A temperature-resistant and wear-resistant dual-phase high-entropy ceramic particle coating and its preparation method

Abstract

This invention relates to the field of surface engineering technology, and discloses a temperature-sensitive and wear-resistant dual-phase high-entropy ceramic particle coating and its preparation method. The coating consists of transition metal main components, osteogenic active elements, broad-spectrum antibacterial elements, carbon elements, and nitrogen elements, forming a dual-phase high-entropy solid solution containing a carbide main phase and a nitride secondary phase. During preparation, the powders are mixed and ball-milled, then deposited under vacuum plasma spraying. The chamber pressure is adjusted to suppress the volatilization of biochemical elements, allowing them to dissolve in the crystal lattice. This coating utilizes the stress field of the dual-phase structure to anchor the biochemical functional elements, suppressing temperature-sensitive stress cracking and element loss, achieving structural stability and long-term synergistic effects of osteogenic and antibacterial properties.

Description

Technical Field

[0001] This invention relates to the field of surface engineering technology, and discloses a temperature-sensitive and wear-resistant dual-phase high-entropy ceramic particle coating and its preparation method. Background Technology

[0002] Existing medical metal implants often employ ceramic coatings for surface modification. Conventional techniques typically utilize single-phase or simple two-phase transition metal carbide or nitride coatings, such as depositing titanium carbide or titanium nitride coatings on titanium alloy substrates using thermal spraying. These conventional coatings primarily rely on the combination of transition metal elements with carbon and nitrogen to provide hardness and wear resistance. Their chemical composition systems are relatively simple, mainly focusing on mechanical protection. The preparation process is usually carried out under atmospheric or low-pressure conditions, without specific control over the solid solution behavior of certain easily oxidized or volatile elements.

[0003] The aforementioned conventional solutions suffer from a single core problem: structural instability of the coating under temperature-dependent conditions and difficulty in long-term preservation of biochemical functional elements. Conventional single-phase or simple two-phase ceramic coatings cannot effectively relax thermal stress under alternating hot and cold conditions, leading to the initiation of microcracks and subsequent peeling. Simultaneously, due to the lack of constraint of biochemical functional elements by a multi-principal high-entropy lattice, lattice distortion and microcrack propagation caused by temperature changes accelerate the uncontrollable loss of biochemical elements, making it impossible for the coating to maintain a long-term stable release of bone-promoting and antibacterial functions while withstanding temperature-dependent wear. Summary of the Invention

[0004] To address the shortcomings of existing technologies, such as structural instability of coatings under temperature-dependent conditions and difficulty in long-term preservation of biochemical functional elements, this invention provides a temperature-dependent and wear-resistant dual-phase high-entropy ceramic particle coating and its preparation method.

[0005] To address the aforementioned technical problems, this invention provides a temperature- and wear-resistant dual-phase high-entropy ceramic particle coating, comprising the following technical features: the coating is composed of the following molar percentage components: 30%–45% transition metals, 15%–25% osteogenic elements, 10%–20% broad-spectrum antibacterial elements, 15%–25% carbon, and 5%–15% nitrogen; the transition metals include titanium, zirconium, hafnium, and vanadium; the osteogenic elements include strontium and zinc; the broad-spectrum antibacterial elements include silver and copper; the transition metals, the osteogenic elements, and the broad-spectrum antibacterial elements form a dual-phase high-entropy solid solution in the interstitial sites formed by the carbon and nitrogen elements, the dual-phase high-entropy solid solution comprising a face-centered cubic carbide primary phase and a face-centered cubic nitride secondary phase.

[0006] When the coating operates in the body fluid microenvironment, the biphase high-entropy framework composed of the carbide main phase and the nitride secondary phase maintains the phase stability of the structure through the high-entropy effect and the hysteresis diffusion effect, resisting phase transformation cracking caused by temperature stress. Osteogenic active elements and broad-spectrum antibacterial elements dissolved in interstitial sites and inside the crystal lattice are slowly dissolved through body fluid-mediated ion exchange. Strontium ions and zinc ions participate in the signal transduction and metabolic pathways of osteoblasts, while silver ions and copper ions penetrate the bacterial cell membrane to interfere with enzyme activity. The distorted stress field of the high-entropy crystal lattice creates a barrier to hinder the dissolution process of ions, achieving long-term retention and slow release of biochemical functional elements.

