Artificial skeletal joint and preparation method thereof

Abstract

The present invention provides an artificial skeletal joint and a preparation method thereof, wherein the artificial skeletal joint comprises a skeletal joint body, a first micro-arc oxidation film layer, and a second micro-arc oxidation film layer; the skeletal joint body is made of a titanium alloy; the first micro-arc oxidation film layer is disposed on the joint movable surface of the skeletal joint body, and the second micro-arc oxidation film layer is disposed on the human bone contact surface of the skeletal joint body. The above-mentioned artificial skeletal joint adopts a double-surface treatment method to modify the surface of the titanium alloy skeletal joint body, and performs a micro-arc oxidation process strengthening treatment on the joint movable surface to prepare a first micro-arc oxidation film layer with high hardness, high elastic modulus, and low friction coefficient. The human bone contact surface is subjected to a micro-arc oxidation roughening treatment to prepare a second micro-arc oxidation film layer with low elastic modulus and biocompatibility, thereby meeting the requirements of different characteristics of different positions of the artificial skeletal joint and improving wear and stress shielding of bone tissue.

Description

Technical Field

[0001] The present invention relates to the technical field of medical implants, and in particular to an artificial skeletal joint and a preparation method thereof. Background Art

[0002] Artificial joints consist of an artificial skeletal joint made of metal and a spacer made of a polymer material. These two elements are placed side by side to replace human cartilage and enable joint movement. Artificial joints have important clinical applications, but wear and tear has long been a major factor affecting their lifespan.

[0003] To reduce wear between artificial bone joints and gaskets, the current approach is to use high-hardness cobalt-chromium-molybdenum alloys in their manufacture. The elastic modulus of human bone is 10-40 GPa, while that of cobalt-chromium-molybdenum alloy is 200-230 GPa, with a yield strength of 275-1585 MPa. Therefore, the elastic modulus of cobalt-chromium-molybdenum alloy is much greater than that of human bone joints. This creates a problem: under load-bearing conditions, the alloy can cause stress shielding at the contact surface of the bone joint, leading to bone tissue cell dissolution and implant loosening. Even though bone cement is commonly used as a buffering adhesive in clinical practice, it still cannot solve this problem. According to statistics, 2% of artificial joints require revision due to loosening / dissolution within 12 years after surgery, accounting for more than two-thirds of all revisions. Therefore, developing composite materials to replace cobalt-chromium-molybdenum alloys in the manufacture of tibial trays, while simultaneously addressing the issues of backplate wear and bone interface stress shielding, could help extend the lifespan of artificial knee joints and improve patients' quality of life.

[0004] Titanium alloys are ideal medical metal materials due to their high strength, excellent corrosion resistance, heat resistance, non-toxicity, light weight, and excellent biocompatibility. With an elastic modulus of 55 to 105 GPa and a yield strength of 100 to 1000 MPa, titanium alloys have become a popular choice for medical applications. However, the use of titanium alloys in artificial joints is prone to wear on the articulating surfaces.

[0005] Micro-arc oxidation technology is a relatively common surface modification technology for titanium alloys. It uses an oxide film layer grown in situ on valve metals (aluminum, magnesium, titanium) to protect the metal inside. Currently, there are many units at home and abroad researching this technology, and related books, papers and patents are emerging in an endless stream. The research focuses on the exploration of treatment fluid formulations and treatment electrical parameters, the improvement of processing technology and the characterization of film properties. For titanium metal and its alloys, micro-arc oxidation technology has greatly improved its surface hardness, corrosion resistance and biocompatibility indicators, greatly expanding the application areas of titanium and its alloys. In the medical field, micro-arc oxidation technology can enhance the corrosion resistance of titanium alloys in the human body environment and enhance the wear resistance of active parts. However, according to public papers, patents and other information, the film indicators prepared by the current micro-arc oxidation process are not sufficient to meet the mechanical requirements of the active parts of artificial joints. First, for artificial joints with weight-bearing areas, such as the knee, ankle, and femoral head, a film thickness of at least 100 μm is required. However, currently available data shows few processes capable of producing micro-arc oxidation films thicker than this. Even in the few reports that claim to have achieved this thickness, the films are often loose and easily peeled, failing to meet practical requirements. Therefore, there are no application cases for micro-arc oxidation films in movable joints.

[0006] In addition, in conventional micro-arc oxidation processing, fluoride is often used as a surface modifier to enhance the mechanical properties and density of the film. However, the film produced by this process often has trace amounts of residual fluorine. Since fluorine can have adverse effects on cell growth when entering the human body, the method of using fluoride to improve the performance of micro-arc oxidation films cannot be used in the field of orthopedic implants.

[0007] Based on the above background, this application proposes a design and preparation method for titanium alloy artificial joints. The design is based on an improved micro-arc oxidation process to prepare a high-hardness, high-thickness, wear-resistant micro-arc oxidation film layer as the active part of the bone joint. The preparation method uses a fluoride-free process, is non-toxic and harmless, and can be used for orthopedic implants. Summary of the Invention

[0008] In view of this, it is necessary to provide an artificial bone joint and its preparation method that can solve the wear problem of the joint movable surface of the artificial joint and the stress shielding problem of the human bone surface and has a long service life.

[0009] An artificial bone joint comprises a bone joint body, a first micro-arc oxidation film layer and a second micro-arc oxidation film layer;

[0010] The material of the skeletal joint body is titanium alloy;

[0011] The first micro-arc oxidation film layer is provided on the joint movable surface of the skeletal joint body, wherein the first micro-arc oxidation film layer is a pure rutile phase titanium dioxide film layer;

[0012] The second micro-arc oxidation film layer is provided on the human bone contact surface of the skeletal joint body, the second micro-arc oxidation film layer is a mixed phase of rutile titanium dioxide and anatase titanium dioxide, and the second micro-arc oxidation film layer has a rough surface;

[0013] Wherein, the first micro-arc oxidation film layer is prepared by the following method:

[0014] subjecting the joint movable surface of the skeletal joint body to micro-arc oxidation treatment in a first treatment solution to form the first micro-arc oxidation film layer on the joint movable surface;

[0015] The first treatment liquid is a suspension liquid, which is obtained by adding raw materials into water and stirring uniformly. The raw materials include aluminum sulfate and sodium silicate, and the hydrolysis products include sodium sulfate, aluminum hydroxide and silicic acid. In the first treatment liquid, the concentration of sodium sulfate is 0.03mol / L to 3mol / L, the concentration of the aluminum hydroxide suspension is 0.02mol / L to 2mol / L, and the concentration of the silicic acid suspension is 0.03mol / L to 3mol / L.

