CN114732945B - Method for improving bioactivity of titanium alloy bone - Google Patents

Method for improving bioactivity of titanium alloy bone Download PDF

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CN114732945B
CN114732945B CN202210389874.5A CN202210389874A CN114732945B CN 114732945 B CN114732945 B CN 114732945B CN 202210389874 A CN202210389874 A CN 202210389874A CN 114732945 B CN114732945 B CN 114732945B
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titanium alloy
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gelatin
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CN114732945A (en
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杨剑冰
庞兴志
赵玲峰
谢聪
莫青凤
王金燕
郑述芳
黄春燕
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Guangxi Agricultural Vocational University
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    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
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    • A61L27/00Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/50Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
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    • A61L2430/02Materials or treatment for tissue regeneration for reconstruction of bones; weight-bearing implants

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Abstract

The invention discloses a method for improving the bioactivity of titanium alloy bone, which comprises the following steps: soaking and cleaning the surface of the titanium alloy by using an alkaline solution, spraying and brushing alcohol, acetone and clear water in sequence, and drying in a vacuum environment; quickly placing the titanium alloy in an atomization box, performing pitting corrosion on the surface of the titanium alloy by using acid mist, and drying the titanium alloy after the pitting corrosion is completed; soaking the titanium alloy into a collagen solution, taking out the titanium alloy, uniformly spraying metal powder to the surface of the titanium alloy in a vacuum environment before the collagen solution is completely dried, soaking the titanium alloy into the collagen solution containing the gelatin slow-release ball, taking out the titanium alloy, and drying the titanium alloy in a nitrogen environment by adopting nitrogen; and then soaking the titanium alloy into the chondroitin sulfate solution, taking out after full soaking, and drying by adopting nitrogen in a nitrogen environment to obtain the treated titanium alloy. The method of the invention can fully improve the bioactivity of the titanium alloy, is beneficial to the combination of muscle tissues and titanium alloy bones, and is beneficial to the rehabilitation of patients.

Description

Method for improving bioactivity of titanium alloy bone
Technical Field
The invention relates to the technical field of biomedical materials, in particular to a method for improving the bioactivity of a titanium alloy bone.
Background
Biomedical titanium and titanium alloys are widely used for intracorporeal implants because of their excellent biocompatibility and resistance to physical corrosion. In recent years, titanium and titanium alloys have transformed typical inert medical titanium and titanium alloy materials into bioactive and tissue-inducing materials capable of inducing tissue regeneration and repair in vivo by applying surface modification techniques. In the field of biomedical materials, titanium and titanium alloy have wider application prospect.
Titanium alloys that can be used for implantation in the human body tend to have the following properties: 1. has good biocompatibility; 2. has sufficient mechanical strength and anti-fatigue capability; 3. the elastic modulus is proper, and the mechanical conduction of a bone-material interface is facilitated; 4. has certain bone growth inductivity and the like. Therefore, it is necessary to improve the bioactivity of the titanium alloy surface.
Disclosure of Invention
The invention aims to: aiming at the existing problems, the method for improving the bioactivity of the titanium alloy bone is provided, and the titanium alloy treated by the method has high bioactivity on the surface and is suitable for repairing the human skeleton loss.
In order to achieve the purpose of the invention, the technical scheme adopted by the invention is as follows:
a method for improving the bioactivity of titanium alloy bone comprises the following steps:
(1) Surface cleaning: soaking and cleaning the surface of the titanium alloy by using an alkaline solution, spraying and brushing alcohol, acetone and clear water in sequence, and drying in a vacuum environment;
(2) Atomizing and pitting corrosion: quickly placing the dried titanium alloy in the step (1) into an atomization box, vacuumizing, spraying acid mist particles into the atomization box, filling the entire atomization box with acid mist to surround the titanium alloy, performing pitting corrosion on the surface of the titanium alloy by the acid mist, and drying by using nitrogen after the completion;
(3) Spraying metal powder: immersing the titanium alloy into a collagen solution, taking out the titanium alloy, grinding metal powder to a proper particle size before the collagen solution is completely dried, uniformly spraying the metal powder on the surface of the titanium alloy in a vacuum environment, and quickly relieving pressure to embed the metal powder into the collagen solution layer;
(4) Filling gelatin slow-release balls: preparing gelatin slow-release balls, uniformly dispersing the gelatin slow-release balls in a collagen solution, soaking the titanium alloy in the collagen solution containing the gelatin slow-release balls, taking out the titanium alloy, and drying the titanium alloy in a nitrogen environment by adopting nitrogen;
(5) Surface covering: and (4) soaking the titanium alloy treated in the step (4) in a chondroitin sulfate solution, taking out after full soaking, and drying by adopting nitrogen in a nitrogen environment to obtain the treated titanium alloy.
