with an intrinsic viscosity of 0.88–1.12 dL / g is selected as the matrix resin, with hydroxyl (-OH) and fluorine end groups as the main end groups, of which the hydroxyl content accounts for approximately 65% ​​of the total end groups. The PEEK powder is placed in a rotary evaporator with a vacuum of less than 5 Pa, and 0.4% (by weight of resin) of 4-phenylethynyl phthalic anhydride (PEPA) is added. One end of the phenylethynyl phthalic anhydride molecule has an anhydride functional group, which undergoes esterification with the hydroxyl groups of PEEK; the other end has an alkynyl group (-C≡CH), which can participate in click chemistry or thermosetting crosslinking at subsequent high temperatures. Approximately 0.7 PEPA molecules react with every 100 PEEK molecular chains, thus achieving single-sided end-capping rather than double-sided end-capping. High-purity argon gas at a flow rate of 0.8 L / min is injected into the evaporator to form an inert protective atmosphere, preventing the hydroxyl groups from being oxidized to ketones at high temperatures. The temperature was slowly increased to 335 °C. The powder was in a high-viscosity flow state but not completely melted, allowing for sufficient peristalsis of the molecular chain segments. Simultaneously, the anhydride ring of phenylethynyl phthalic anhydride exhibited the highest ring-opening activity at 335 °C. A rotary evaporator was continuously tumbling at 30 rpm to ensure uniform contact between PEPA molecules and PEEK powder. After stirring for 120 minutes, the esterification reaction equation between the anhydride and hydroxyl groups was: PEEK-OH + PEPA → PEEK-OC(O)-Ph-C≡CH + Ph-COOH. The byproduct benzoic acid was simultaneously removed under vacuum. After the 120-minute reaction, approximately 70% of the PEEK molecular chains had one end capped with an alkynyl group, forming an alkynylated macro-end; the other end retained a free hydroxyl group, forming a hydroxyl micro-end. Asymmetric end capping creates a polarity difference in the molecular chain. The large end of the alkynyl group has a high electron cloud density, increasing its reactivity to 3.2 times that of the original end group. During subsequent melt blending, it preferentially undergoes click chemistry with the amine group. The small end of the hydroxyl group retains its hydrogen bond donor characteristics and can penetrate into the epoxy network to form a flexible buffer. The rotary evaporation process continuously removes trace amounts of moisture and benzoic acid to prevent thermal degradation. After treatment, the PEEK powder remains pale yellow, and the product is a pale yellow, highly free-flowing powder.

[0024] S2: After dispersing the mixed filler particles in a mixed solution containing a silane coupling agent and stirring, the stirred composite filler is melt-mixed with the end-capped polyether ether ketone to obtain a composite melt; In step S2, in one example, the mixed filler particles are selected from boron nitride particles with an average particle size of 35 nm and alumina particles with an average particle size of 150 nm, mixed in a mass ratio of 6:4 to form a filler system. The filler system is dispersed in an isopropanol solution containing 0.9% by mass of γ-glycidoxypropyltrimethoxysilane (silane coupling agent, whose molecular structure contains epoxy groups and methoxy groups, which can form covalent bonds with the surface of inorganic fillers after hydrolysis) and 0.7% by mass of polyetheramine (amine-functionalized polymer that can provide flexible segments and reactive amine groups). Surface modification was performed under conditions of pH 9.0 and 70℃ by magnetic stirring for 150 minutes. Silane molecules hydrolyzed on the surface of boron nitride particles to form an epoxy functional inner shell, while polyetheramine gradually condensed on the surface of alumina particles to form an amine functional outer shell. By adjusting the solution temperature to 55℃, an interfacial ring-opening reaction was initiated between the two shells, resulting in a gradient density structure with boron nitride as the core inner shell, polyetheramine as the transition outer shell, and alumina as the outer core. In this structure, the macromolecular ends of the polyetheramine chains extend into the epoxy inner shell, while the small molecular ends anchor to the alumina outer core, causing the filler surface to exhibit a gradual increase in density from the inside out. The inner shell density was 1.8 g / cm³. 3 Gradually transitioning to 3.9 g / cm³ in the outer core 3This improves the settling stability and interfacial compatibility of the filler in the melt. The filler assembly appears as a white to light gray powder, with a surface contact angle that gradually changes from 32° to 78° on the outer core. In actual operation, the asymmetrically end-capped polyetheretherketone powder and the filler system are added to a planetary mixer at a mass ratio of 100:22 and mixed for 55 minutes at 365°C and 75 rpm. This temperature setting is slightly higher than the melting point of polyetheretherketone (approximately 343°C), allowing the matrix resin to completely melt into a viscous flow state while avoiding excessive thermal degradation. The 75 rpm speed provides moderate shear force, promoting the depolymerization and uniform distribution of the filler particles. In this process, the alkynyl macroterminus of polyetheretherketone preferentially undergoes a click chemical reaction with the amino shell of the alumina outer core, forming a covalently interlocked outer interface. The hydroxyl microterminus penetrates into the epoxy network of the boron nitride inner shell through hydrogen bonds, forming an inner flexible anchor. The alkynyl macroterminus located on the outer layer of the filler provides high-strength crosslinking, while the microterminus located on the inner layer forms an elastic buffer. At the same time, the thermal effect generated during the blending process promotes the local ring-opening of epoxy residues and their reaction with polyetheramine, further strengthening the multi-level interfacial bonding, thereby constructing an asymmetric molecular chain anchored interfacial interlocked network. The composite melt after this melt-mixing treatment exhibits a uniform milky white appearance, and its elastic modulus is increased to 1.9 times that of pure resin. It is noteworthy that the methoxy group of γ-glycidoxypropyltrimethoxysilane hydrolyzes under alkaline conditions to generate a silanol group, which forms a Si-OB or Si-ON covalent bond with the hydroxyl group or boron-oxygen bond on the boron nitride surface. Simultaneously, the epoxy group provides reaction sites for the ring-opening of the amino group in the polyetheramine, thereby achieving a multi-level shell construction on the filler surface. The polyetheramine acts as a flexible spacer arm, enhancing the entanglement and diffusion ability between the filler and the polyether ether ketone chain segment. Regarding the specific mechanism of melt mixing, click chemistry refers to the cycloaddition or similar efficient bonding between the alkynyl group and the amino group under thermal excitation, generating a stable triazole ring or a direct covalent link. This reaction can proceed efficiently at 365℃ without a catalyst. Hydrogen bond anchoring occurs through the formation of multi-point hydrogen bonds between the small end of the hydroxyl group and the oxygen atoms in the epoxy network, with bond energies of approximately 20-40 kJ / mol, providing a reversible elastic buffer.

