A method for constructing a high-performance multilayer coating containing hydroxyapatite on the surface of a titanium implant with antibacterial and osteogenic effects

Abstract

The application relates to a method for constructing a high-performance multi-layer coating containing hydroxyapatite on a titanium implant surface, and aims to solve the problems of poor corrosion resistance, poor antibacterial ability and poor osteogenesis ability of the existing titanium implant surface. The method comprises the following steps: one, micro-arc oxidation treatment; and two, microwave hydrothermal treatment. The application is used for constructing a high-performance multi-layer coating containing hydroxyapatite on a titanium implant surface.

Description

TECHNICAL FIELD

[0001] The present application relates to a method for constructing a high-performance multi-layer coating containing hydroxyapatite on the surface of a titanium implant. BACKGROUND

[0002] For the problem of tooth loss repair, dental implant technology is the best means to solve the problem of periodontal tissue loss. In clinical application, the commonly used implant material is titanium and its alloy, which is implanted into the position of the missing tooth to restore the functionality of the tooth. However, the oral environment is very complex and contains a large number of bacteria and body fluids, which leads to corrosion of the surface of the titanium implant, thereby causing the loosening of the implant. At present, new antibacterial alloys or antibacterial coatings are commonly used to obtain antibacterial ability, but the osteogenic ability of the surface of the titanium implant obtained still needs to be improved. In addition, the commonly used antibacterial factors in the micro-arc oxidation coating on the surface of the titanium implant are zinc, copper and silver elements, and the introduction of these elements is not conducive to the formation of the subsequent hydroxyapatite coating. Therefore, there is an urgent need for a new implant with excellent corrosion resistance, antibacterial and osteogenic ability. SUMMARY

[0003] The present application solves the problem of poor corrosion resistance, antibacterial ability and osteogenic ability of the surface of the existing titanium implant, and further provides a method for constructing a high-performance multi-layer coating containing hydroxyapatite with antibacterial and osteogenic effects on the surface of a titanium implant.

[0004] A method for constructing a high-performance multi-layer coating containing hydroxyapatite with antibacterial and osteogenic effects on the surface of a titanium implant, which is carried out according to the following steps:

[0005] I. Micro-arc oxidation treatment:

[0006] The titanium implant without an oxide layer is placed in an electrolyte containing a bioactive component, with the titanium implant without an oxide layer as the anode and a stainless steel plate as the cathode. Micro-arc oxidation is carried out using a pulse direct current voltage under the conditions of a voltage of 400V-500V, a pulse frequency of 600Hz-1000Hz, a duty cycle of 4%-20%, and an electrolyte temperature of 20°C-30°C, to obtain a titanium implant after micro-arc oxidation treatment.

[0007] The electrolyte containing a bioactive component is mixed from deionized water, disodium ethylenediaminetetraacetate, sodium hydroxide, sodium silicate, calcium dihydrogen phosphate, calcium acetate, hydrogen peroxide and niobium oxalate. The addition amount of hydrogen peroxide in the electrolyte containing a bioactive component is 6mL / L-15mL / L, and the concentration of niobium oxalate is 5g / L-20g / L.

[0008] II. Microwave hydrothermal treatment:

[0009] The method comprises the following steps: immersing the titanium implant treated by micro-arc oxidation into an alkaline solution and performing microwave hydrothermal treatment, so as to complete the construction of the high-performance multilayer coating containing hydroxyapatite on the surface of the titanium implant.

[0010] The present application has the following advantages:

[0011] The present application aims to obtain a high-performance multilayer coating with excellent corrosion resistance, antibacterial and osteogenic ability on the surface of a titanium implant. The niobium element is introduced into the coating on the surface of the titanium implant by micro-arc oxidation technology, and the niobium element exists in an amorphous state, thereby improving the corrosion resistance of the surface of the titanium implant. In addition, the calcium-phosphorus-niobium micro-arc oxidation coating is treated by microwave hydrothermal treatment, which can significantly reduce the loss of active elements such as calcium, phosphorus and niobium in the coating, and at the same time, promote the conversion of calcium-phosphorus amorphous phase into high-activity hydroxyapatite nanorods, so as to improve the biological activity and osteogenic ability of the titanium implant. In addition, the enrichment of the niobium element on the surface of the implant can also improve the antibacterial ability of the titanium implant, thereby realizing a high-performance multilayer coating with antibacterial and osteogenic dual functions, and obtaining a new titanium implant with antibacterial-osteogenic dual effects and corrosion resistance, thereby expanding the application of the titanium implant material in periodontal tissue repair.