[0007] Furthermore, in the above technical solution, the molar percentage of the transition metal main element is 35%~42%, the molar ratio of the osteogenic active element to the broad-spectrum antibacterial element is (1.2~1.5):1; the molar ratio of the strontium element to the zinc element is 1:1, and the molar ratio of the silver element to the copper element is 1:(1.5~2).

[0008] In practice, this ratio ensures that the mixing entropy of the high-entropy solid solution is maximized to stabilize the crystal structure, and promotes the specific molar ratio of osteoactive elements and broad-spectrum antibacterial elements to match the temporal requirements of bone repair and antibacterial action. The molar ratio of silver to copper is set based on the synergistic mechanism of copper ions interfering with bacterial metabolism at multiple targets and silver ions damaging bacterial cell membranes.

[0009] Furthermore, in the above technical solution, the lattice constant difference between the carbide main phase and the nitride secondary phase is 0.5%~2.0%, and a semi-coherent interface is formed between the carbide main phase and the nitride secondary phase; the osteogenic active element and the broad-spectrum antibacterial element are segregated at the semi-coherent interface.

[0010] In practice, the lattice distortion stress field generated at the semi-coherent interface forms a potential energy valley, which provides a driving force for the segregation of bone-active elements and broad-spectrum antibacterial elements. During body fluid erosion, this stress field hinders the desolvation and loss of segregated elements, thus controlling the ion release rate.

[0011] Furthermore, in the above technical solution, the surface of the coating has a micro-nano hierarchical porous structure, which includes micron-level pits and nano-level pores; the osteogenic active element is enriched in the inner wall of the nano-level pores, and the broad-spectrum antibacterial element is dispersed in the bottom wall of the micron-level pits.

[0012] In practice, micron-sized pits guide bone tissue ingrowth to achieve macroscopic mechanical locking, while nano-sized pores increase the specific surface area for protein adsorption, promoting the combination of osteogenic elements with adsorbed proteins on the inner wall of nano-sized pores to form a local osteogenic microenvironment. Broad-spectrum antibacterial elements contact and kill invading bacteria on the bottom wall of micron-sized pits, achieving spatial targeting of biochemical functions.

[0013] Furthermore, in the above technical solution, the molar ratio of carbon to nitrogen is in the range of (1.5~2.5):1; the carbon element occupies the octahedral interstitial sites of the two-phase high-entropy solid solution to form the carbide main phase, the nitrogen element occupies the octahedral interstitial sites to form the nitride secondary phase, and the nitride secondary phase encapsulates the carbide main phase.

[0014] In practice, the nitride secondary phase preferentially undergoes weak hydrolysis in the body fluid environment to form a hydrated oxide layer. The encapsulation structure protects the carbide main phase from direct corrosion, and the hydrolysis layer acts as an ion exchange channel to control the dissolution path of internal active elements.

[0015] Furthermore, in the above technical solution, the coating further includes an interface transition layer located between the coating and the medical titanium alloy substrate, the interface transition layer being composed of the titanium element, the carbon element, and the aluminum element in the substrate; the molar ratio of the titanium element to the aluminum element in the interface transition layer decreases in the direction away from the substrate.

[0016] In practice, the gradient change in the molar ratio of titanium to aluminum causes the thermal expansion coefficient of the interface transition layer to exhibit a gradient transition. During the temperature change process, the interfacial thermal stress is absorbed layer by layer, eliminating stress concentration at the interface between the ceramic coating and the metal substrate.

[0017] To address the aforementioned technical problems, this invention provides a method for preparing a temperature- and wear-resistant dual-phase high-entropy ceramic particle coating, comprising the following technical features: mixing transition metal main component powder, osteogenic active element powder, broad-spectrum antibacterial element powder, carbon powder, and silicon nitride powder in a specific ratio, and performing wet ball milling in a high-energy ball mill to obtain a composite powder; roughening a medical titanium alloy substrate by sandblasting, and then placing it in the vacuum chamber of a vacuum plasma spraying device; under a protective atmosphere of mixed argon and hydrogen, feeding the composite powder into a plasma jet for melting, and spraying it onto the surface of the medical titanium alloy substrate for deposition; during the deposition process, adjusting the pressure of the vacuum chamber to suppress the volatilization of the osteogenic active element and the broad-spectrum antibacterial element, so that the osteogenic active element and the broad-spectrum antibacterial element are dissolved into the dual-phase high-entropy lattice formed by the transition metal main component and carbon and nitrogen, and obtaining the coating after cooling.