[0025] S32: The composite melt is hot-pressed to obtain a crystal structure with a crystallization zone on the surface of the composite melt. The crystal structure is then subjected to thermal cycling diffusion treatment to allow the small end of the end-capped polyether ether ketone to diffuse into the interior of the crystal structure to form an interface diffusion layer, thereby obtaining a heat-treated product. The composite melt is hot-pressed to form a crystal structure. The crystal structure is then subjected to thermal cycling diffusion treatment to obtain a heat-treated product including an interface diffusion layer. In step S3, the composite melt is transferred to a hot press mold. The melt contains a complete interlocking system where the large alkynyl ends are preferentially anchored in the alumina outer core amine shell, and the small hydroxyl ends penetrate into the boron nitride inner shell epoxy network. The mold is designed with an upper mold temperature of 380°C and a lower mold temperature of 350°C. A high pressure of 95 MPa is applied and held for 35 seconds. Utilizing the semi-crystalline properties of polyetheretherketone (PEEK) which are extremely sensitive to temperature and stress, the surface melt is rapidly pushed to the crystallization window with the lowest supercooling on the high-temperature side (upper mold 380°C). The molecular chains quickly align along the pressure direction to form a highly oriented, highly crystallized (up to 42%) surface crystal structure with a stable thickness of 20–30 μm. On the low-temperature side (lower mold 350°C), the core melt is kept below the crystallization temperature, preserving the quasi-amorphous interlocking network. Simultaneously, the high pressure forces the filler particles to migrate directionally under the dual drive of thermal flow and stress fields, resulting in a denser alumina outer core (3.9 g / cm³). 3 Boron nitride tends to accumulate towards the high-temperature side, with a lower density inner shell (1.8 g / cm³). 3The material is extruded towards the low-temperature side, forming a clear filler density gradient distribution from the surface to the core. This results in an inlaid crystal structure on the surface where large grains are embedded in the high-crystallinity region and small grains are fused with the interlocking network. This improves the heat distortion temperature (increased to 342℃) and Rockwell hardness (118HRR) of the composite material. The surface flatness of the product obtained after demolding after hot pressing is better than 0.2mm. The hot-pressed crystalline product is immediately placed in a circulating heat treatment furnace using a thermal circulation process. The entire process is carried out under a high-purity nitrogen protective atmosphere. The first stage involves holding at 155℃ for 65 minutes. This temperature is above the glass transition temperature of polyetheretherketone (PEEK) (143℃) but far below the cold crystallization temperature (170℃). Its main function is to promote local rearrangement of microcrystals in the highly crystalline region of the surface, eliminate residual internal stress from the hot pressing process, and make the grains more dense and uniform. The second stage involves rapidly heating to 210℃ and holding for 45 minutes. This temperature has entered the peak cold crystallization region of PEEK. At this point, the small ends of the hydroxyl groups in the interlocked network (i.e., unclosed free hydroxyl groups) gain sufficient migration ability and diffuse deeply into the epoxy residue network of the boron nitride inner shell along the formed filler density gradient channels, forming an inner interface diffusion layer. The third stage continues to heat to... The product is held at 280℃ for 30 minutes. This temperature is close to the melting point of polyetheretherketone (343℃) but still remains solid. At this time, the large end of the outer alkyne group is fully activated at high temperature and undergoes a secondary click crosslinking reaction with the residual amine group of the alumina core to form a thermosetting crosslinking network, which further improves the surface hardness and prevents excessive melting during subsequent laser treatment. The fourth stage involves cooling to 180℃ and holding for 50 minutes. The main function of this intermediate temperature plateau is to stabilize the interface area between the inner and outer diffusion layers formed in the second and third stages, avoiding microcracks caused by the difference in thermal expansion and contraction coefficients. The fifth stage involves cooling to 60℃ and holding for a long time for 150 minutes, which allows the entire system to slowly lock in. All diffusion layers, crosslinking points, and crystal structures reach the thermodynamically most stable state. The tensile strength of the heat-treated product is stable above 195MPa, and the elongation at break remains at 12.8%.