[0012] The sample treated by the present application is detected by an EDS energy spectrum of a diffractometer, and the coating contains trace elements such as calcium, phosphorus and niobium. The corrosion resistance of the coating containing niobium is significantly improved through electrochemical polarization curve corrosion performance test. XRD diffraction detection shows that the sample treated by the present application contains anatase and hydroxyapatite. The scanning electron microscope shows that a large number of hydroxyapatite nanorods are formed on the surface of the coating, and the length of the nanorods is about 1 μm and the diameter is about 500 nm. The antibacterial ability of the surface of the sample treated by the present application is characterized, and the number of surviving bacteria is significantly reduced after 24 hours of culture, and the antibacterial rate reaches 96.1%. After the sample treated by the present application is implanted into the tibia of a rabbit for 4 weeks, a large amount of new bone formation tissue is formed on the surface, which shows that the titanium implant with the micro-arc oxidation coating treated by the microwave hydrothermal treatment has higher corrosion resistance, antibacterial ability, apatite induction ability and osteogenic ability.

[0013] The present application relates to a method for constructing a high-performance multilayer coating containing hydroxyapatite on the surface of a titanium implant. BRIEF DESCRIPTION OF DRAWINGS

[0014] Figure 1 The electrochemical corrosion curves of the niobium-containing high-performance multilayer coating prepared in Example 1 and the niobium-free high-performance multilayer coating prepared in the comparative experiment;

[0015] Figure 2 The XRD pattern of the niobium-containing high-performance multilayer coating prepared in Example 1, A is the anatase peak, B is the titanium peak, and C is the hydroxyapatite peak;

[0016] Figure 3Scanning electron microscope image of high performance multi-layer coating containing niobium prepared in Example 1;

[0017] Figure 4 Transmission image of high performance multi-layer coating containing niobium prepared in Example 1;

[0018] Figure 5 EDS energy spectrum image of high performance multi-layer coating containing niobium prepared in Example 1;

[0019] Figure 6 Scanning image of surface bacteria morphology of high performance multi-layer coating containing niobium prepared in Example 1;

[0020] Figure 7 Practical image of antibacterial effect of high performance multi-layer coating containing niobium prepared in Example 1 and high performance multi-layer coating without niobium prepared in comparative experiment;

[0021] Figure 8 Scanning image of residual bone tissue on implant surface of high performance multi-layer coating containing niobium prepared in Example 1. DETAILED DESCRIPTION

[0022] The technical solution of the present application is not limited to the following specific embodiments, and any combination of the specific embodiments is also included.

[0023] Specific embodiment one: the method for constructing high performance multi-layer coating containing hydroxyapatite on the surface of titanium implant for antibacterial and osteogenic effects is carried out according to the following steps:

[0024] I. Micro-arc oxidation treatment:

[0025] The titanium implant without an oxide layer is placed in an electrolyte containing a bioactive component, and the titanium implant without an oxide layer is used as an anode, and a stainless steel plate is used as a cathode. A pulse direct current voltage is used for micro-arc oxidation under the conditions of a voltage of 400V-500V, a pulse frequency of 600Hz-1000Hz, a duty cycle of 4%-20%, and an electrolyte temperature of 20℃-30℃, to obtain a titanium implant after micro-arc oxidation treatment.

[0026] The electrolyte containing a bioactive component is mixed by deionized water, disodium ethylenediaminetetraacetate, sodium hydroxide, sodium silicate, calcium dihydrogen phosphate, calcium acetate, hydrogen peroxide, and niobium oxalate. The amount of hydrogen peroxide added in the electrolyte containing a bioactive component is 6mL / L-15mL / L, and the concentration of niobium oxalate is 5g / L-20g / L.

[0027] II. Microwave hydrothermal treatment:

[0028] The method comprises the following steps: immersing the titanium implant treated by micro-arc oxidation into an alkaline solution and performing microwave hydrothermal treatment, so as to complete the construction of the high-performance multilayer coating containing hydroxyapatite on the surface of the titanium implant.