[0018] The vacuum plasma environment avoids the oxidation and deactivation of bone-active elements and broad-spectrum antibacterial elements at high temperatures. The chamber pressure is adjusted to control the saturated vapor pressure of low-melting-point biochemical functional elements to inhibit their volatilization. The high-energy plasma jet causes the multi-principal element powder to melt instantly and cool rapidly on the substrate surface. The thermodynamic hysteresis effect of the high-entropy system inhibits element segregation and forces the bone-active elements and broad-spectrum antibacterial elements to dissolve in the biphase high-entropy lattice.

[0019] Furthermore, in the above technical solution, in the wet ball milling step, the ball milling medium is anhydrous ethanol, the ball-to-material ratio is 8:1 to 12:1, and the ball milling speed is 300 rpm to 400 rpm; the osteogenic active element powder and the broad-spectrum antibacterial element powder are mechanically alloyed before ball milling, so that the strontium element and the zinc element, and the silver element and the copper element respectively form pre-alloyed powders.

[0020] In practice, mechanical alloying enables active elements to form metal bonds in advance, reducing the vapor pressure in the subsequent plasma spraying process. Anhydrous ethanol prevents powder oxidation, and a specific ball-to-powder ratio and rotation speed ensure that the pre-alloyed powder grains are refined to the nanoscale, improving the efficiency of subsequent solid solution treatment.

[0021] Furthermore, in the above technical solution, after the step of obtaining the coating after cooling, a surface reconstruction step is also included: immersing the coating in an acidic etching solution containing fluoride ions for selective etching to dissolve the silver and copper elements on the surface of the biphase high-entropy lattice, forming micron-sized pits; subsequently performing electrochemical deposition in an alkaline electrolyte containing strontium ions to precipitate oxides of the strontium element on the inner wall of the micron-sized pits and form nano-sized pores.

[0022] In practice, the acidic fluorine-containing etching solution selectively complexes and dissolves silver and copper elements. Electrochemical deposition utilizes an electric field to drive strontium ions to be reduced and deposited in micron-sized pits, accompanied by hydrogen evolution reaction to create pores, thereby achieving spatial reconstruction and targeted localization of active elements on the coating surface.

[0023] Furthermore, in the above technical solution, before the deposition molding step of spraying onto the surface of the medical titanium alloy substrate, pure titanium powder is first pre-sprayed as the bottom layer powder to form a bottom layer on the surface of the substrate; in the deposition molding step, the power of the plasma jet is adjusted to make the bottom layer powder and the composite powder melt simultaneously, and the titanium in the bottom layer reacts with the aluminum in the substrate and the carbon in the composite powder to generate the interface transition layer in situ.

[0024] In practice, pre-sprayed pure titanium powder and composite powder are melted simultaneously to form a mutually soluble zone. In the molten pool, titanium atoms, aluminum atoms and carbon atoms generate a ternary phase of titanium aluminum carbide through diffusion reaction. The in-situ grown interface transition layer forms a metallurgical bond with the substrate and coating, eliminating the physical interface between layers.

[0025] Compared with the prior art, the beneficial effects of the present invention are as follows: 1. By introducing osteogenic and broad-spectrum antibacterial elements into the coating composition to replace some of the transition metal main components, and combining them with a specific proportion of carbon and nitrogen elements, a two-phase high-entropy solid solution consisting of a carbide main phase and a nitride secondary phase is formed. The osteogenic and broad-spectrum antibacterial elements are dissolved within the two-phase high-entropy lattice. The stress field generated by the semi-coherent interface formed by the lattice constant difference of the two-phase structure anchors the biochemical functional elements in the lattice, inhibiting the loss of elements under temperature-induced alternating stress. This allows the coating to achieve long-term synergistic and sustained release of osteogenic and antibacterial ions while maintaining the integrity of its temperature-resistant and wear-resistant structure.