[0016] The anode pulse time of the micro-arc oxidation treatment is 5 to 60 minutes, the voltage of the anode pulse is 400 to 650V, and the pulse duty ratio is 10 to 30%.

[0017] In one embodiment, the thickness of the first micro-arc oxidation film layer is 205 μm.

[0018] In one embodiment, in the first treatment solution, the concentration of sodium sulfate is 0.30 mol / L, the concentration of aluminum hydroxide is 0.20 mol / L, and the concentration of silicic acid is 0.30 mol / L;

[0019] The anode pulse time of the micro-arc oxidation treatment is 15 minutes, the anode pulse voltage is 550V, and the pulse duty cycle is 20%.

[0020] In one embodiment, the thickness of the second micro-arc oxidation film layer is 64 μm.

[0021] In one embodiment, the diameter of the micropores on the second micro-arc oxidation film layer is 0.44 μm.

[0022] In one embodiment, the second micro-arc oxidation film layer is prepared by the following method:

[0023] subjecting the human bone contact surface of the skeletal joint body to micro-arc oxidation treatment in a second treatment solution to form a second micro-arc oxidation film layer on the human bone contact surface;

[0024] Wherein, the second treatment liquid is a suspension, and the second treatment liquid is obtained by adding raw materials into water and stirring uniformly, and the raw materials include sodium silicate, sodium phosphate, sodium sulfate, sodium citrate and aluminum hydroxide. In the second treatment liquid, the concentration of sodium silicate is 0.01mol / L~4mol / L, the concentration of sodium phosphate is 0.05mol / L~4mol / L, the concentration of sodium citrate is 0.01mol / L~1mol / L, the concentration of aluminum hydroxide is 0.01mol / L~4mol / L, and the concentration of sodium sulfate is 0.03mol / L~4mol / L;

[0025] The anode pulse time of the micro-arc oxidation treatment is 5 to 60 minutes, the voltage of the anode pulse is 400 to 600V, and the pulse duty ratio is 10 to 30%.

[0026] In one embodiment, in the second treatment solution, the concentration of sodium silicate is 0.07 mol / L; the concentration of sodium phosphate is 0.07 mol / L; the concentration of sodium citrate is 0.02 mol / L; the concentration of aluminum hydroxide is 0.08 mol / L; the concentration of sodium sulfate is 0.03 mol / L;

[0027] The anode pulse time of the micro-arc oxidation treatment is 20 minutes, the anode pulse voltage is 550V, and the pulse duty cycle is 20%.

[0028] In addition, a method for preparing an artificial skeletal joint is provided, comprising the following steps:

[0029] subjecting the joint movable surface of the skeletal joint body to micro-arc oxidation treatment in a first treatment solution to form a first micro-arc oxidation film layer on the joint movable surface;

[0030] The first treatment liquid is a suspension liquid, which is obtained by adding raw materials into water and stirring uniformly. The raw materials include aluminum sulfate and sodium silicate, and the hydrolysis products include sodium sulfate, aluminum hydroxide and silicic acid. In the first treatment liquid, the concentration of sodium sulfate is 0.03mol / L to 3mol / L, the concentration of the aluminum hydroxide suspension is 0.02mol / L to 2mol / L, and the concentration of the silicic acid suspension is 0.03mol / L to 3mol / L.

[0031] The anodic pulse time of the micro-arc oxidation treatment is 5 to 60 minutes, the anodic pulse voltage is 400 to 650 V, and the pulse duty cycle is 10 to 30%;

[0032] The human bone contact surface of the skeletal joint body is subjected to micro-arc oxidation treatment in a second treatment liquid to form a second micro-arc oxidation film layer on the human bone contact surface to obtain the artificial skeletal joint.

[0033] In one embodiment, the following steps are also included:

[0034] The second treatment liquid is a suspension, which is obtained by adding raw materials into water and stirring uniformly, wherein the raw materials include sodium silicate, sodium phosphate, sodium sulfate, sodium citrate, and aluminum hydroxide suspension, wherein the concentration of the sodium silicate is 0.01mol / L to 4mol / L, the concentration of the sodium phosphate is 0.05mol / L to 4mol / L, the concentration of the sodium citrate is 0.01mol / L to 1mol / L, the concentration of the aluminum hydroxide is 0.01mol / L to 4mol / L, and the concentration of the sodium sulfate is 0.03mol / L to 4mol / L;

[0035] The anode pulse time of the micro-arc oxidation treatment is 5 to 60 minutes, the voltage of the anode pulse is 400 to 600V, and the pulse duty ratio is 10 to 30%.

[0036] In one embodiment, the following steps are included before the step of micro-arc oxidation treatment of the joint movable surface of the skeletal joint body in the first treatment solution:

[0037] Adhere the area outside the joint movable surface of the skeletal joint body with waterproof insulating tape to prevent the area outside the joint movable surface of the skeletal joint body from being micro-arc oxidized; and / or,

[0038] The step of micro-arc oxidation treatment of the human bone contact surface of the skeletal joint body in the second treatment liquid includes the following steps:

[0039] The area outside the human bone contact surface of the skeletal joint body is adhered with waterproof insulating tape to prevent the area outside the human bone contact surface of the skeletal joint body from being micro-arc oxidized.

[0040] The above-mentioned artificial skeletal joint has a first micro-arc oxidation film layer provided on the joint movable surface of the skeletal joint body. The microhardness of the first micro-arc oxidation film layer is greater than 1000HV, the yield strength is greater than 10GPa, and the elastic modulus is greater than 150GPa. That is, the first micro-arc oxidation film layer has high hardness, high elastic modulus, and low friction coefficient, which effectively solves the wear problem of the artificial joint. In addition, the first micro-arc oxidation film layer is metallurgically bonded to the titanium alloy skeletal joint body, and has a stronger bonding force than conventional composite materials. The second micro-arc oxidation film layer has a low elastic modulus, which is similar to the elastic modulus of human bones. As a contact surface with human bones, it reduces stress shielding. The second micro-arc oxidation film layer has a rough surface and is biocompatible, which is conducive to cell attachment and improves the attachment ability of bone cells. In addition, the second micro-arc oxidation film layer is metallurgically bonded to the titanium alloy skeletal joint body, and has a stronger bonding force than conventional composite materials.