[0026] S3: The surface of the heat-treated product is scanned with a pulsed laser and silane vapor is introduced to covalently anchor the large end of the acetylation layer in the crystalline region. The small end of the interfacial diffusion layer undergoes a polycondensation reaction with the silane vapor to form a micro-protrusion structure, thereby obtaining a wear-resistant composite material. Based on the scanning treatment of the heat-treated product with a pulsed laser, the polyether ether ketone on the surface is melted and the interfacial diffusion layer is activated to form a wear-resistant composite material including a wear-resistant coating.

[0027] In step S3, the heat-treated product is placed in a laser processing chamber, and a pulsed laser with a wavelength of 1064 nm is used as the energy source. The laser has a scanning speed of 450 mm / s and a power density of 28 W / cm². 2The process parameters are uniformly scanned on the surface of the product for approximately 25 minutes. During this process, the instantaneous high energy density of the pulsed laser causes selective melting of the surface polyether ether ketone (PEEK). Only the highly crystalline surface region, approximately 20–30 μm thick, is transformed into a molten state, while the underlying interfacial diffusion layer and core structure remain solid. This selective melting is due to the fact that the melting point of the crystalline PEEK region is about 5°C higher than that of the amorphous region. Combined with the short duration (nanosecond level) of the laser pulse, the heat-affected zone is controlled within 50 μm below the surface, avoiding overall thermal degradation. As the surface PEEK melts, the laser energy simultaneously activates the epoxy residues in the interfacial diffusion layer. These epoxy residues are the epoxy functional inner shell of the boron nitride particles in step S1. Some of them remain and are embedded in the diffusion layer during the aforementioned melt blending and thermal cycling process. At this time, under the laser-induced local high temperature (approximately 380–420°C), highly reactive oxygen anions and carbocation sites are exposed, which undergo rapid cross-linking reactions with the large end of the alkynyl group and the small end of the hydroxyl group in the molten surface layer, thereby forming the skeletal basis of the wear-resistant coating. Trimethylchlorosilane vapor, accounting for 0.3% of the volume, is introduced into the processing chamber and rapidly diffuses into the molten surface under laser assistance. After scanning and processing for 15 minutes, the molten polyether ether ketone undergoes an in-situ polycondensation reaction with the silane. Specifically, the Si-Cl bond in the silane hydrolyzes to generate silanol (Si-OH), which then dehydrates and condenses with the hydroxyl groups or epoxy ring-opening products on the PEEK chain segment to form a Si-OC or Si-O-Si bonded siloxane network, generating an adaptive wear-resistant coating. The large chain segments of the wear-resistant coating refer to the longer polyetheretherketone-siloxane hybrid segments in the siloxane polymer. These large chain segments are firmly anchored to the large grain ends of the surface crystalline region through laser-activated covalent bonds (such as alkynyl click crosslinking or epoxy ring-opening esterification), forming high-strength chemical bonds that prevent peeling between the coating and the substrate. The small chain segments refer to the shorter trimethylsilane ends or oligomeric siloxane chains in the siloxane polymer. These small chain segments extend flexibly to the underlying interfacial diffusion layer, utilizing the high density of hydrogen bond donors (hydroxyl small ends) and acceptors (epoxy residues) in the diffusion layer to form a micro-protrusion structure. This micro-protrusion structure is similar to the composite protrusions on the surface of a biomimetic lotus leaf. These micro-protrusions reduce the actual contact area and reduce the coefficient of friction to below 0.08. When external shear force is applied, the small chain segments achieve a self-lubricating effect through the reversible breakage and reconstruction of hydrogen bonds, while releasing the lubricating components remaining in the polyetheramine outer shell layer in step S2, further reducing the wear rate. The resulting wear-resistant composite material has a stable tensile strength of over 195 MPa and a Rockwell hardness of 118 HRR. In another embodiment, by fine-tuning the laser parameters, the coating thickness and micro-protrusion density can be further controlled to achieve customized wear resistance.

[0028] It is worth noting that although the above embodiments do not list all possible raw material ratios and process parameter ranges, those skilled in the art can adjust the raw material ratios within the recommended range according to actual needs. For example, they can adjust the mass ratio of PEEK powder to filler system, or change the ratio of boron nitride particles to alumina particles, as well as the amount of silane coupling agent and polyetheramine added, to optimize the performance of the composite material.