[0026] 2. By constructing a micro-nano hierarchical porous structure on the coating surface, osteogenic elements are enriched in the inner walls of nano-sized pores, and broad-spectrum antibacterial elements are dispersed in the bottom walls of micron-sized pits, thus achieving spatial targeted distribution of biochemical functional elements on the coating surface. An interfacial transition layer composed of titanium, carbon, and aluminum is set between the substrate and the coating, and the molar ratio of titanium to aluminum decreases along the direction away from the substrate, eliminating the abrupt change in composition at the coating-substrate interface and releasing residual thermal stress at the interface. Detailed Implementation

[0027] The present invention will be further described in detail below with reference to embodiments. Those skilled in the art can reproduce the technical solution of the present invention and achieve its claimed technical effects based on the content disclosed in this specification. It should be noted that the following embodiments are only used to explain the present invention and are not intended to limit the scope of protection of the present invention. Any non-substantial improvements and adjustments made based on the core concept of the present invention should fall within the scope of protection of the present invention.

[0028] Example 1: This example provides a temperature- and wear-resistant dual-phase high-entropy ceramic particle coating. Its formula, by molar percentage, is as follows: 38.5% transition metals (10% titanium, 10% zirconium, 10% hafnium, 8.5% vanadium), 20% osteogenic elements (10% strontium, 10% zinc), 16% broad-spectrum antibacterial elements (5.33% silver, 10.67% copper, with a silver-copper molar ratio of 1:2), 19.5% carbon, and 6% nitrogen (the carbon-nitrogen molar ratio is 3.25:1, which needs to be adjusted to the appropriate range; for example, 19% carbon and 9.5% nitrogen, with a carbon-nitrogen molar ratio of 2:1, and the transition metals are supplemented to 38%, specifically 9.5% titanium, 9.5% zirconium, 9.5% hafnium, and 9.5% vanadium). The preparation method is as follows: Strontium powder is mechanically alloyed with zinc powder, and silver powder is mechanically alloyed with copper powder to form pre-alloyed powders; transition metal main component powders, the above pre-alloyed powders, carbon powder, and silicon nitride powder are mixed in a certain proportion and placed in a high-energy ball mill. Anhydrous ethanol is used as the ball milling medium, the ball-to-material ratio is 10:1, and the ball milling speed is 350 rpm to perform wet ball milling to obtain composite powder; medical titanium alloy substrate is roughened by sandblasting and then placed in the vacuum chamber of a vacuum plasma spraying equipment; pure titanium powder is first used as the bottom layer powder for pre-spraying to form a bottom layer on the surface of the substrate; under the protective atmosphere of mixed argon and hydrogen, the composite powder is fed into the plasma jet, and the power of the plasma jet is adjusted to make the bottom layer powder and composite powder adhere to each other. The powder is simultaneously melted and sprayed to form a deposition structure. The titanium in the bottom layer reacts with the aluminum in the substrate and the carbon in the composite powder to form an in-situ interface transition layer. In this interface transition layer, the molar ratio of titanium to aluminum decreases away from the substrate. During the deposition process, the vacuum chamber pressure is adjusted to 80 Pa to inhibit the volatilization of osteogenic and broad-spectrum antibacterial elements, allowing them to dissolve into the biphase high-entropy lattice. After cooling, a primary coating is obtained. The primary coating is then immersed in an acidic etching solution containing fluoride ions for selective etching, dissolving the silver and copper elements on the surface of the biphase high-entropy lattice to form micron-sized pits. Subsequently, electrochemical deposition is performed in an alkaline electrolyte containing strontium ions, precipitating strontium oxides on the inner walls of the micron-sized pits and forming nanoscale pores, resulting in the final coating.

[0029] Example 2: The only difference between this example and Example 1 is the formulation ratio: 30% transition metals (7.5% titanium, 7.5% zirconium, 7.5% hafnium, 7.5% vanadium), 25% osteogenic elements (12.5% ​​strontium, 12.5% ​​zinc), 20% broad-spectrum antibacterial elements (6.67% silver, 13.33% copper), 15% carbon, and 10% nitrogen. All other conditions are the same as in Example 1.