[0041] The artificial skeletal joint and its preparation method utilize a dual-surface treatment approach to modify the titanium alloy skeletal joint body. The active surface of the joint, i.e., the contact surface between the artificial skeletal joint and the gasket, is strengthened with micro-arc oxidation to produce a first micro-arc oxidation film with high hardness, high elastic modulus, and low friction coefficient. The interface with human bone, i.e., the contact surface with human bone, is roughened with micro-arc oxidation to produce a second micro-arc oxidation film with low elastic modulus and biocompatibility. This approach addresses the need for different properties at different locations in the artificial skeletal joint, improving wear and stress shielding for bone tissue. BRIEF DESCRIPTION OF THE DRAWINGS

[0042] Figure 1 Schematic diagram of the structure of an artificial skeletal joint according to one embodiment;

[0043] Figure 2 A schematic structural diagram of an artificial bone joint applied to a knee joint according to one embodiment;

[0044] Figure 3 It is a structural diagram of the micro-arc oxidation process experimental system;

[0045] Figure 4 This is the surface image of the first micro-arc oxidation film;

[0046] Figure 5 is a cross-sectional view of the first micro-arc oxidation film;

[0047] Figure 6 This is the surface image of the second micro-arc oxidation film;

[0048] Figure 7 is the XRD pattern of the first micro-arc oxidation film;

[0049] Figure 8 This is the XRD pattern of the second micro-arc oxidation film;

[0050] Figure 9 The load-displacement curves of the first micro-arc oxidation film at different longitudinal positions of the film;

[0051] Figure 10 The hardness and elastic modulus of the first micro-arc oxidation film vary with the longitudinal position;

[0052] Figure 11 Schematic diagram of friction and wear testing equipment;

[0053] Figure 12 This is the principle diagram of membrane shear force test. DETAILED DESCRIPTION

[0054] To make the objectives, technical solutions, and advantages of the embodiments of the present invention more apparent, the technical solutions of the embodiments of the present invention will be described clearly and completely below in conjunction with the accompanying drawings of the embodiments of the present invention. It should be understood that the described embodiments are only a portion of the embodiments of the present invention, not all of them. Generally, the components of the embodiments of the present invention described and illustrated in the drawings herein may be arranged and designed in a variety of different configurations.

[0055] Therefore, the following detailed description of the embodiments of the present invention provided in the accompanying drawings is not intended to limit the scope of the invention as claimed, but rather merely represents selected embodiments of the present invention. All other embodiments derived by persons of ordinary skill in the art based on the embodiments of the present invention without creative effort shall fall within the scope of protection of the present invention.

[0056] It should be noted that similar reference numerals and letters denote similar items in the following drawings, and therefore, once an item is defined in one drawing, it does not need to be further defined or explained in subsequent drawings.

[0057] In the description of the present invention, it should be understood that the directions or positions indicated by “upper” and the like are based on the directions or positions shown in the accompanying drawings, or are the directions or positions in which the product of the invention is usually placed when in use, or are the directions or positions commonly understood by those skilled in the art. These directions or positions are only for the convenience of describing the present invention and simplifying the description, and are not intended to indicate or imply that the device or component referred to must have a specific direction, be constructed and operated in a specific direction, and therefore should not be understood as a limitation on the present invention.

[0058] Furthermore, the terms “first”, “second”, etc. are merely used for distinguishing descriptions and should not be understood as indicating or implying relative importance.

[0059] The specific embodiments of the present invention are described in detail below with reference to the accompanying drawings.

[0060] Please refer to Figure 1An artificial skeletal joint according to one embodiment includes a skeletal joint body 10 , a first micro-arc oxidation film layer 20 and a second micro-arc oxidation film layer 30 .

[0061] The bone joint body 10 is made of titanium alloy.

[0062] The first micro-arc oxidation film layer 20 is disposed on the joint movable surface of the skeletal joint body 10 , wherein the first micro-arc oxidation film layer is a pure rutile phase titanium dioxide film layer.

[0063] The second micro-arc oxidation film 30 is disposed on the human bone contact surface of the skeletal joint body 10 . The second micro-arc oxidation film 30 is a mixed phase of rutile titanium dioxide and anatase titanium dioxide. The second micro-arc oxidation film has a rough surface.

[0064] The first micro-arc oxidation film layer is prepared by the following method:

[0065] The joint movable surface of the skeletal joint body is subjected to micro-arc oxidation treatment in a first treatment liquid to form a first micro-arc oxidation film layer on the joint movable surface.

[0066] Among them, the first treatment liquid is a suspension liquid, which is obtained by adding raw materials into water and stirring evenly. The raw materials include aluminum sulfate and sodium silicate. The hydrolysis products include sodium sulfate, aluminum hydroxide and silicic acid. In the first treatment liquid, the concentration of sodium sulfate is 0.03mol / L~3mol / L, the concentration of aluminum hydroxide suspension is 0.02mol / L~2mol / L, and the concentration of silicic acid suspension is 0.03mol / L~3mol / L.

[0067] The anode pulse time of the micro-arc oxidation treatment is 5 to 60 minutes, the voltage of the anode pulse is 400 to 650V, and the pulse duty ratio is 10 to 30%.

[0068] The above-mentioned artificial skeletal joint has a first micro-arc oxidation film layer 20 provided on the joint movable surface of the skeletal joint body 10. The microhardness of the first micro-arc oxidation film layer 20 is greater than 1000HV, the yield strength is greater than 10GPa, and the elastic modulus is greater than 150GPa. That is, the first micro-arc oxidation film layer 20 has high hardness, high elastic modulus, and low friction coefficient, which effectively solves the wear problem of the artificial joint. In addition, the first micro-arc oxidation film layer 20 is metallurgically bonded to the titanium alloy skeletal joint body 10, and has a stronger bonding force than conventional composite materials. The second micro-arc oxidation film layer 30 has a low elastic modulus, which is similar to the elastic modulus of human bones. As a contact surface with human bones, it reduces stress shielding. The second micro-arc oxidation film layer 30 has a rough surface and is biocompatible, which is conducive to cell attachment and improves the attachment ability of bone cells. In addition, the second micro-arc oxidation film layer 30 is metallurgically bonded to the titanium alloy skeletal joint body 10, and has a stronger bonding force than conventional composite materials.