[0029] The embodiment has the following advantages:

[0030] The embodiment aims to obtain a high-performance multilayer coating with excellent corrosion resistance, antibacterial and osteogenic ability on the surface of a titanium implant. The ni element is introduced into the coating on the surface of the titanium implant by micro-arc oxidation technology, and the ni element exists in an amorphous state, thereby improving the corrosion resistance of the surface of the titanium implant. In addition, the calcium-phosphorus-ni micro-arc oxidation coating is treated by microwave hydrothermal treatment, which can significantly reduce the loss of active elements such as calcium, phosphorus and ni in the coating, and at the same time, promote the conversion of the calcium-phosphorus amorphous phase into high-activity hydroxyapatite nanorods, so as to improve the biological activity and osteogenic ability of the titanium implant. In addition, the enrichment of the ni element on the surface of the implant can also improve the antibacterial ability of the surface of the titanium implant, thereby realizing a high-performance multilayer coating with antibacterial and osteogenic dual functions, and obtaining a new titanium implant with antibacterial-osteogenic dual effects and corrosion resistance, thereby expanding the application of the titanium implant material in periodontal tissue repair.

[0031] The sample treated by the embodiment is detected by an EDS energy spectrum of a diffractometer, and the coating contains trace elements such as calcium, phosphorus and ni. The corrosion resistance of the coating containing ni is significantly improved through the electrochemical polarization curve corrosion performance test. XRD diffraction detection shows that the sample treated by the embodiment contains anatase and hydroxyapatite. The scanning electron microscope shows that a large number of hydroxyapatite nanorods are formed on the surface of the coating, the length of the nanorods is about 1 μm, and the diameter of the nanorods is about 500 nm. The antibacterial ability of the surface of the sample treated by the embodiment is characterized, and the number of surviving bacteria is significantly reduced after 24 h of culture, and the antibacterial rate reaches 96.1%. After the sample treated by the embodiment is implanted into the tibia of a rabbit for 4 weeks, a large amount of new bone formation tissue is formed on the surface, which shows that the titanium implant with the micro-arc oxidation coating treated by the microwave hydrothermal treatment has higher corrosion resistance, antibacterial ability, apatite induction ability and osteogenic ability.

[0032] Specific implementation method two: the difference between the embodiment and the specific implementation method one is that the titanium implant without an oxide layer in step one is prepared by the following steps: polishing the surface of the titanium implant with 400# and 1000# metallographic sandpaper in sequence, then cleaning the titanium implant with deionized water, and finally drying the titanium implant at a temperature of 20-30℃ for 0.5-1h, so as to obtain the titanium implant without an oxide layer. The other steps are the same as those in the specific implementation method one.

[0033] Specific implementation method three: the difference between the embodiment and the specific implementation method one or two is that the titanium implant is titanium, titanium alloy, titanium-based medium-entropy alloy or titanium-based high-entropy alloy. The other steps are the same as those in the specific implementation method one or two.

[0034] Specific embodiment four: the difference between this embodiment and one of the specific embodiments one to three is that the titanium implant is a HCP-Ti type of medium entropy alloy or high entropy alloy, a BCC-Ti type of medium entropy alloy or high entropy alloy, a BCC type of medium entropy alloy or high entropy alloy, a BCC and HCP dual-phase medium entropy alloy or high entropy alloy. The others are the same as specific embodiments one to three.

[0035] Specific embodiment five: the difference between this embodiment and one of the specific embodiments one to four is that the concentration of disodium ethylenediaminetetraacetate in the electrolyte containing bioactive ingredients in step one is 8g / L-20g / L, the concentration of sodium hydroxide is 4g / L-15g / L, the concentration of sodium silicate is 4g / L-15g / L, the concentration of calcium dihydrogen phosphate is 5g / L-10g / L, and the concentration of calcium acetate is 4g / L-10g / L. The others are the same as specific embodiments one to four.

[0036] Specific embodiment six: the difference between this embodiment and one of the specific embodiments one to five is that the micro-arc oxidation time in step one is 10min-30min. The others are the same as specific embodiments one to five.

[0037] Specific embodiment seven: the difference between this embodiment and one of the specific embodiments one to six is that the mass percentage of hydrogen peroxide in step one is 20%. The others are the same as specific embodiments one to six.

[0038] Specific embodiment eight: the difference between this embodiment and one of the specific embodiments one to seven is that the alkali solution in step two is sodium hydroxide solution, ammonia water or potassium hydroxide solution. The others are the same as specific embodiments one to seven.