[0029] In another embodiment, referring to Table 1, comparative examples were selected for performance testing. Comparative Example 1 is a PEEK composite material directly melt-blended and then injection-molded. Specifically, PEEK powder with an intrinsic viscosity of 0.95 dL / g, boron nitride particles with an average particle size of 50 nm, and alumina particles with an average particle size of 200 nm were directly added to a twin-screw extruder at a mass ratio of 100:15. The mixture was melt-blended for 30 minutes at 360°C and a screw speed of 100 rpm, and then injection-molded without any end-capping treatment, surface modification, or subsequent hot pressing / laser processing. The hardness was improved through the physical dispersion of the fillers, and the interfacial bonding relied on van der Waals forces, resulting in a tensile strength of only 105 MPa, an elongation at break of 8.5%, a Rockwell hardness of 98 HRR, a coefficient of friction of 0.35, and a wear rate of 28.5 × 10⁻⁶. -6 mm 3 / N·m, the coating has no chemical bonds bridging it, making it easy to peel off during service; Comparative Example 2 involves a method of melt blending followed by surface spraying of a polytetrafluoroethylene (PTFE) coating. The substrate is the same as in Comparative Example 1, but the surface of the injection-molded part is sprayed with a PTFE lubricating layer of approximately 50μm thickness. After spraying, it is baked and cured at 200℃ for 1h. PTFE provides low friction but only mechanically interlocks with the PEEK substrate, without a transition layer. In the test, the tensile strength was 128MPa (because the coating does not affect the body), the elongation at break was 9.2%, the Rockwell hardness was 104HRR (slightly increased), the coefficient of friction decreased to 0.28, and the wear rate was 18.2×10. - 6 mm 3 / N·m, but the coating is prone to peeling off under cyclic loads, resulting in poor durability; Comparative Example 3 is a MoS2 solid lubricant coating sprayed onto the surface after melt blending, with the matrix filler ratio increased to 100:20. The blending process is the same as Comparative Example 1. After molding, a 40μm thick MoS2 layer is sprayed and vacuum cured at 150℃ for 2h. The layered structure of MoS2 provides better lubrication, and the interface is still physically bonded. The tensile strength is 142MPa, the elongation at break is 10.1%, the Rockwell hardness is 109HRR, the coefficient of friction is 0.22, and the wear rate is 12.4×10 -6 mm 3 / N·m, an improvement over the previous two, but MoS2 is prone to oxidation and failure at high temperatures, and insufficient coating adhesion results in a lifespan of only 50% of the expected lifespan; the tensile strength of 195MPa in this application is due to the alkyne click crosslinking + epoxy ring-opening reinforcement network, which is 85.7% higher than Comparative Example 1, 52.3% higher than Comparative Example 2, and 37.3% higher than Comparative Example 3; the elongation at break of 12.8% is due to the hydrogen bond buffer at the small end of the hydroxyl group and the flexible arm of polyetheramine, which is 50.6% higher than Comparative Example 1, 39.1% higher than Comparative Example 2, and 26.7% higher than Comparative Example 3; the Rockwell hardness of 118HRR comes from the 42% high crystallinity of the surface layer, alumina enrichment and secondary crosslinking, which is 20.4% higher than Comparative Example 1, 13.5% higher than Comparative Example 2, and 8.3% higher than Comparative Example 3; the coefficient of friction of 0.08 is attributed to siloxane micro-protrusions, hydrogen bond self-lubrication and residual lubricating components of polyetheramine, which is 77.1% lower than Comparative Example 1, 71.4% lower than Comparative Example 2, and 63.6% lower than Comparative Example 3; the wear rate is 2.1×10 -6 mm 3 / N·m energy consumption is reduced by 92.6% compared to Comparative Example 1, 88.5% compared to Comparative Example 2, and 83.1% compared to Comparative Example 3 through covalent interlocking coating and reversible hydrogen bonding. The overall service life is more than 3 times that of the expected life, solving the pain point of weak bonding at the interface in the background technology.

[0030] Table 1:

[0031] In one embodiment, the mixed filler particles are particles formed by mixing boron nitride with at least one of silicon oxide, aluminum oxide, or silicon carbide, wherein the boron nitride accounts for 60-70% of the total mass of the mixed filler particles by mass ratio. The mixed solution includes a solution of γ-glycidoxypropyltrimethoxysilane, polyetheramine, and isopropanol, wherein the γ-glycidoxypropyltrimethoxysilane accounts for 0.9-1% of the total mass of the mixed filler particles by mass ratio, and the polyetheramine accounts for 0.6-0.7% of the total mass of the mixed filler particles.

[0032] In one embodiment, the step of preparing a polyetheretherketone (PEEK) with acetylenic phthalic anhydride by evaporation and end-capping to form an acetylenized large-end and small-end polyetheretherketone includes: Polyether ether ketone powder was pretreated by vacuum rotary evaporation in a rotary evaporator. Phenylacetyl phthalic anhydride was added to the pretreated ether ether ketone powder under an argon protective atmosphere to obtain a capped reaction system. Under conditions of 330~335℃, the end-capping reaction system was slowly heated and stirred to carry out unilateral esterification treatment, resulting in end-capped polyether ether ketone powder with unilaterally alkynylated large end and free hydroxyl small end.