[0069] The artificial skeletal joint utilizes a dual-surface treatment approach to modify the titanium alloy skeletal joint body 10. The active surface of the joint, i.e., the contact surface between the artificial skeletal joint and the gasket, is strengthened with a micro-arc oxidation process to produce a first micro-arc oxidation film 20 with high hardness, high elastic modulus, and low friction coefficient. The interface with human bone, i.e., the contact surface with human bone, is roughened with a micro-arc oxidation process to produce a second micro-arc oxidation film 30 with low elastic modulus and biocompatibility, thus meeting the requirements for different characteristics at different locations of the artificial skeletal joint.

[0070] Traditional titanium alloy MAO films have an elastic modulus of 20 to 150 GPa and a yield strength of 300 to 10,000 MPa. However, the first micro-arc oxidation film 20 of the artificial skeletal joint in the present invention has a yield strength greater than 10 GPa and an elastic modulus greater than 150 GPa, outperforming the performance of titanium alloy MAO films prepared by traditional methods. As the articular surface of the artificial skeletal joint, it effectively improves the hardness and wear resistance.

[0071] The above artificial bone joints can be applied to Figure 2 The knee joint and other positions are shown. Reference numeral 100 represents the artificial skeletal joint of the artificial joint, 200 represents the articulating surface of the artificial skeletal joint, 300 represents the human bone contact surface of the artificial skeletal joint, 400 represents the gasket portion of the artificial joint, and 500 represents the human body. The gasket 400 is positioned between the two artificial skeletal joints 100. The articulating surface 200 of the artificial skeletal joint 100 contacts the gasket. The regular contact surface 300 of the artificial skeletal joint 100 contacts the human skeletal joint.

[0072] Preferably, in the first treatment liquid, the concentration of sodium silicate is 0.3 mol / L, the concentration of aluminum hydroxide is 0.2 mol / L, and the concentration of silicic acid is 0.3 mol / L.

[0073] Preferably, the anodic pulse time of the micro-arc oxidation treatment is 15 minutes, the anodic pulse voltage is 550 V, and the pulse duty cycle is 20%. The titanium alloy material can be a metal material containing titanium, such as industrial pure titanium, α-phase titanium alloy, β-phase titanium alloy, or α+β mixed phase titanium alloy.

[0074] Furthermore, the first micro-arc oxidation film layer 20 is a film layer of pure rutile phase titanium dioxide with small grain size. The grain size of pure rutile phase titanium dioxide can be 5nm to 50nm. (The grain size of the rutile lattice structure is calculated to be 26nm through XRD diagram.) The surface structure and cross-sectional structure of the first micro-arc oxidation film layer 20 are respectively as follows: Figure 4 and Figure 5 shown. Figure 4 The scanning electron microscope image of the first micro-arc oxidation film layer 20 before polishing is as follows: Figure 4As shown in A, the scanning electron microscope image after polishing is as follows Figure 4 As shown in B.

[0075] In one embodiment, the thickness of the first micro-arc oxidation film 20 is 67 μm to 205 μm. If the thickness of the first micro-arc oxidation film 20 is too thin, the protective capability is weak and the film is useless. If the thickness of the first micro-arc oxidation film 20 is too thick, it is difficult to ensure the density of the film. In clinical practice, 67 μm to 205 μm is a relatively suitable range.

[0076] Micro-arc oxidation equipment such as Figure 3 As shown, 1 is the power supply for micro-arc oxidation; 2 is the artificial bone joint; 3 is the stainless steel tank; 4 is the base; 5 is the stirrer; 6 is the thermometer; and 7 is the cooling system.

[0077] Micro-arc oxidation (MAO) is a surface modification process for valve metals (titanium, aluminum, and magnesium). By immersing the metal in a treatment solution and applying a high voltage, a dense oxide film forms on the surface, modifying the material. The resulting film, composed of metal oxides, exhibits high hardness, corrosion resistance, and excellent biocompatibility.

[0078] The first micro-arc oxidation film layer 20 is prepared by a micro-arc oxidation process. The first micro-arc oxidation film layer 20 prepared by the micro-arc oxidation process is metallurgically bonded to the skeletal joint body 10 and has a strong bonding force.

[0079] In one embodiment, the thickness of the second micro-arc oxidation film 30 is 15 μm to 64 μm. This thickness range is sufficient to induce cell growth. A thickness less than 15 μm cannot maintain the porous morphology of the film. A thickness greater than 64 μm increases the film preparation time and does not improve the bio-performance of the film.

[0080] like Figure 6 As shown, the second micro-arc oxidation film layer 30 has a rough surface. The rough surface of the second micro-arc oxidation film layer 30 is biocompatible, which is conducive to cell attachment and improves the attachment ability of bone cells.

[0081] Specifically, the diameter of the micropores on the second micro-arc oxidation film layer 30 is 0.44 μm to 13.7 μm.

[0082] In one embodiment, the second micro-arc oxidation film layer 30 is prepared by the following method:

[0083] The human bone contact surface of the skeletal joint body 10 is subjected to micro-arc oxidation treatment in the second treatment solution to form a second micro-arc oxidation film layer 30 on the human bone contact surface 10 .

[0084] The second treatment liquid is a suspension, which is obtained by adding raw materials into water and stirring evenly. The raw materials include sodium silicate, sodium phosphate, sodium sulfate, sodium citrate and aluminum hydroxide. In the second treatment liquid, the concentration of sodium silicate is 0.01mol / L~4mol / L, the concentration of sodium phosphate is 0.05mol / L~4mol / L, the concentration of sodium citrate is 0.01mol / L~1mol / L, the concentration of aluminum hydroxide is 0.01mol / L~4mol / L, and the concentration of sodium sulfate is 0.03mol / L~4mol / L.

[0085] The anode pulse time of the micro-arc oxidation treatment is 5 to 60 minutes, the voltage of the anode pulse is 400 to 600V, and the pulse duty ratio is 10 to 30%.

[0086] Preferably, in the second treatment liquid, the concentration of sodium silicate is 0.07 mol / L; the concentration of sodium phosphate is 0.07 mol / L; the concentration of sodium citrate is 0.02 mol / L; the concentration of aluminum hydroxide is 0.08 mol / L; and the concentration of sodium sulfate is 0.03 mol / L.

[0087] Preferably, the anodic pulse time of the micro-arc oxidation treatment is 20 minutes, the anodic pulse voltage is 550 V, and the pulse duty cycle is 20%.

[0088] In another embodiment, since the material of the skeletal joint body 10 is titanium alloy, the elastic modulus of titanium alloy is not much different from that of human bone. In some applications with low requirements, a surface sandblasting process can be used to prepare a sandblasting layer to replace the second micro-arc oxidation film layer 30.