[0030] Example 3: The only difference between this example and Example 1 is the formulation ratio: 45% transition metals (11.25% titanium, 11.25% zirconium, 11.25% hafnium, 11.25% vanadium), 15% osteogenic elements (7.5% strontium, 7.5% zinc), 10% broad-spectrum antibacterial elements (3.33% silver, 6.67% copper), 20% carbon, and 10% nitrogen. All other conditions are the same as in Example 1.

[0031] Example 4: The only difference between this example and Example 1 is that the molar ratio of the osteopromoting active element to the broad-spectrum antibacterial element is 1.2:1. Specifically, the osteopromoting active element is 19.2% (9.6% strontium and 9.6% zinc), and the broad-spectrum antibacterial element is 16% (5.33% silver and 10.67% copper). All other conditions are the same as in Example 1.

[0032] Example 5: The only difference between this example and Example 1 is that the molar ratio of the osteopromoting active element to the broad-spectrum antibacterial element is 1.5:1. Specifically, the osteopromoting active element is 22.5% (strontium 11.25%, zinc 11.25%), and the broad-spectrum antibacterial element is 15% (silver 5%, copper 10%). All other conditions are the same as in Example 1.

[0033] Example 6: The only difference between this example and Example 1 is that the molar ratio of silver to copper is 1:1.5. Specifically, it contains 16% broad-spectrum antibacterial element (6.4% silver and 9.6% copper). All other conditions are the same as in Example 1.

[0034] Example 7: The only difference between this example and Example 1 is that the molar ratio of carbon to nitrogen is 1.5:1. Specifically, carbon accounts for 16.5% and nitrogen accounts for 11%. All other conditions are the same as in Example 1.

[0035] Example 8: The only difference between this example and Example 1 is that the molar ratio of carbon to nitrogen is 2.5:1. Specifically, carbon accounts for 21.4% and nitrogen accounts for 8.6%. All other conditions are the same as in Example 1.

[0036] Example 9: The only difference between this example and Example 1 is that the transition metal main element contains 15% titanium, 15% zirconium, 5% hafnium, and 3% vanadium. All other conditions are the same as in Example 1.

[0037] Example 10: This example has the same formulation and preparation method as Example 1, except for the preparation method parameters: in the wet ball milling step, the ball-to-material ratio is 8:1, and the ball milling speed is 300 rpm. All other conditions are the same as in Example 1.

[0038] Example 11: This example has the same formulation and preparation method as Example 1, except for the preparation method parameters: in the wet ball milling step, the ball-to-material ratio is 12:1, and the ball milling speed is 400 rpm. All other conditions are the same as in Example 1.

[0039] Example 12: This example uses the same formulation and preparation method as Example 1, except for the preparation method parameters: during the vacuum plasma spraying deposition process, the vacuum chamber pressure is adjusted to 50 Pa. All other conditions are the same as in Example 1.

[0040] Comparative Example 1: The only difference between this comparative example and Example 1 is that the osteogenic element is missing from the formulation, and its proportion is made up by transition metals. Specifically, the formulation consists of 58% transition metals (14.5% titanium, 14.5% zirconium, 14.5% hafnium, and 14.5% vanadium), 16% broad-spectrum antibacterial element, 19% carbon, and 7% nitrogen. All other conditions are the same as in Example 1.

[0041] Comparative Example 2: This comparative example uses a conventional single-phase titanium carbide coating. Titanium carbide powder was deposited on the surface of a medical titanium alloy substrate using an atmospheric plasma spraying process, without any biochemical element doping, pre-coating of the underlayer, or surface reconstruction steps.

[0042] Comparative Example 3: The only difference between this comparative example and Example 1 is that the molar ratio of carbon to nitrogen deviates from the specified range and is set to 1:1. Specifically, carbon accounts for 13% and nitrogen accounts for 13%. All other conditions are the same as in Example 1.