[0033] In the above embodiments, polyetheretherketone (PEEK) powder with a purity higher than 99.9% and an intrinsic viscosity of 0.88–1.12 dL / g was selected as the matrix raw material. It was placed in a rotary evaporator with a vacuum degree lower than 5 Pa for vacuum rotary evaporation pretreatment. Trace amounts of volatiles were continuously removed by vacuum extraction to prevent thermal degradation. Simultaneously, phenylacetylene phthalic anhydride was added to the pretreated PEEK powder as an asymmetric end-capping agent. PEEK is a compound containing acetylene and phthalic anhydride structures, and its addition amount was 0.4% of the resin mass. An argon atmosphere with a flow rate of 0.8 L / min was injected to prevent oxidation. The end-capping reaction system was slowly heated and stirred at 330–335 °C for unilateral esterification treatment. This process lasted for 120 minutes, allowing the phenylacetylene group to preferentially react with the hydroxyl groups at one end of the PEEK molecular chain to form a unilaterally endcapped acetylene-enriched large end. That is, one end of the molecular chain was enriched with acetylene, increasing its reactivity to 3.2 times the original level, while the other end retained free hydroxyl groups to form a small end. Asymmetric end capping results in a difference between alkynyl-rich ends and hydroxyl-rich ends in the molecular chain, while the hydroxyl end retains hydrogen bond donor properties, forming end-capped polyether ether ketones that include both alkynylated large and small ends.

[0034] In one embodiment, the step of dispersing the mixed filler particles in an isopropanol solution and stirring, or the step of dispersing the mixed filler particles in a mixed solution containing a silane coupling agent and stirring to form a composite filler, includes: The mixed filler particles were dispersed in an isopropanol solution to obtain a filler dispersion. The filler dispersion was magnetically stirred at a pH of 8-9 and a temperature of 70-75℃ to obtain a double-shell filler comprising an epoxy inner shell and an outer shell. The double-shell packing was cooled to 50-55℃ to undergo an interfacial ring-opening reaction treatment to obtain a gradient core-shell composite packing.

[0035] In the above embodiments, the mixed filler particles are dispersed in an isopropanol solution for dispersion treatment. The mixed filler particles are particles formed by mixing boron nitride with at least one of silicon oxide, alumina, or silicon carbide. The boron nitride accounts for 60-70% of the total mass by mass ratio. For example, boron nitride particles with an average particle size of 35 nm and alumina particles with an average particle size of 150 nm are mixed in a mass ratio of 6:4 to form a filler system. This system is dispersed in an isopropanol solution containing 0.9% γ-glycidoxypropyltrimethoxysilane by mass of the filler and 0.7% polyetheramine by mass of the filler. γ-glycidyl etheroxypropyltrimethoxysilane is a silane coupling agent that can hydrolyze to form epoxy functional groups. Polyetheramine is an amino functional polymer. The filler dispersion is magnetically stirred for 150 minutes at pH 8–9 and temperature 70–75℃. This causes silane molecules to first hydrolyze on the surface of boron nitride particles to form an epoxy inner shell, while polyetheramine gradually condenses on the surface of alumina particles to form an amino functional outer shell, resulting in a double-shell filler comprising an epoxy inner shell and an outer shell. The double-shell filler is then cooled to 50–55℃ for interfacial ring-opening reaction treatment. This reaction initiates interfacial ring opening between the two shells, forming a gradient core-shell composite filler with boron nitride as the core inner shell, polyetheramine as the transition outer shell, and alumina as the outer core. In this structure, the macromolecular ends of the polyetheramine segments extend into the epoxy inner shell, while the small molecular ends anchor to the alumina outer core, causing the filler surface to exhibit a gradual increase in density from the inside out. The inner shell density is 1.8 g / cm³. 3 Gradually transitioning to 3.9 g / cm³ in the outer core 3 This improves the settling stability and interfacial compatibility of the filler in the melt, resulting in a gradient core-shell composite filler.

[0036] In one embodiment, the step of melting and mixing the stirred composite filler with the end-capped polyether ether ketone to obtain a composite melt includes: The gradient core-shell composite filler and the end-capped polyether ether ketone powder are added to a mixer at a mass ratio of 100:20~22. The mixture is then subjected to shear melt dispersion treatment at a temperature of 360~365℃, which causes the alkynylated large end to undergo a click chemical reaction with the outer shell layer, and the free hydroxyl small end is embedded in the epoxy inner shell layer to obtain the composite melt.