[0089] In addition, the present application also provides a method for preparing the above-mentioned artificial skeletal joint according to an embodiment, comprising the following steps:

[0090] S10 , performing micro-arc oxidation treatment on the joint movable surface of the skeletal joint body 10 in a first treatment liquid to form a first micro-arc oxidation film layer 20 on the joint movable surface.

[0091] The first treatment liquid is a suspension liquid, which is obtained by adding raw materials into water and stirring uniformly. The raw materials include aluminum sulfate and sodium silicate, and the hydrolysis products include sodium sulfate, aluminum hydroxide and silicic acid. In the first treatment liquid, the concentration of sodium sulfate is 0.03mol / L to 3mol / L, the concentration of the aluminum hydroxide suspension is 0.02mol / L to 2mol / L, and the concentration of the silicic acid suspension is 0.03mol / L to 3mol / L.

[0092] The anode pulse time of the micro-arc oxidation treatment is 5 to 60 minutes, the voltage of the anode pulse is 400 to 650V, and the pulse duty ratio is 10 to 30%.

[0093] S20, performing micro-arc oxidation treatment on the human bone contact surface of the skeletal joint body 10 in a second treatment liquid to form a second micro-arc oxidation film layer 30 on the human bone contact surface to obtain the artificial skeletal joint.

[0094] The above-mentioned method for preparing an artificial skeletal joint is to prepare a first micro-arc oxidation film layer 20 through a micro-arc oxidation process. By adopting a suitable first treatment liquid and coordinating corresponding electrical parameters, the crystal phase composition of the film layer is changed and the lattice size is reduced. The microhardness of the prepared first micro-arc oxidation film layer 20 is greater than 1000HV, the yield strength is greater than 10GPa, and the elastic modulus is greater than 150GPa. It has high hardness, high elastic modulus, and low friction coefficient, which effectively solves the wear problem of artificial joints. By adopting micro-arc oxidation, by adopting a suitable treatment liquid and appropriate micro-arc oxidation process parameters, the second micro-arc oxidation film layer 30 is prepared, which has a low elastic modulus, close to the elastic modulus of human bones, and reduces stress shielding. The prepared second micro-arc oxidation film layer 30 has a rough surface and is biocompatible, which is conducive to cell attachment and improves the attachment ability of bone cells.

[0095] In one embodiment, before the step of subjecting the joint movable surface of the skeletal joint body 10 to micro-arc oxidation treatment in the first treatment liquid, the following step is included: polishing the joint movable surface to be smooth.

[0096] In one embodiment, before the step of micro-arc oxidation treatment of the joint movable surface of the skeletal joint body 10 in the first treatment liquid, the following steps are also included:

[0097] The area outside the joint movable surface of the skeletal joint body 10 is taped with a waterproof insulating tape to prevent the area outside the joint movable surface of the skeletal joint body 10 from being micro-arc oxidized.

[0098] In one embodiment, after the step of micro-arc oxidation treatment of the joint movable surface of the skeletal joint body 10 in the first treatment liquid, the following steps are further included:

[0099] The first micro-arc oxidation film layer 20 is ground and polished to reduce the friction coefficient.

[0100] In one embodiment, the second treatment liquid is a suspension, which is obtained by adding raw materials into water and stirring uniformly, wherein the raw materials include sodium silicate, sodium phosphate, sodium sulfate, sodium citrate, and aluminum hydroxide suspension, wherein the concentration of the sodium silicate is 0.01mol / L to 4mol / L, the concentration of the sodium phosphate is 0.01mol / L to 4mol / L, the concentration of the sodium citrate is 0.01mol / L to 1mol / L, the concentration of the aluminum hydroxide is 0.01mol / L to 4mol / L, and the concentration of the sodium sulfate is 0.03mol / L to 4mol / L;

[0101] The anode pulse time of the micro-arc oxidation treatment is 5 to 60 minutes, the voltage of the anode pulse is 400 to 600V, and the pulse duty ratio is 10 to 30%.

[0102] In one embodiment, before the step of subjecting the human bone contact surface of the skeletal joint body 10 to micro-arc oxidation in the second treatment liquid, the following step is included: polishing the human bone contact surface to be smooth.

[0103] It is understood that in the above-mentioned method for preparing an artificial skeletal joint, when forming the first micro-arc oxidation film layer 20 on the joint movable surface of the skeletal joint body 10 and forming the second micro-arc oxidation film layer 30 on the human bone contact surface, S10 can be performed first and then S20, or S20 can be performed first and then S10. That is, when the above-mentioned method for preparing an artificial skeletal joint includes both steps S10 and S20, the order in which the two steps are performed is not limited.

[0104] In one embodiment, the following steps are included before the step of micro-arc oxidation treatment of the human bone contact surface of the skeletal joint body 10 in the second treatment liquid:

[0105] The area outside the human bone contact surface of the skeletal joint body 10 is taped with waterproof insulating tape to prevent the area outside the human bone contact surface of the skeletal joint body 10 from being micro-arc oxidized.

[0106] Preferably, in S10, in the first treatment liquid, the concentration of sodium sulfate is 0.30 mol / L, the concentration of aluminum hydroxide is 0.20 mol / L, the concentration of silicic acid is 0.30 mol / L, the anode pulse time of micro-arc oxidation treatment is 15 minutes, the voltage of the anode pulse is 550 V, and the pulse duty cycle is 20%.

[0107] Preferably, in S20, the concentration of sodium silicate in the second treatment solution is 0.07 mol / L; the concentration of sodium phosphate is 0.07 mol / L; the concentration of sodium citrate is 0.02 mol / L; the concentration of aluminum hydroxide is 0.08 mol / L; and the concentration of sodium sulfate is 0.03 mol / L. Preferably, the anodic pulse time of the micro-arc oxidation treatment is 20 minutes, the anodic pulse voltage is 550 V, and the pulse duty cycle is 20%.

[0108] The above-mentioned method for preparing an artificial skeletal joint adopts a double-surface micro-arc oxidation treatment method to perform surface modification on the titanium alloy skeletal joint body 10, and by adjusting the appropriate first treatment liquid and reaction electrical parameters, the joint movable surface is subjected to a micro-arc oxidation process strengthening treatment to prepare a first micro-arc oxidation film layer 20 with high hardness, high elastic modulus, and low friction coefficient. By adjusting the appropriate second treatment liquid and reaction electrical parameters, the human bone contact surface is subjected to a micro-arc oxidation roughening treatment to prepare a second micro-arc oxidation film layer 30 with low elastic modulus and biocompatibility, thereby meeting the requirements of different characteristics of different positions of the artificial skeletal joint. Therefore, the above-mentioned method for preparing an artificial skeletal joint prepares two micro-arc oxidation film layers with different properties, which effectively solves the wear and stress shielding problems of the artificial skeletal joints in the prior art. A high-hardness film layer is prepared on the joint movable surface to solve the wear problem of the artificial joint; a low-elastic modulus film layer is prepared on the human bone contact surface to solve the stress shielding problem between the artificial joint and the human bone.