Further, in the step (1), the alkali solution is a dilute sodium hydroxide solution, the soaking and cleaning time is 1-3 hours, and the spraying and washing is to uniformly wash the surface of the titanium alloy by sequentially pressurizing and spraying alcohol, acetone and clear water.
Further, in step (2), the atomization case is a closed box body provided with an opening and closing door, a spraying system is arranged in the atomization case to atomize and spray the solution to permeate the solution in the atomization case, and the atomization case is further connected with a vacuum pump to dry the inner space of the atomization case.
Further, in the step (2), the particle size of the acid mist particles is 20-100um, and the acid mist is formed by spraying hydrochloric acid solution.
Further, in the step (3), the metal powder is magnesium powder and titanium powder, wherein the mass ratio of the magnesium powder to the titanium powder is 1:2, and the titanium powder is sprayed firstly and then the magnesium powder is sprayed when the metal powder is sprayed.
The collagen solution is formed by dissolving collagen in hexafluoroisopropanol, wherein the mass fraction of the collagen is 3-5%.
Further, in the step (4), the preparation method of the gelatin sustained-release ball is as follows: adding gelatin into water for dissolving and diluting, stirring and drying to form gelatin granules, soaking the gelatin granules into rhBMP-2 solution prepared by PBS, keeping the temperature constant, soaking for 10-24 hours, washing and drying by PBS, adding genipin, standing and curing at room temperature in a dark place for 12-24 hours, washing the genipin by absolute ethyl alcohol, drying in vacuum and sieving to obtain the gelatin sustained-release balls.
Further, the particle size of the gelatin particles is 0.01-0.2mm, the concentration of the rhBMP-2 solution is 150-200ng/mL, and the addition amount of the genipin is 8-10mL of genipin with the mass concentration of 1% added in every 1g of gelatin.
Further, in the step (5), the chondroitin sulfate solution has a chondroitin sulfate mass fraction of 3-5%, and is immersed in the chondroitin sulfate solution for 1-5min.
In summary, due to the adoption of the technical scheme, the invention has the beneficial effects that:
(1) The atomization pitting corrosion method adopted on the surface of the titanium alloy is beneficial to increasing the surface area of the titanium alloy, pit points formed by pitting corrosion are beneficial to filling and attaching of metal powder, and acid mist adopted by the pitting corrosion is fine and dense in corrosion points, so that the surface area is increased while the integral surface structure of the titanium alloy is not influenced, the adhesion of a regenerated tissue and an implant is improved, and rejection reaction is reduced.
(2) The coating formed by metal powder is firstly embedded in the collagen coating, the structure is stable, the coating is not easy to slip off, the thickness of the coating is smaller than that of the surface active coating formed by direct stacking, the two layers of metal powder embedded in the collagen coating are beneficial to forming tiny gaps among metal particles and the adhesion, proliferation and differentiation growth of cells, and the regenerated cell tissues can be tightly combined with the porous titanium alloy coating.
(3) The rhBMP-2 is slowly released by arranging the gelatin slow-release ball, and controllable and stable drug release is realized by diffusion and gradual decomposition or dissolution of the carrier, so that the sustained osteoinduction effect can be exerted, the early osseointegration and the osseointegration are promoted, and the long-term stable effect is achieved.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in further detail below with reference to preferred embodiments. However, it should be noted that the numerous details set forth in the description are merely intended to provide a thorough understanding of one or more aspects of the present invention, even though such aspects of the invention may be practiced without these specific details.