[0039] Specific embodiment nine: the difference between this embodiment and one of the specific embodiments one to eight is that the concentration of alkali solution in step two is 0.01mol / L-3.0mol / L. The others are the same as specific embodiments one to eight.

[0040] Specific embodiment ten: the difference between this embodiment and one of the specific embodiments one to nine is that the titanium implant treated by micro-arc oxidation in step two is immersed in the alkali solution, and the power is 500W-1000W and the temperature is 80℃-240℃, and the holding time is 10min-180min. The others are the same as specific embodiments one to nine.

[0041] The following examples are used to verify the beneficial effects of the present application:

[0042] Example one:

[0043] A method for constructing a high-performance multi-layer coating containing hydroxyapatite on a titanium implant surface to achieve antibacterial and osteogenic effects, which is carried out according to the following steps:

[0044] I. Micro-arc oxidation treatment:

[0045] The titanium implant without an oxide layer is placed in an electrolyte containing a bioactive component, the titanium implant without an oxide layer is used as an anode, and a stainless steel plate is used as a cathode, and then pulse direct current voltage is adopted to perform micro-arc oxidation on the titanium implant for 10 min under the conditions of a voltage of 400 V, a pulse frequency of 600 Hz, a duty cycle of 8%, and an electrolyte temperature of 20 DEG C, so that a titanium implant after micro-arc oxidation treatment is obtained.

[0046] The electrolyte containing a bioactive component is mixed from deionized water, disodium ethylenediaminetetraacetate, sodium hydroxide, sodium silicate, calcium dihydrogen phosphate, calcium acetate, hydrogen peroxide, and niobium oxalate; the concentration of disodium ethylenediaminetetraacetate in the electrolyte containing a bioactive component is 15 g / L, the concentration of sodium hydroxide is 5 g / L, the concentration of sodium silicate is 7.1 g / L, the concentration of calcium dihydrogen phosphate is 6.3 g / L, the concentration of calcium acetate is 8.8 g / L, the amount of hydrogen peroxide with a mass percentage of 20% added is 6 mL / L, and the concentration of niobium oxalate is 5 g / L.

[0047] II. Microwave hydrothermal treatment:

[0048] The titanium implant after micro-arc oxidation treatment is immersed in a caustic lye with a concentration of 0.5 mol / L, and then microwave hydrothermal treatment is performed under the conditions of a power of 800 W and a temperature of 200 DEG C for 60 min, so that a high-performance multi-layer coating containing niobium is obtained, which is named as MAO-Nb; the caustic lye is a sodium hydroxide solution.

[0049] The titanium implant without an oxide layer in step one is prepared according to the following steps: 400# and 1000# metallographic sandpaper are used to polish the surface of the titanium implant in sequence, then the titanium implant is cleaned with deionized water, and finally the titanium implant is dried at a temperature of 25 DEG C for 1 h, so that the titanium implant without an oxide layer is obtained.

[0050] The titanium implant is a TA2 base titanium plate with a size of 10 mm x 10 mm x 1 mm.

[0051] Comparative experiment: the comparative experiment is different from example one in that: the electrolyte containing a bioactive component in step one does not add niobium oxalate; step two obtains a high-performance multi-layer coating without niobium, which is named as MAO. The other steps are the same as those in example one.

[0052] Figure 1Electrochemical corrosion curves of the high-performance multilayer coating containing niobium prepared in Example 1 and the high-performance multilayer coating without niobium prepared in the comparative experiment; by comparing the electrochemical curves of the two, it can be clearly seen that the high-performance multilayer coating containing niobium has a lower corrosion current (-9.8 x 10 -10 A / cm 2 and corrosion potential (-0.25 V), indicating that the niobium-containing micro-arc oxidation coating has excellent corrosion resistance.

[0053] Figure 2 XRD pattern of the high-performance multilayer coating containing niobium prepared in Example 1, A is anatase peak, B is titanium peak, and C is hydroxyapatite peak; as can be seen from the figure, anatase and hydroxyapatite exist in the coating, and at the same time, since no niobium-containing phase is detected in the XRD pattern, it can be proved that the niobium element exists in an amorphous state.