[0037] In the above embodiments, the gradient core-shell composite filler and end-capped polyether ether ketone powder were added to a mixer at a mass ratio of 100:20-22, for example, to a planetary mixer, and subjected to shear melt dispersion treatment at a temperature of 360-365°C. The mixture was then blended at 75 rpm for 55 minutes to induce a click chemical reaction between the alkynylated large end and the outer shell layer. This click chemical reaction involves the coupling of alkynyl and amine groups to form a covalently interlocked outer interface. The free hydroxyl small end is embedded in the epoxy inner shell layer and penetrates into the epoxy network of the boron nitride inner shell through hydrogen bonding, forming a flexible inner layer anchor. In the interlocked network, the alkynyl large end located on the outer layer of the filler provides high-strength crosslinking, while the small end located on the inner layer forms an elastic buffer. Simultaneously, the thermal effect generated during blending promotes local ring-opening of epoxy residues and reaction with the polyether amine, further strengthening the multi-level interfacial bonding to obtain a composite melt.

[0038] In one embodiment, the step of hot-pressing the composite melt to form a crystal structure, namely, hot-pressing the composite melt to obtain a crystal structure with a crystalline region on the surface of the composite melt, includes: The composite melt is placed in a hot press mold, and the upper mold temperature is set to 380~190℃ and the lower mold temperature to 340~350℃. The pressure of the hot press mold is set to 90~95MPa, and the composite melt is hot-pressed to obtain the primary crystal melt. The nascent crystal melt is depressurized and shaped to form highly oriented crystalline regions on the surface of the polyether ether ketone molecular chains, thus obtaining a crystal structure.

[0039] In the above embodiment, the composite melt is placed in a hot press mold, with the upper mold temperature set to 380–190°C and the lower mold temperature to 340–350°C, for example, 380°C for the upper mold and 350°C for the lower mold, allowing heat to flow from top to bottom. The pressure of the hot press mold is set to 90–95 MPa, for example, 95 MPa, and the composite melt is hot-pressed for 35 seconds. This allows the melt to fill the mold under temperature gradient and high pressure, while the polyether ether ketone (PEEK) molecular chains selectively crystallize along the pressure direction, forming a highly oriented crystalline region on the surface with a thickness of 20–30 μm. The core retains a quasi-amorphous structure with an interlocking network. Simultaneously, stress causes the filler particles to be oriented along the heat flow field, with the high-density end of the alumina outer core facing the high-temperature side and the low-density end pointing towards the low-temperature side, forming a crystallinity gradient from the surface to the core. In the gradient layer, the large grain ends of the crystalline region are embedded in the surface layer, and the small grain ends are fused with the interlocking network, which improves the thermal stability and mechanical strength of the composite material. It also depressurizes and shapes the nascent crystal melt, allowing the polyether ether ketone molecular chains to form highly oriented crystalline regions on the surface layer, thus obtaining a crystal structure.

[0040] In one embodiment, the step of performing thermal cycling diffusion treatment on the crystal structure to obtain a heat-treated article including an interface diffusion layer includes: Under a nitrogen protective atmosphere, the crystal structure was kept at 150~155℃ for 60~65 minutes to obtain a micro-rearranged crystal structure. The micro-rearranged crystal structure is heated to 200-210°C and held for 40-45 minutes to allow the small ends of free hydroxyl groups to diffuse into the epoxy inner shell, thus obtaining an intermediate product containing an inner interface diffusion layer. The intermediate product is heated to 270-280°C and held for 25-30 minutes to induce thermally induced click crosslinking of the acetylation macro-end in the outer shell layer, thereby obtaining the transition product. After cooling the transition product to 170-180°C and holding it at that temperature for 45-50 minutes, the temperature is further reduced to 50-60°C and held at that temperature for 70-80 minutes to obtain the heat-treated product.

[0041] In this embodiment, under a nitrogen protective atmosphere, the crystal structure is held at 150–155°C for 60–65 minutes, for example, at 155°C for 65 minutes, to obtain a micro-rearranged crystal structure, causing microcrystal rearrangement in the surface crystalline region. The micro-rearranged crystal structure is then heated to 200–210°C and held for 40–45 minutes, for example, at 210°C for 45 minutes, to allow the small ends of free hydroxyl groups to diffuse into the epoxy inner shell layer, resulting in an intermediate product containing an inner interface diffusion layer with a thickness of 65 nm. The intermediate product is then heated to 270–280°C and held for 25–30 minutes, for example, at 280°C for 30 minutes, to induce thermal induction of the large ends of alkynylation in the outer shell layer. Click crosslinking to obtain a transition product. This crosslinking forms a thermosetting network. The transition product is then cooled to 170–180°C and held for 45–50 minutes, for example, 180°C for 50 minutes to stabilize the intermediate transition zone. After that, it is cooled to 50–60°C and held for 70–80 minutes, for example, 60°C for 150 minutes to lock the overall structure and obtain a heat-treated product. The entire process is carried out under nitrogen protection to avoid thermo-oxidative degradation. The tensile strength of the product treated in this step is increased to 195 MPa, and the hydrogen bond density in the interfacial diffusion layer reaches 4.2 per square nanometer. The multi-stage thermal cycling process achieves regulation and crosslinking strengthening of the interfacial diffusion layer through temperature control.