A method for improving the bioactivity of titanium alloy bone comprises the following steps:
(1) Surface cleaning: soaking and cleaning the surface of the titanium alloy by using an alkaline solution, spraying and brushing alcohol, acetone and clear water in sequence, and drying in a vacuum environment;
(2) Atomization pitting corrosion: quickly placing the dried titanium alloy in the step (1) into an atomization box, vacuumizing, spraying acid mist particles into the atomization box, filling the entire atomization box with acid mist to surround the titanium alloy, performing pitting corrosion on the surface of the titanium alloy by the acid mist, and drying by using nitrogen after the completion;
(3) Spraying metal powder: immersing the titanium alloy into a collagen solution, taking out the titanium alloy, grinding metal powder to a proper particle size before the collagen solution is completely dried, uniformly spraying the metal powder on the surface of the titanium alloy in a vacuum environment, and quickly relieving pressure to embed the metal powder into the collagen solution layer;
(4) Filling the gelatin slow-release ball: preparing gelatin slow-release balls, uniformly dispersing the gelatin slow-release balls in a collagen solution, soaking the titanium alloy in the collagen solution containing the gelatin slow-release balls, taking out the titanium alloy, and drying the titanium alloy in a nitrogen environment by adopting nitrogen;
(5) Surface covering: and (5) soaking the titanium alloy treated in the step (4) in a chondroitin sulfate solution, taking out after full soaking, and drying by adopting nitrogen in a nitrogen environment to obtain the treated titanium alloy.
In the step (1), the alkali solution is a dilute sodium hydroxide solution, the soaking and cleaning time is 1-3 hours, and the spraying and washing is to uniformly wash the surface of the titanium alloy by sequentially pressurizing and spraying alcohol, acetone and clear water. The oxide and the impurities on the surface can be cleaned by using sodium hydroxide, and the subsequent cleaning by using alcohol, acetone and clean water in sequence is favorable for activating the surface activity of the titanium alloy.
In step (2), the atomization box is a closed box body provided with a switch door, a spraying system is arranged in the atomization box to atomize and spray solution to permeate into the atomization box body, and a vacuum pump is further connected with the atomization box to pump the inner space of the atomization box to be dry. Wherein the spraying system in the atomizing box is any one of the existing atomizing devices which can spray acid solution at micron level, and the spraying outlet is arranged in the atomizing box.
In the step (2), the particle size of the acid mist particles is 20-100um, and the acid mist is formed by spraying hydrochloric acid solution. The small grain size makes pits formed by corrosion dense and small, and ensures that the titanium alloy integrally finishes a microscopic pit structure.
In the step (3), the metal powder is magnesium powder and titanium powder, wherein the mass ratio of the magnesium powder to the titanium powder is 1:2, and the titanium powder is sprayed firstly and then the magnesium powder is sprayed when the metal powder is sprayed. The collagen solution is formed by dissolving collagen in hexafluoroisopropanol, wherein the mass fraction of the collagen is 3-5%. Because the substrate is made of titanium alloy, the titanium powder is firstly sprayed, and then the magnesium powder is sprayed on the outer surface, so that the metal powder layer is more stably attached to the substrate.
In the step (4), the preparation method of the gelatin sustained-release ball is as follows: adding gelatin into water for dissolving and diluting, stirring and drying to form gelatin granules, soaking the gelatin granules into rhBMP-2 solution prepared by PBS, keeping the temperature constant, soaking for 10-24 hours, washing and drying by PBS, adding genipin, standing and curing at room temperature in a dark place for 12-24 hours, washing the genipin by absolute ethyl alcohol, drying in vacuum and sieving to obtain the gelatin sustained-release balls. The rhBMP-2 is soaked in gelatin and can be slowly released to act on the tissue osteogenesis.