[0109] The following are specific examples.

[0110] Example 1

[0111] A titanium alloy with a material grade of TC4 is used as the skeletal joint body. The area outside the joint movable surface of the skeletal joint body is pasted with waterproof insulating tape. Then, the joint movable surface of the skeletal joint body is subjected to micro-arc oxidation treatment in a first treatment liquid to form a first micro-arc oxidation film layer on the joint movable surface. The first treatment liquid is a suspension liquid, which is obtained by adding raw materials into water and stirring evenly. The raw material ratio is 0.01 mol / L of aluminum sulfate and 0.04 mol / L of sodium silicate; after hydrolysis, the concentration of sodium sulfate in the suspension is 0.03 mol / L, the concentration of aluminum hydroxide is 0.02 mol / L, and the concentration of silicic acid is 0.03 mol / L. The anode pulse time of the micro-arc oxidation treatment is 60 minutes, the voltage of the anode pulse is 650V, and the pulse duty cycle is 30%.

[0112] The thickness of the prepared first micro-arc oxidation film layer is 67 μm, the microhardness is 1120 HV, the yield strength is 10.6 GPa, the elastic modulus is 165 GPa, and the friction coefficient is 0.10-0.20 (1 N load).

[0113] The area outside the human bone contact surface of the skeletal joint body is taped with waterproof insulating tape. Then, the human bone contact surface of the skeletal joint body is subjected to micro-arc oxidation treatment in a second treatment liquid to form a second micro-arc oxidation film layer on the human bone contact surface. The second treatment liquid is a suspension, and the second treatment liquid is obtained by adding raw materials into water and stirring evenly. The raw materials include sodium silicate, sodium phosphate, sodium sulfate, sodium citrate and aluminum hydroxide. The concentration of sodium silicate is 0.01 mol / L, the concentration of sodium phosphate is 0.05 mol / L, the concentration of sodium citrate is 0.01 mol / L, the concentration of aluminum hydroxide is 0.01 mol / L, and the concentration of sodium sulfate is 0.2 mol / L. The anode pulse time of the micro-arc oxidation treatment is 60 minutes, the voltage of the anode pulse is 600 V, and the pulse duty cycle is 30%.

[0114] The thickness of the prepared second micro-arc oxidation film layer is 15 μm, the average micropore diameter is 13.7 μm, and the elastic modulus is 62 GPa.

[0115] Example 2

[0116] A titanium alloy with a material grade of TC4 is used as the skeletal joint body. The area outside the joint movable surface of the skeletal joint body is pasted with waterproof insulating tape. Then, the joint movable surface of the skeletal joint body is subjected to micro-arc oxidation treatment in a first treatment liquid to form a first micro-arc oxidation film layer on the joint movable surface. The first treatment liquid is a suspension liquid, which is obtained by adding raw materials into water and stirring evenly. The raw material ratio is 1 mol / L of aluminum sulfate and 4 mol / L of sodium silicate; after hydrolysis, the concentration of sodium silicate in the suspension is 3 mol / L, the concentration of aluminum hydroxide is 2 mol / L, and the concentration of silicic acid is 3 mol / L. The anode pulse time of the micro-arc oxidation treatment is 5 minutes, the voltage of the anode pulse is 400V, and the pulse duty cycle is 10%.

[0117] The thickness of the prepared first micro-arc oxidation film layer is 120 μm, the microhardness is 1003 HV, the yield strength is 11.7 GPa, the elastic modulus is 152 GPa, and the friction coefficient is 0.15-0.20 (1N load).

[0118] The area outside the human bone contact surface of the skeletal joint body is taped with waterproof insulating tape. Then, the human bone contact surface of the skeletal joint body is subjected to micro-arc oxidation treatment in a second treatment liquid to form a second micro-arc oxidation film layer on the human bone contact surface. The second treatment liquid is a suspension, and the second treatment liquid is obtained by adding raw materials into water and stirring evenly. The raw materials include sodium silicate, sodium phosphate, sodium sulfate, sodium citrate and aluminum hydroxide. The concentration of sodium silicate is 4 mol / L, the concentration of sodium phosphate is 4 mol / L, the concentration of sodium citrate is 1 mol / L, the concentration of aluminum hydroxide is 4 mol / L, and the concentration of sodium sulfate is 4 mol / L. The anode pulse time of the micro-arc oxidation treatment is 5 minutes, the voltage of the anode pulse is 400 V, and the pulse duty cycle is 10%.

[0119] The thickness of the prepared second micro-arc oxidation film layer is 57 μm, the micropore diameter is 1.02 μm, and the elastic modulus is 47 GPa.

[0120] Example 3

[0121] A titanium alloy with a material grade of TC4 is used as the skeletal joint body. The area outside the joint movable surface of the skeletal joint body is pasted with waterproof insulating tape. Then, the joint movable surface of the skeletal joint body is subjected to micro-arc oxidation treatment in a first treatment liquid to form a first micro-arc oxidation film layer on the joint movable surface. The first treatment liquid is a suspension liquid, which is obtained by adding raw materials into water and stirring evenly. The raw material ratio is 0.1 mol / L of aluminum sulfate and 0.3 mol / L of sodium silicate; after hydrolysis, the concentration of sodium sulfate in the suspension is 0.30 mol / L, the concentration of aluminum hydroxide is 0.20 mol / L, and the concentration of silicic acid is 0.30 mol / L. The anode pulse time of the micro-arc oxidation treatment is 15 minutes, the voltage of the anode pulse is 550V, and the pulse duty cycle is 20%.