[0043] Comparative Example 4: The only difference between this comparative example and Example 1 is that the surface reconstruction step is omitted; that is, after cooling to obtain the initial coating, etching with a fluoride-containing acidic etching solution and electrochemical deposition with a strontium-containing alkaline electrolyte are not performed. All other conditions are the same as in Example 1.

[0044] Test method: The coatings obtained in the above embodiments and comparative examples were subjected to performance tests.

[0045] Bond strength test after temperature change cycle: After the sample is cycled 50 times between 37℃ and 200℃, the bond strength between the coating and the substrate is tested by tensile method. 30-day cumulative dissolution rate test of biochemical elements: The sample was immersed in simulated body fluid for 30 days, and the cumulative dissolution ratio of strontium and silver ions was determined. Osteoblast proliferation rate test: Cells were seeded on the coating surface and cultured for 7 days, and the absorbance value was measured; Antibacterial rate test: Staphylococcus aureus was inoculated and cultured for 24 hours, and the bactericidal rate was calculated.

[0046] The test results are shown in Table 1.

[0047] Table 1 Performance test results of each embodiment and comparative example ; Results analysis: After temperature cycling in Examples 1 to 12, the binding strength remained above 52 MPa, the cumulative dissolution rate of strontium and silver ions after 30 days was less than 15%, and the osteoblast proliferation rate and antibacterial rate remained at high levels, verifying the feasibility of the formulation range and preparation method parameter range of the present invention. All data in Example 1 were at the optimal balance point.

[0048] Comparative Example 1, lacking osteogenic elements, resulted in a decrease in osteoblast proliferation rate to 0.65%, and the absence of synergistic occupancy of osteogenic elements in the crystal lattice led to a surge in silver ion dissolution rate to 22%, disrupting the long-term retention mechanism of biochemical elements. Comparative Example 2, using a conventional single-phase titanium carbide coating, lacked high-entropy lattice constraints and an interface transition layer, resulting in a binding strength of only 28 MPa after temperature changes and complete loss of biochemical function. Comparative Example 3, with a carbon-nitrogen molar ratio deviating to 1:1, failed to form a stable biphase semi-coherent interface structure, leading to an imbalance in coating internal stress and a decrease in binding strength to 32 MPa. The failure of lattice anchoring caused a surge in the dissolution rate of biochemical elements. Comparative Example 4, omitting the surface reconstruction step, lacked a micro-nano hierarchical porous structure on the coating surface, preventing the spatially targeted distribution of biochemical elements. Initial dissolution was hindered, resulting in a low overall dissolution rate, and a significant decrease in both osteoblast proliferation rate and antibacterial rate. This comparison confirms that the combination of a biphase high-entropy solid solution formulation and a specific preparation process is a core prerequisite for maintaining temperature-sensitive structural stability and long-term retention of biochemical elements.

Claims

1. A temperature-sensitive and wear-resistant dual-phase high-entropy ceramic particle coating, characterized in that, The coating consists of the following components in molar percentage: Transition metals 30%~45%, osteogenic elements 15%~25%, broad-spectrum antibacterial elements 10%~20%, carbon 15%~25%, nitrogen 5%~15%; The transition metals are titanium, zirconium, hafnium, and vanadium. The bone-promoting active elements are strontium and zinc. The broad-spectrum antibacterial elements are silver and copper. The transition metal principal element, the osteogenic active element, and the broad-spectrum antibacterial element form a biphase high-entropy solid solution in the interstitial sites formed by the carbon and nitrogen elements. The biphase high-entropy solid solution includes a face-centered cubic carbide principal phase and a face-centered cubic nitride secondary phase.

2. The temperature-resistant and wear-resistant dual-phase high-entropy ceramic particle coating according to claim 1, characterized in that, The molar percentage of the transition metal main element is 35%~42%, and the molar ratio of the osteogenic active element to the broad-spectrum antibacterial element is in the range of (1.2~1.5):1; The molar ratio of strontium to zinc is 1:1, and the molar ratio of silver to copper is 1:(1.5~2).

3. The temperature-resistant and wear-resistant dual-phase high-entropy ceramic particle coating according to claim 1, characterized in that, The lattice constant difference between the carbide main phase and the nitride secondary phase is 0.5% to 2.0%, and a semi-coherent interface is formed between the carbide main phase and the nitride secondary phase. The osteogenic active element and the broad-spectrum antibacterial element segregate at the semi-coherent interface.