[0042] In one embodiment, the step of scanning the heat-treated product with a pulsed laser to melt the surface polyetheretherketone and activate the interfacial diffusion layer to form a wear-resistant composite material including a wear-resistant coating, and then scanning the surface of the heat-treated product with a pulsed laser and introducing silane vapor to covalently anchor the large end of the acetylation in the crystalline region, and having the small end of the interfacial diffusion layer undergo a polycondensation reaction with the silane vapor to form a micro-protrusion structure, thereby obtaining the wear-resistant composite material, includes: The heat-treated product is subjected to a first-stage scanning process using pulsed laser light, with a scanning speed and power density of 28~30W / cm². 2 This yields a surface-melted activated product. Trimethylchlorosilane vapor, accounting for 0.3% of the volume of the laser processing chamber, is introduced into the chamber, and laser scanning is continued for 10-15 minutes to obtain an intermediate composite material containing a siloxane prepolymer layer. The intermediate composite material was subjected to a second-stage scanning process, with the scanning speed and power density reduced to 20-22 W / cm². 2 The siloxane prepolymer layer is cured to form a wear-resistant coating, resulting in a wear-resistant composite material including the wear-resistant coating.

[0043] In the above embodiments, the heat-treated product is subjected to a first-stage scanning process based on pulsed laser, with a scanning speed and power density of 28–30 W / cm². 2 For example, power density 28W / cm² 2 The scanning speed is 450 mm / s, and the surface is treated with pulsed laser for 25 minutes to obtain a surface-melted activated product. This causes selective melting of the polyether ether ketone (PEEK) layer on the surface of the product and activates the epoxy residues in the interfacial diffusion layer. Trimethylchlorosilane vapor, accounting for 0.3% of the chamber volume, is then introduced into the laser processing chamber, and laser scanning continues for 10–15 minutes, for example, 15 minutes, to obtain an intermediate composite material containing a siloxane prepolymer layer. This allows the molten surface layer to undergo in-situ polycondensation with the silane. The intermediate composite material undergoes a second-stage scanning treatment, with the scanning speed and power density reduced to 20–22 W / cm². 2 The process involves curing a siloxane prepolymer layer to form a wear-resistant coating. In this coating, the large chain segments form covalent bonds with the surface crystalline region, while the smaller chain segments extend to the interfacial diffusion layer, forming micro-protrusion structures. The laser-induced microstructures have high-density ends on the surface and low-density ends penetrating deep into the interior. This adaptive coating dynamically adjusts its morphology and releases lubricating components during friction. The surface roughness Ra of the composite material treated in this step is controlled at 0.6 μm, and the wear rate is reduced by 7.5 times compared to the baseline. Through laser-assisted surface microstructuring and in-situ generation, the wear-resistant composite material is functionalized, resulting in a wear-resistant composite material including the wear-resistant coating.

[0044] This application also discloses a wear-resistant PEEK composite material, which is prepared by any of the above-described methods for preparing wear-resistant PEEK composite materials, and includes the corresponding technical features in the above-described preparation methods, which will not be repeated here.

[0045] The above description is merely a preferred embodiment of the present invention and does not limit the patent scope of the present invention. Any equivalent structural or procedural transformations made based on the content of the present invention's specification and drawings, or direct or indirect applications in other related technical fields, are similarly included within the patent protection scope of the present invention.

Claims

1. A method for producing a wear-resistant PEEK composite material, characterized by, The method comprises: evaporation end-capping treatment is performed on polyether ether ketone powder by adding phenylacetylenyl phthalic anhydride to form end-capped polyether ether ketone comprising acetylenyl large end and small end; after the mixed filler particles are dispersed in the mixed solution comprising the silane coupling agent and stirred, a composite filler is formed, the composite filler after stirring is subjected to melt mixing treatment with the end-capped polyether ether ketone, and a composite melt is obtained; the composite melt is subjected to hot pressing to obtain a crystal structure of a crystallization region formed on a surface layer of the composite melt, the crystal structure is subjected to thermal cycle diffusion treatment, the small end of the end-capped polyether ether ketone diffuses into the crystal structure to form an interfacial diffusion layer, and a heat-treated product is obtained; the heat-treated product comprising the interfacial diffusion layer is obtained; the surface of the heat-treated product is subjected to scanning treatment based on a pulsed laser and silane vapor is introduced, the acetylenyl large end is covalently anchored in the crystallization region, the small end of the interfacial diffusion layer is subjected to polycondensation reaction with the silane vapor to form a micro-protrusion structure, and a wear-resistant composite material is obtained. the surface layer of the polyether ether ketone is melted and the interfacial diffusion layer is activated to form a wear-resistant composite material comprising a wear-resistant coating; wherein a large segment end of the wear-resistant coating forms a covalent bond with the crystallization region of the surface layer, and a small segment end extends to the interfacial diffusion layer to form a micro-protrusion structure.

2. The method for preparing the wear-resistant PEEK composite material according to claim 1, characterized in that, The mixed filler particles are particles formed by mixing boron nitride with at least one of silicon oxide, aluminum oxide or silicon carbide, and the boron nitride accounts for 60-70% of the total mass of the mixed filler particles.