The particle size of the gelatin particles is 0.01-0.2mm, the concentration of the rhBMP-2 solution is 150-200ng/mL, and the addition amount of the genipin is 8-10mL of genipin with the mass concentration of 1% added in every 1g of gelatin.
In the step (5), the chondroitin sulfate solution contains 3-5% of chondroitin sulfate by mass, and the soaking time in the chondroitin sulfate solution is 1-5min.
Example 1
A method for improving the bioactivity of titanium alloy bone comprises the following steps:
(1) Surface cleaning: soaking and cleaning the surface of the titanium alloy by adopting an alkaline solution, sequentially spraying and brushing alcohol, acetone and clear water, and drying in a vacuum environment, wherein the alkaline solution is a dilute sodium hydroxide solution, the soaking and cleaning time is 1 hour, and the spraying and brushing step is to uniformly wash the surface of the titanium alloy by sequentially pressurizing and spraying the alcohol, the acetone and the clear water;
(2) Atomizing and pitting corrosion: quickly placing the dried titanium alloy in the step (1) into an atomization box, vacuumizing, spraying acid mist particles into the atomization box, enabling the whole atomization box to be filled with acid mist to surround the titanium alloy, performing pitting corrosion on the surface of the titanium alloy by the acid mist, drying the titanium alloy by using nitrogen after the completion of the pitting corrosion, wherein the atomization box is a closed box body provided with a switch door, a spraying system is arranged in the atomization box, atomizing and spraying the solution to be diffused in the atomization box body, the atomization box is also connected with a vacuum pump, the internal space of the atomization box is dried, the particle size of the acid mist particles is 20 microns, and the acid mist is formed by spraying the hydrochloric acid solution;
(3) Spraying metal powder: the method comprises the steps of immersing a titanium alloy into a collagen solution, taking out the titanium alloy, grinding metal powder to be proper in particle size before the collagen solution is completely dried, uniformly spraying the metal powder to the surface of the titanium alloy in a vacuum environment, quickly relieving pressure to enable the metal powder to be embedded into a collagen solution layer, wherein the metal powder is magnesium powder and titanium powder, the mass ratio of the magnesium powder to the titanium powder is 1:2, and spraying the titanium powder and then the magnesium powder when the metal powder is sprayed. The collagen solution is formed by dissolving collagen in hexafluoroisopropanol, wherein the mass fraction of the collagen is 3%;
(4) Filling the gelatin slow-release ball: preparing gelatin slow-release balls, uniformly dispersing the gelatin slow-release balls in a collagen solution, soaking a titanium alloy into the collagen solution containing the gelatin slow-release balls, taking out the titanium alloy, and drying the titanium alloy in a nitrogen environment by adopting nitrogen, wherein the preparation method of the gelatin slow-release balls comprises the following steps: adding gelatin into water for dissolving and diluting, stirring and drying to form gelatin granules, soaking the gelatin granules into rhBMP-2 solution prepared by PBS, keeping the temperature constant, soaking for 10 hours, washing and drying by PBS, adding genipin, standing and curing for 12 hours in a dark place at room temperature, washing the genipin by absolute ethyl alcohol, drying in vacuum and sieving to obtain the gelatin sustained-release balls. The particle size of the gelatin particles is 0.01m, the concentration of the rhBMP-2 solution is 150ng/mL, and the addition amount of the genipin is 8mL of genipin with the mass concentration of 1% added in every 1g of gelatin;
(5) Surface covering: and (3) immersing the titanium alloy treated in the step (4) into a chondroitin sulfate solution, taking out after full immersion, and drying by adopting nitrogen in a nitrogen environment to obtain the treated titanium alloy, wherein the mass fraction of chondroitin sulfate in the chondroitin sulfate solution is 3%, and the time for immersing the chondroitin sulfate solution is 1min.