[0122] The area outside the human bone contact surface of the skeletal joint body is taped with waterproof insulating tape. Next, the human bone contact surface of the skeletal joint body is subjected to micro-arc oxidation treatment in a second treatment liquid to form a second micro-arc oxidation film layer on the human bone contact surface. The second treatment liquid is a suspension liquid, which is obtained by adding raw materials into water and stirring evenly. The raw materials include sodium silicate, sodium phosphate, sodium sulfate, sodium citrate and aluminum hydroxide. The concentration of sodium silicate is 0.07 mol / L; the concentration of the sodium phosphate is 0.07 mol / L; the concentration of the sodium citrate is 0.02 mol / L; the concentration of the aluminum hydroxide is 0.08 mol / L; and the concentration of the sodium sulfate is 0.03 mol / L. The anode pulse time of the micro-arc oxidation treatment is 20 minutes, the voltage of the anode pulse is 550V, and the pulse duty cycle is 20%.

[0123] The thickness of the first micro-arc oxidation film prepared is 205 μm, the microhardness is 1550 HV, the yield strength is 15.0 GPa, the elastic modulus is 196 GPa, and the friction coefficient is 0.17-0.22 (load 1 N). The XRD pattern of the first micro-arc oxidation film is as follows: Figure 7 As shown in FIG. 1 , the XRD (X-ray diffraction) test pattern of the first micro-arc oxidation film only contains rutile phase titanium dioxide. The diffraction peak of titanium in the pattern comes from the titanium substrate, not from the components in the film.

[0124] The thickness of the second micro-arc oxidation film prepared is 64 μm, the micropore diameter is 0.44 μm, and the elastic modulus is 50 GPa. The XRD pattern of the second micro-arc oxidation film is as follows: Figure 8 As shown, this is the XRD test pattern of the second micro-arc oxidation film, which is a mixed phase of rutile and anatase. The diffraction peak of titanium in the figure comes from the titanium substrate, not the component in the film.

[0125] Performance Testing

[0126] Nanoindentation testing

[0127] The microhardness and elastic modulus of the first micro-arc oxidation film prepared in Example 3 were tested using a NanoindenterXP nanoindentation tester produced by MTS Corporation of the United States. During the test, a Berkovich diamond indenter was used, and the ambient temperature variation was less than 1°C. The test was carried out using the Oliver and Pharr method, with the indenter pressed into the sample surface at a speed of 10 nm / s to a depth of 2000 nm. The loading and unloading forces were recorded in real time during the experiment and plotted as a curve. Please refer to Figure 9 For each sample, five points at different locations were selected for testing, and the test results were averaged.

[0128] Figure 10 The yield strength and elastic modulus values ​​of the first micro-arc oxidation film at different longitudinal locations are shown. As can be seen from the figure, the film hardness and elastic modulus vary slightly at different locations; the elastic modulus is greater than 140 GPa at 60 μm to 120 μm, reaching a maximum of 196 GPa. Considering that the outermost layer of the film (here corresponding to 150 μm) will be polished away, the film specifications are yield strength > 10 GPa and elastic modulus > 140 GPa.

[0129] Friction test

[0130] The friction test was carried out using the MM-2000 friction and wear testing machine of Jinan Yinuo Experimental Instrument Co., Ltd. The experimental instrument is controlled by a microcomputer and can simulate friction and wear tests of various materials under different working conditions such as dry friction, wet friction, and abrasive wear. It can display parameters such as test force, friction torque, friction coefficient, and test time in real time, and can record the friction coefficient-time curve during the experiment. The test results of this tester are in line with GB / T12444.2-90 Metal Wear Test Method-MM Wear Test. After the friction test, the mass loss of the test component was weighed using an AL204 electronic balance (precision 0.1 mg) produced by Mettler-Toledo Instruments.

[0131] The wear resistance of the first micro-arc oxidation film prepared in Example 3 was tested on an MM-2000 friction and wear tester. The current density of the preparation process of the first micro-arc oxidation film was 23A / dm 2 . Using ring-ring sliding and dry friction, the friction diagram is as follows Figure 11 The wear parts were made of GCr15 bearing steel, with a hardness greater than HRC62 after heat treatment. The test load was either 40 Newton or 1 Newton; the relative sliding rate was 1 m / s, and the friction travel was 18 km. A Mettler-Toledo AL204 electronic balance (0.1 mg accuracy) was used to weigh the sample and the wear parts before and after friction to calculate the wear rate. The test results are shown in Table 1.

[0132] Table 1 Friction test results of titanium and the first micro-arc oxidation film

[0133]

[0134] *Note: “-” in the table means the value is too small to be measured.

[0135] As shown in the table, under a load of 40N, the friction coefficient between the first micro-arc oxidation film and the bearing steel is 0.55-0.63, lower than that between titanium and bearing steel. The wear loss of the specimen is 45.3mg, far lower than the 73.6mg wear loss of the titanium specimen. This demonstrates that the first micro-arc oxidation film has superior wear resistance compared to the titanium substrate.

[0136] Film shear force test

[0137] The test objects are the first micro-arc oxidation film layer and the second micro-arc oxidation film layer prepared in Example 3. Figure 12 , is the test principle diagram, where 110 is the sample, 120 is the fixture, and 130 is the bonding point between the fixture and the sample. The test method is to use epoxy adhesive to bond the film layer, and the bonding area is about 20mm 2 , apply stress parallel to the film until the film fails, and record the maximum stress. Divide the maximum stress by the bonding area to get the shear strength. The calculation formula is:

[0138]

[0139] Table 2 Shear force test results of the first micro-arc oxidation film and the second micro-arc oxidation film

[0140]

[0141] Cytocompatibility testing

[0142] The second micro-arc oxidation film prepared in Example 3 was subjected to a cell culture CCK-8 test. Rat SD osteoblasts were cultured in H-DMEM medium, and the experimental results were statistically analyzed after 24 hours, 3 days, and 7 days. The control samples were a traditional micro-arc oxidation film, a titanium substrate, and a titanium substrate with a sandblasted surface. The data were statistically analyzed using ANOVA analysis of variance. The statistical results are shown in the table:

[0143] Table 3 Statistical results of CCK-8 cell proliferation assay

[0144]

[0145] As can be seen from Table 3, the test values ​​of the second micro-arc oxidation film at 24 hours, 3 days, and 7 days are all greater than those of the control group, which indicates that the second micro-arc oxidation film has better biocompatibility.

[0146] The above are only preferred embodiments of the present invention. It should be pointed out that ordinary technicians in this technical field can make several improvements and modifications without departing from the principles of the present invention. These improvements and modifications should also be regarded as within the scope of protection of the present invention.