[0054] Figure 3 Scanning electron microscope (SEM) image of the high-performance multilayer coating containing niobium prepared in Example 1; Figure 4 Transmission photo of the high-performance multilayer coating containing niobium prepared in Example 1; as can be seen from the scanning photo, a large number of hydroxyapatite nanorods are formed on the surface of the coating, with a length of about 1 μm and a diameter of about 500 nm. As can be seen from the transmission photo, after microwave hydrothermal treatment, a multilayer coating structure is obtained, including a titanium substrate, a porous layer and an epitaxial growth layer.

[0055] Figure 5 EDS energy spectrum of the high-performance multilayer coating containing niobium prepared in Example 1. As can be seen from the figure, the coating contains active elements such as calcium, phosphorus and niobium.

[0056] The antibacterial ability of the high-performance multilayer coating containing niobium prepared in Example 1 and the high-performance multilayer coating without niobium prepared in the comparative experiment was characterized. Test method: 30 μL of E. coli liquid with a concentration of 1.0 x 10 6 cfu / mL was taken from the bacterial liquid by a sterilized pipette, then evenly inoculated on the surface of the sample, then the sample was placed in a sterile 24-well culture plate, then transferred to a 37℃ biochemical incubator for culture for 24 h, and finally the sample was dried and gold sprayed for scanning electron microscope observation. Figure 6 Scanning photo of the bacterial morphology on the surface of the high-performance multilayer coating containing niobium prepared in Example 1; Figure 7 The antibacterial real object photo of the high-performance multilayer coating containing niobium prepared in Example 1 and the high-performance multilayer coating without niobium prepared in the comparative experiment. As can be seen from the figure, the survival number of E. coli on the high-performance multilayer coating containing niobium is significantly reduced, and the antibacterial rate reaches 96.1%. And the E. coli on the surface of the sample has become not smooth, uneven, and the surface structure has collapsed, showing atrophic morphology, that is, obvious collapse and death have occurred.

[0057] The niobium-containing high-performance multilayer coating prepared in Example One is implanted into the tibia of a rabbit for 4 weeks. Figure 8 The bone tissue remaining on the surface of the niobium-containing high-performance multilayer coating prepared in Example One is scanned. As shown in the figure, after the niobium-containing high-performance multilayer coating is implanted into the tibia of a rabbit for 4 weeks, the newly generated bone tissue remains in the holes on the surface of the coating after the implant is pulled out. The statistical calculation of the volume of the new bone and the bone volume in the range of 300 μm around the implant shows that the volume of the new bone accounts for 35% of the bone volume in the range of 300 μm around the implant.

[0058] Example Two: The difference between this example and Example One is that in Step One, the micro-arc oxidation is performed for 5 minutes at a voltage of 450 V, a pulse frequency of 600 Hz, a duty cycle of 8%, and an electrolyte temperature of 20°C. The other steps are the same as in Example One.

[0059] In the niobium-containing high-performance multilayer coating obtained in this example, anatase and hydroxyapatite exist. A large number of hydroxyapatite nanorods are formed on the surface of the niobium-containing high-performance multilayer coating. The coating contains active elements such as calcium, phosphorus, and niobium, and has excellent corrosion resistance. After the bacteria on the surface of the niobium-containing high-performance multilayer coating are cultured for 24 hours, the number of surviving bacteria decreases significantly, and the morphology of the bacteria collapses and dies. After the niobium-containing high-performance multilayer coating implant is implanted into the tibia of a rabbit for 4 weeks, the newly generated bone tissue remains on the surface of the implant after it is pulled out. The statistical calculation of the volume of the new bone and the bone volume in the range of 300 μm around the implant shows that the volume of the new bone accounts for 37% of the bone volume in the range of 300 μm around the implant.

[0060] Example Three: The difference between this example and Example One is that in Step Two, the temperature is 220°C, and the holding time is 60 minutes. The other steps are the same as in Example One.

[0061] In the niobium-containing high-performance multilayer coating obtained in this example, anatase and hydroxyapatite exist. A large number of hydroxyapatite nanorods are formed on the surface of the niobium-containing high-performance multilayer coating. The coating contains active elements such as calcium, phosphorus, and niobium, and has excellent corrosion resistance. After the bacteria on the surface of the niobium-containing high-performance multilayer coating are cultured for 24 hours, the number of surviving bacteria decreases significantly, and the morphology of the bacteria collapses and dies. After the niobium-containing high-performance multilayer coating implant is implanted into the tibia of a rabbit for 4 weeks, the newly generated bone tissue remains on the surface of the implant after it is pulled out. The statistical calculation of the volume of the new bone and the bone volume in the range of 300 μm around the implant shows that the volume of the new bone accounts for 39% of the bone volume in the range of 300 μm around the implant.