Example 2
A method for improving the bioactivity of titanium alloy bone comprises the following steps:
(1) Surface cleaning: soaking and cleaning the surface of the titanium alloy by adopting an alkaline solution, sequentially spraying and brushing alcohol, acetone and clear water, drying in a vacuum environment, wherein the alkaline solution is a dilute sodium hydroxide solution, the soaking and cleaning time is 3 hours, and the spraying and brushing step is to uniformly wash the surface of the titanium alloy by sequentially pressurizing and spraying the alcohol, the acetone and the clear water;
(2) Atomizing and pitting corrosion: quickly placing the dried titanium alloy in the step (1) into an atomization box, vacuumizing, spraying acid mist particles into the atomization box, enabling the whole atomization box to be filled with acid mist to surround the titanium alloy, performing pitting corrosion on the surface of the titanium alloy by the acid mist, drying the titanium alloy by using nitrogen after the completion of the pitting corrosion, wherein the atomization box is a closed box body provided with a switch door, a spraying system is arranged in the atomization box, atomizing and spraying the solution to be diffused in the atomization box body, the atomization box is also connected with a vacuum pump, the internal space of the atomization box is dried, the particle size of the acid mist particles is 100 microns, and the acid mist is formed by spraying the hydrochloric acid solution;
(3) Spraying metal powder: the method comprises the steps of immersing a titanium alloy into a collagen solution, taking out the titanium alloy, grinding metal powder to be proper in particle size before the collagen solution is completely dried, uniformly spraying the metal powder to the surface of the titanium alloy in a vacuum environment, quickly relieving pressure to enable the metal powder to be embedded into a collagen solution layer, wherein the metal powder is magnesium powder and titanium powder, the mass ratio of the magnesium powder to the titanium powder is 1:2, and spraying the titanium powder and then the magnesium powder when the metal powder is sprayed. The collagen solution is formed by dissolving collagen in hexafluoroisopropanol, wherein the mass fraction of the collagen is 5%;
(4) Filling the gelatin slow-release ball: preparing gelatin slow-release balls, uniformly dispersing the gelatin slow-release balls in a collagen solution, soaking a titanium alloy into the collagen solution containing the gelatin slow-release balls, taking out the titanium alloy, and drying the titanium alloy in a nitrogen environment by adopting nitrogen, wherein the preparation method of the gelatin slow-release balls comprises the following steps: adding gelatin into water for dissolving and diluting, stirring and drying to form gelatin granules, soaking the gelatin granules into rhBMP-2 solution prepared by PBS, keeping the temperature constant, soaking for 24 hours, washing and drying by PBS, adding genipin, standing and curing for 12-24 hours in a dark place at room temperature, washing the genipin by absolute ethyl alcohol, drying in vacuum and sieving to obtain the gelatin sustained-release balls. The particle size of the gelatin particles is 0.2mm, the concentration of the rhBMP-2 solution is 200ng/mL, and the addition amount of the genipin is 10mL of genipin with the mass concentration of 1% added in every 1g of gelatin;
(5) Surface covering: and (3) immersing the titanium alloy treated in the step (4) into a chondroitin sulfate solution, taking out after full immersion, and drying by adopting nitrogen in a nitrogen environment to obtain the treated titanium alloy, wherein the mass fraction of chondroitin sulfate in the chondroitin sulfate solution is 5%, and the time for immersing the chondroitin sulfate solution is 1-5min.