Claims

1. An artificial skeletal joint, characterized in that: It includes a skeletal joint body, a first micro-arc oxidation film layer and a second micro-arc oxidation film layer; The material of the skeletal joint body is titanium alloy; The first micro-arc oxidation film layer is provided on the joint movable surface of the skeletal joint body, wherein the first micro-arc oxidation film layer is a pure rutile phase titanium dioxide film layer; The second micro-arc oxidation film layer is provided on the human bone contact surface of the skeletal joint body, the second micro-arc oxidation film layer is a mixed phase of rutile titanium dioxide and anatase titanium dioxide, and the second micro-arc oxidation film layer has a rough surface; Wherein, the first micro-arc oxidation film layer is prepared by the following method: subjecting the joint movable surface of the skeletal joint body to micro-arc oxidation treatment in a first treatment solution to form the first micro-arc oxidation film layer on the joint movable surface; The first treatment liquid is a suspension liquid, which is obtained by adding raw materials into water and stirring uniformly. The raw materials include aluminum sulfate and sodium silicate, and the hydrolysis products include sodium sulfate, aluminum hydroxide and silicic acid. In the first treatment liquid, the concentration of sodium sulfate is 0.03mol / L~3mol / L, the concentration of the aluminum hydroxide suspension is 0.02mol / L~2mol / L, and the concentration of the silicic acid suspension is 0.03mol / L~3mol / L; The anodic pulse time of the micro-arc oxidation treatment is 5 to 60 minutes, the anodic pulse voltage is 400 to 650 V, and the pulse duty cycle is 10 to 30%; The second micro-arc oxidation film layer is prepared by the following method: subjecting the human bone contact surface of the skeletal joint body to micro-arc oxidation treatment in a second treatment solution to form a second micro-arc oxidation film layer on the human bone contact surface; Wherein, the second treatment liquid is a suspension, and the second treatment liquid is obtained by adding raw materials into water and stirring uniformly, the raw materials include sodium silicate, sodium phosphate, sodium sulfate, sodium citrate and aluminum hydroxide, and the second treatment liquid has a concentration of sodium silicate of 0.01mol / L~4mol / L, a concentration of sodium phosphate of 0.05mol / L~4mol / L, a concentration of sodium citrate of 0.01mol / L~1mol / L, a concentration of aluminum hydroxide of 0.01mol / L~4mol / L, and a concentration of sodium sulfate of 0.03mol / L~4mol / L; The anode pulse time of the micro-arc oxidation treatment is 5 to 60 minutes, the anode pulse voltage is 400 to 600 V, and the pulse duty cycle is 10 to 30%.

2. The artificial skeletal joint according to claim 1, wherein: The thickness of the first micro-arc oxidation film layer is 67 μm to 205 μm.

3. The artificial skeletal joint according to claim 1, wherein: In the first treatment liquid, the concentration of sodium sulfate is 0.3 mol / L, the concentration of aluminum hydroxide is 0.2 mol / L, and the concentration of silicic acid is 0.3 mol / L; The anode pulse time of the micro-arc oxidation treatment is 15 minutes, the anode pulse voltage is 550V, and the pulse duty cycle is 20%.

4. The artificial skeletal joint according to claim 1, wherein: The thickness of the second micro-arc oxidation film layer is 67 μm to 205 μm.

5. The artificial skeletal joint according to claim 4, characterized in that: The diameter of the micropores on the second micro-arc oxidation film layer is 0.44 μm to 13.7 μm.

6. The artificial skeletal joint according to claim 5, characterized in that: In the second treatment liquid, the concentration of sodium silicate is 0.07 mol / L; the concentration of sodium phosphate is 0.07 mol / L; the concentration of sodium citrate is 0.02 mol / L; the concentration of aluminum hydroxide is 0.08 mol / L; and the concentration of sodium sulfate is 0.03 mol / L. The anodic pulse time of the micro-arc oxidation treatment is 20 minutes, the anodic pulse voltage is 550 V, and the pulse duty cycle is 20%.

7. A method for preparing an artificial skeletal joint, the method being applicable to the artificial skeletal joint according to any one of claims 1 to 6, characterized in that: The following steps are involved: subjecting the joint movable surface of the skeletal joint body to micro-arc oxidation treatment in a first treatment solution to form a first micro-arc oxidation film layer on the joint movable surface; The first treatment liquid is a suspension liquid, which is obtained by adding raw materials into water and stirring uniformly. The raw materials include aluminum sulfate and sodium silicate, and the hydrolysis products include sodium sulfate, aluminum hydroxide and silicic acid. In the first treatment liquid, the concentration of sodium sulfate is 0.03mol / L~3mol / L, the concentration of the aluminum hydroxide suspension is 0.02mol / L~2mol / L, and the concentration of the silicic acid suspension is 0.03mol / L~3mol / L. The anodic pulse time of the micro-arc oxidation treatment is 5 to 60 minutes, the anodic pulse voltage is 400 to 650 V, and the pulse duty cycle is 10 to 30%; subjecting the human bone contact surface of the skeletal joint body to micro-arc oxidation treatment in a second treatment solution to form a second micro-arc oxidation film layer on the human bone contact surface to obtain the artificial skeletal joint; The second treatment liquid is a suspension, which is obtained by adding raw materials into water and stirring uniformly, wherein the raw materials include sodium silicate, sodium phosphate, sodium sulfate, sodium citrate, and aluminum hydroxide suspension, wherein the concentration of the sodium silicate is 0.01mol / L~4mol / L, the concentration of the sodium phosphate is 0.05mol / L~4mol / L, the concentration of the sodium citrate is 0.01mol / L~1mol / L, the concentration of the aluminum hydroxide is 0.01mol / L~4mol / L, and the concentration of the sodium sulfate is 0.03mol / L~4mol / L; The anode pulse time of the micro-arc oxidation treatment is 5 to 60 minutes, the anode pulse voltage is 400 to 600 V, and the pulse duty cycle is 10 to 30%.

8. The method for preparing an artificial skeletal joint according to claim 7, wherein: The following steps are included before the step of micro-arc oxidation treatment of the joint movable surface of the skeletal joint body in the first treatment liquid: Adhere the area outside the joint movable surface of the skeletal joint body with waterproof insulating tape to prevent the area outside the joint movable surface of the skeletal joint body from being micro-arc oxidized; and / or, The step of micro-arc oxidation treatment of the human bone contact surface of the skeletal joint body in the second treatment liquid includes the following steps: The area outside the human bone contact surface of the skeletal joint body is adhered with waterproof insulating tape to prevent the area outside the human bone contact surface of the skeletal joint body from being micro-arc oxidized.

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