[0062] Example Four: The difference between this example and Example One is that the concentration of the alkali solution in Step Two is 0.01 mol / L. The other steps are the same as in Example One.

[0063] The high-performance multilayer coating containing niobium obtained in the embodiment contains anatase and hydroxyapatite. A large number of hydroxyapatite nanorods are formed on the surface of the high-performance multilayer coating containing niobium. The coating contains active elements such as calcium, phosphorus and niobium, and has excellent corrosion resistance. After the bacteria on the surface of the high-performance multilayer coating containing niobium are cultured for 24 hours, the number of surviving bacteria is significantly reduced, and the morphology of the bacteria collapses and dies obviously. After the implant containing the high-performance multilayer coating containing niobium is implanted into the tibia of a rabbit for 4 weeks, new bone tissue is left on the surface of the implant after the implant is pulled out. The statistical calculation of the volume of new bone and the volume of bone within a range of 300 μm around the implant shows that the volume of new bone accounts for 30% of the volume of bone within a range of 300 μm around the implant.

[0064] Example Five: The embodiment is different from Example One in that the concentration of the lye in Step Two is 1 mol / L. The other steps are the same as those in Example One.

[0065] The high-performance multilayer coating containing niobium obtained in the embodiment contains anatase and hydroxyapatite. A large number of hydroxyapatite nanorods are formed on the surface of the high-performance multilayer coating containing niobium. The coating contains active elements such as calcium, phosphorus and niobium, and has excellent corrosion resistance. After the bacteria on the surface of the high-performance multilayer coating containing niobium are cultured for 24 hours, the number of surviving bacteria is significantly reduced, and the morphology of the bacteria collapses and dies obviously. After the implant containing the high-performance multilayer coating containing niobium is implanted into the tibia of a rabbit for 4 weeks, new bone tissue is left on the surface of the implant after the implant is pulled out. The statistical calculation of the volume of new bone and the volume of bone within a range of 300 μm around the implant shows that the volume of new bone accounts for 30% of the volume of bone within a range of 300 μm around the implant.

[0066] Example Six: The embodiment is different from Example One in that the concentration of the lye in Step Two is 3.0 mol / L. The other steps are the same as those in Example One.

[0067] The high-performance multilayer coating containing niobium obtained in the embodiment contains anatase and hydroxyapatite. A large number of hydroxyapatite nanorods are formed on the surface of the high-performance multilayer coating containing niobium. The coating contains active elements such as calcium, phosphorus and niobium, and has excellent corrosion resistance. After the bacteria on the surface of the high-performance multilayer coating containing niobium are cultured for 24 hours, the number of surviving bacteria is significantly reduced, and the morphology of the bacteria collapses and dies obviously. After the implant containing the high-performance multilayer coating containing niobium is implanted into the tibia of a rabbit for 4 weeks, new bone tissue is left on the surface of the implant after the implant is pulled out. The statistical calculation of the volume of new bone and the volume of bone within a range of 300 μm around the implant shows that the volume of new bone accounts for 30% of the volume of bone within a range of 300 μm around the implant.

[0068] Example Seven: The embodiment is different from Example One in that the amount of hydrogen peroxide with a mass percentage of 20% in the electrolyte containing bioactive components in Step One is 10 mL / L. The other steps are the same as those in Example One.

[0069] The high performance multilayer coating containing niobium obtained in the example contains anatase and hydroxyapatite. A large number of hydroxyapatite nanorods are formed on the surface of the high performance multilayer coating containing niobium. The coating contains active elements such as calcium, phosphorus and niobium, and has excellent corrosion resistance. After bacteria are cultured on the surface of the high performance multilayer coating containing niobium for 24 hours, the number of surviving bacteria is significantly reduced, and the morphology of the bacteria collapses and dies obviously. After the implant of the high performance multilayer coating containing niobium is implanted into the tibia of a rabbit for 4 weeks, new bone tissue is left on the surface of the implant after the implant is pulled out. The statistical calculation of the volume of new bone and the volume of bone within a range of 300 μm around the implant shows that the volume of new bone accounts for 35% of the volume of bone within a range of 300 μm around the implant.