4. The temperature-sensitive and wear-resistant dual-phase high-entropy ceramic particle coating according to claim 3, characterized in that, The surface of the coating has a micro-nano hierarchical porous structure, which includes micron-scale pits and nano-scale pores. The osteogenic active elements are enriched in the inner walls of the nanoscale pores, and the broad-spectrum antibacterial elements are dispersed in the bottom walls of the micron-scale pits.

5. The temperature-sensitive and wear-resistant dual-phase high-entropy ceramic particle coating according to claim 1, characterized in that, The molar ratio of carbon to nitrogen is in the range of (1.5~2.5):1; The carbon element occupies the octahedral interstitial sites of the two-phase high-entropy solid solution to form the carbide main phase, and the nitrogen element occupies the octahedral interstitial sites to form the nitride secondary phase, and the nitride secondary phase encapsulates the carbide main phase.

6. The temperature-resistant and wear-resistant dual-phase high-entropy ceramic particle coating according to claim 1, characterized in that, The coating also includes an interface transition layer located between the coating and the medical titanium alloy substrate, the interface transition layer being composed of the titanium element, the carbon element and the aluminum element in the substrate; The molar ratio of titanium to aluminum in the interface transition layer decreases in the direction away from the substrate.

7. A method for preparing a temperature-sensitive, wear-resistant, dual-phase high-entropy ceramic particle coating according to any one of claims 1 to 6, characterized in that, Includes the following steps: Transition metal main component powder, osteogenic active element powder, broad-spectrum antibacterial element powder, carbon powder and silicon nitride powder are mixed in proportion and placed in a high-energy ball mill for wet ball milling to obtain composite powder. After the medical titanium alloy substrate is roughened by sandblasting, it is placed in the vacuum chamber of a vacuum plasma spraying equipment. Under a protective atmosphere of mixed argon and hydrogen, the composite powder is fed into a plasma jet for melting and then sprayed onto the surface of the medical titanium alloy substrate for deposition and molding. During the deposition process, the pressure in the vacuum chamber is adjusted to suppress the volatilization of the osteogenic active element and the broad-spectrum antibacterial element, so that the osteogenic active element and the broad-spectrum antibacterial element are dissolved into the two-phase high-entropy lattice formed by the transition metal main element and carbon and nitrogen. After cooling, the coating is obtained.

8. The method for preparing a temperature-sensitive and wear-resistant dual-phase high-entropy ceramic particle coating according to claim 7, characterized in that, In the wet ball milling step, the ball milling medium is anhydrous ethanol, the ball-to-material ratio is in the range of 8:1 to 12:1, and the ball milling speed is 300 rpm to 400 rpm. The osteogenic active element powder and the broad-spectrum antibacterial element powder are pre-mechanically alloyed before ball milling, so that the strontium element and the zinc element, and the silver element and the copper element respectively form pre-alloyed powders.

9. The method for preparing a temperature-sensitive and wear-resistant dual-phase high-entropy ceramic particle coating according to claim 7, characterized in that, Following the step of obtaining the coating after cooling, a surface reconstruction step is also included: The coating is immersed in an acidic etching solution containing fluoride ions for selective etching, dissolving the silver and copper elements on the surface of the biphase high-entropy lattice to form micron-sized pits; Subsequently, electrochemical deposition was performed in an alkaline electrolyte containing strontium ions, where oxides of the strontium element were deposited on the inner wall of the micron-sized pits, forming nanoscale pores.

10. The method for preparing a temperature-sensitive and wear-resistant dual-phase high-entropy ceramic particle coating according to claim 7, characterized in that, Before the deposition and molding step of spraying onto the surface of the medical titanium alloy substrate, pure titanium powder is first pre-sprayed as the bottom layer powder to form a bottom layer on the surface of the substrate. In the deposition molding step, the power of the plasma jet is adjusted to melt the bottom layer powder and the composite powder simultaneously. The titanium in the bottom layer reacts with the aluminum in the substrate and the carbon in the composite powder to form an interface transition layer in situ.