3. The method for preparing the wear-resistant PEEK composite material according to claim 1, characterized in that, The mixed solution comprises a solution of γ-glycidoxypropyltrimethoxysilane, polyether amine and isopropanol, and the γ-glycidoxypropyltrimethoxysilane accounts for 0.9-1% of the total mass of the mixed filler particles and the polyether amine accounts for 0.6-0.7% of the total mass of the mixed filler particles.

4. The method for preparing the wear-resistant PEEK composite material according to claim 1, characterized in that, The step of performing evaporation end-capping treatment on polyether ether ketone powder by adding phenylacetylenyl phthalic anhydride to form end-capped polyether ether ketone comprising acetylenyl large end and small end comprises: vacuum rotary evaporation pretreatment is performed on polyether ether ketone powder in a rotary evaporator, phenylacetylenyl phthalic anhydride is added to the pretreated ether ether ketone powder under argon protection atmosphere, and an end-capping reaction system is obtained; under the condition of 330-335℃, the end-capping reaction system is slowly heated and stirred to perform one-sided esterification treatment, and end-capped polyether ether ketone powder with one-sided acetylenyl large end and free hydroxyl small end is obtained.

5. The method for preparing the wear-resistant PEEK composite material according to claim 1, characterized in that, The step of dispersing the mixed filler particles in isopropanol solution and stirring and the step of dispersing the mixed filler particles in the mixed solution comprising the silane coupling agent to form a composite filler after stirring comprise: the mixed filler particles are dispersed in isopropanol solution to obtain a filler dispersion liquid; the filler dispersion liquid is subjected to magnetic stirring under the condition of pH value 8-9 and temperature 70-75℃ to obtain double-shell filler comprising an inner shell layer and an outer shell layer; the double-shell filler is cooled to 50-55℃ to perform interfacial ring-opening reaction treatment, and a gradient core-shell structure composite filler is obtained.

6. The method for preparing the wear-resistant PEEK composite material according to claim 5, characterized in that, The step of melt mixing the stirred composite filler with the capped polyether ether ketone to obtain a composite melt, comprises: The gradient core-shell structure composite filler and the capped polyether ether ketone powder are added into a mixer at a mass ratio of 100:20-22, and shear melt dispersion treatment is carried out at a temperature of 360-365℃, so that the acetylenic large end reacts with the outer shell layer through click chemistry, and the free hydroxyl small end is embedded into the epoxy inner shell layer to obtain a composite melt.

7. The method for preparing the wear-resistant PEEK composite material according to claim 1, characterized in that, The step of heat pressing the composite melt to form a crystal structure, comprises: The composite melt is placed in a heat press mold, and the upper mold temperature is set to 380-190℃ and the lower mold temperature is set to 340-350℃; The pressure of the heat press mold is set to 90-95MPa, and the composite melt is heat pressed to obtain a nascent crystal melt; The nascent crystal melt is pressure-released to be shaped, so that the polyether ether ketone molecular chain forms a high-orientation crystal region on the surface layer to obtain a crystal structure.

8. The method for preparing the wear-resistant PEEK composite material according to claim 1, characterized in that, The step of heat cycle diffusion treatment of the crystal structure to obtain a heat-treated product comprising an interface diffusion layer, comprises: The crystal structure is kept at 150-155℃ for 60-65 minutes under a nitrogen protective atmosphere to obtain a slightly rearranged crystal structure; The slightly rearranged crystal structure is heated to 200-210℃ for 40-45 minutes, so that the free hydroxyl small end diffuses to the epoxy inner shell layer to obtain an intermediate product containing an inner interface diffusion layer; The intermediate product is heated to 270-280℃ for 25-30 minutes, so that the acetylenic large end is heat-induced to crosslink on the outer shell layer to obtain a transition product; The transition product is cooled to 170-180℃ for 45-50 minutes, and then cooled to 50-60℃ for 70-80 minutes to obtain a heat-treated product.

9. The method for preparing the wear-resistant PEEK composite material according to claim 1, characterized in that, The step of scanning the heat-treated product based on a pulsed laser to melt the polyether ether ketone on the surface layer and activate the interface diffusion layer to form a wear-resistant composite material comprising a wear-resistant coating, comprises: The heat treated product is subjected to a first stage scanning treatment based on pulsed laser, the scanning speed power density being 28-30 W / cm 2 , to obtain a surface fusion activated product; Trimethylchlorosilane vapor accounting for 0.3% of the volume of the cabin is introduced into the laser processing cabin, and laser scanning is continued for 10-15 minutes to obtain an intermediate composite material containing a siloxane prepolymer layer; The intermediate composite material is subjected to a second stage scanning treatment, and the scanning speed power density is reduced to 20-22 W / cm 2 The siloxane prepolymer layer is cured to form a wear-resistant coating layer, and a wear-resistant composite material comprising the wear-resistant coating layer is obtained.

10. A wear resistant PEEK composite material, characterized in that, The wear-resistant PEEK composite material is prepared by the method of any one of claims 1-9. The wear-resistant PEEK composite material is prepared by the method of any one of claims 1-9.

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