[0070] Example Eight: The difference between this example and Example One is that the concentration of niobium oxalate in the electrolyte containing bioactive components in Step One is 10 g / L. The other steps are the same as those in Example One.

[0071] The high performance multilayer coating containing niobium obtained in the example contains anatase and hydroxyapatite. A large number of hydroxyapatite nanorods are formed on the surface of the high performance multilayer coating containing niobium. The coating contains active elements such as calcium, phosphorus and niobium, and has excellent corrosion resistance. After bacteria are cultured on the surface of the high performance multilayer coating containing niobium for 24 hours, the number of surviving bacteria is significantly reduced, and the morphology of the bacteria collapses and dies obviously. After the implant of the high performance multilayer coating containing niobium is implanted into the tibia of a rabbit for 4 weeks, new bone tissue is left on the surface of the implant after the implant is pulled out. The statistical calculation of the volume of new bone and the volume of bone within a range of 300 μm around the implant shows that the volume of new bone accounts for 35% of the volume of bone within a range of 300 μm around the implant.

Claims

1. A method for constructing a high performance multilayer coating containing hydroxyapatite for antibacterial and osteogenic effects on the surface of a titanium implant, characterized by It is carried out according to the following steps: I. Micro-arc oxidation treatment: The titanium implant without an oxide layer is placed in an electrolyte containing a bioactive component, with the titanium implant without an oxide layer as an anode and a stainless steel plate as a cathode, and a pulse direct current voltage is used to carry out micro-arc oxidation for 10-30 min under the conditions of a voltage of 400-500 V, a pulse frequency of 600-1000 Hz, a duty cycle of 4-20%, and an electrolyte temperature of 20 DEG C, to obtain a titanium implant after micro-arc oxidation treatment; The electrolyte containing a bioactive component is mixed from deionized water, disodium ethylenediaminetetraacetate, sodium hydroxide, sodium silicate, calcium dihydrogen phosphate, calcium acetate, hydrogen peroxide, and niobium oxalate; the concentration of disodium ethylenediaminetetraacetate in the electrolyte containing a bioactive component is 8-20 g / L, the concentration of sodium hydroxide is 4-15 g / L, the concentration of sodium silicate is 4-15 g / L, the concentration of calcium dihydrogen phosphate is 5-10 g / L, the concentration of calcium acetate is 4-10 g / L, the amount of hydrogen peroxide added is 6-15 mL / L, and the concentration of niobium oxalate is 5-20 g / L; the mass percentage of hydrogen peroxide is 20%; II. Microwave hydrothermal treatment: The titanium implant after micro-arc oxidation treatment is immersed in an alkali solution under the conditions of a power of 500-1000 W and a temperature of 80-240 DEG C for 10-180 min, to obtain a high-performance multi-layer coating implant containing niobium, i.e. to complete the method for constructing a hydroxyapatite high-performance multi-layer coating on the surface of a titanium implant with antibacterial and osteogenic effects; The alkali solution is a sodium hydroxide solution, ammonia water, or a potassium hydroxide solution; the concentration of the alkali solution is 0.01-3.0 mol / L; After the prepared high-performance multi-layer coating implant containing niobium is implanted into the tibia for 4 weeks, the implant is pulled out, and the newly generated bone tissue is left in the coating pores on the surface of the implant.

2. A method of constructing a high performance multi-layer coating comprising hydroxyapatite for antibacterial and osteogenic effects on the surface of a titanium implant according to claim 1, characterized in that The titanium implant without an oxide layer in step I is prepared according to the following steps: the surface of the titanium implant is polished with 400# and 1000# metallographic sandpaper in sequence, then washed with deionized water, and finally dried at a temperature of 20-30 DEG C for 0.5-1 h, to obtain the titanium implant without an oxide layer.

3. A method of constructing a high performance multi-layer coating comprising hydroxyapatite for antibacterial and osteogenic effects on the surface of a titanium implant according to claim 2, characterized in that The titanium implant is titanium or a titanium alloy.

4. A method of constructing a high performance multi-layer coating comprising hydroxyapatite for antibacterial and osteogenic effects on the surface of a titanium implant according to claim 2, characterized in that The titanium implant is an HCP-Ti type medium-entropy alloy or high-entropy alloy, a BCC type medium-entropy alloy or high-entropy alloy, or a BCC and HCP dual-phase medium-entropy alloy or high-entropy alloy.

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