Example 3
A method for improving the bioactivity of titanium alloy bone comprises the following steps:
(1) Surface cleaning: soaking and cleaning the surface of the titanium alloy by adopting an alkaline solution, sequentially spraying and brushing alcohol, acetone and clear water, drying in a vacuum environment, wherein the alkaline solution is a dilute sodium hydroxide solution, the soaking and cleaning time is 2 hours, and the spraying and brushing step is to uniformly wash the surface of the titanium alloy by sequentially pressurizing and spraying the alcohol, the acetone and the clear water;
(2) Atomizing and pitting corrosion: quickly placing the dried titanium alloy in the step (1) into an atomization box, vacuumizing, spraying acid mist particles into the atomization box, enabling the whole atomization box to be filled with acid mist to surround the titanium alloy, performing pitting corrosion on the surface of the titanium alloy by the acid mist, drying the titanium alloy by using nitrogen after the completion of the pitting corrosion, wherein the atomization box is a closed box body provided with a switch door, a spraying system is arranged in the atomization box, atomizing and spraying the solution to be diffused in the atomization box body, the atomization box is also connected with a vacuum pump, the internal space of the atomization box is dried, the particle size of the acid mist particles is 80 microns, and the acid mist is formed by spraying the hydrochloric acid solution;
(3) Spraying metal powder: the method comprises the steps of immersing a titanium alloy into a collagen solution, taking out the titanium alloy, grinding metal powder to be proper in particle size before the collagen solution is completely dried, uniformly spraying the metal powder to the surface of the titanium alloy in a vacuum environment, quickly relieving pressure to enable the metal powder to be embedded into a collagen solution layer, wherein the metal powder is magnesium powder and titanium powder, the mass ratio of the magnesium powder to the titanium powder is 1:2, and spraying the titanium powder and then the magnesium powder when the metal powder is sprayed. The collagen solution is formed by dissolving collagen in hexafluoroisopropanol, wherein the mass fraction of the collagen is 4%;
(4) Filling the gelatin slow-release ball: preparing gelatin slow-release balls, uniformly dispersing the gelatin slow-release balls in a collagen solution, soaking a titanium alloy into the collagen solution containing the gelatin slow-release balls, taking out the titanium alloy, and drying the titanium alloy in a nitrogen environment by adopting nitrogen, wherein the preparation method of the gelatin slow-release balls comprises the following steps: adding gelatin into water for dissolving and diluting, stirring and drying to form gelatin granules, soaking the gelatin granules into rhBMP-2 solution prepared by PBS, keeping the temperature constant, soaking for 18 hours, washing and drying by PBS, adding genipin, standing and curing for 16 hours in a dark place at room temperature, washing the genipin by absolute ethyl alcohol, drying in vacuum and sieving to obtain the gelatin sustained-release balls. The particle size of the gelatin particles is 0.1m, the concentration of the rhBMP-2 solution is 180ng/mL, and the addition amount of the genipin is that 9mL of genipin with the mass concentration of 1% is added into every 1g of gelatin;
(5) Surface covering: and (5) immersing the titanium alloy treated in the step (4) in a chondroitin sulfate solution, taking out after full immersion, and drying by adopting nitrogen in a nitrogen environment to obtain the treated titanium alloy, wherein the mass fraction of chondroitin sulfate in the chondroitin sulfate solution is 4%, and the time for immersing the chondroitin sulfate solution is 3min.
In the titanium alloy treated in the above embodiment, the surface part has very good osteogenesis inducing capability, the chondroitin sulfate is firstly immersed in the outermost layer, which is favorable for promoting the formation of cartilage and regulating the biological activity of the surface, and the chondroitin sulfate is internally provided with the gelatin slow-release ball, wherein the gelatin is a main organic component of bone tissues, namely a collagen hydrolysate, and can be obtained by hydrolyzing and refining animal collagen, and the titanium alloy is low in price, easy to obtain, free of antigenicity, low in friction coefficient, biodegradable and safe and effective in use. The rhBMP-2 has a strong effect of inducing osteogenesis, is applied clinically, can obviously promote the conversion of immature osteoblasts and bone precursor cells to mature osteoblasts, and has strong ectopic and in-situ osteogenesis capacity. The rhBMP-2 has obvious bone induction effect on the growth of osteoblasts in vitro and the formation of new bone tissues in vivo. The inner part of the titanium alloy is additionally provided with tiny gaps on the surface of the titanium alloy through the metal powder layer, the adhesion, proliferation and differentiation growth of cells are facilitated, regenerated cell tissues can be tightly combined with the porous titanium alloy coating, the binding force of the gelatin slow-release ball and the metal powder on the titanium alloy can be increased on the basis of not influencing the material performance by adopting a collagen solution, the surface area of the titanium alloy can be greatly increased by carrying out pitting corrosion on the surface of the titanium alloy through an atomized acid solution, after the metal powder and the gelatin slow-release ball are covered, the sinking degree of the surface can be reduced, the surface is modified, meanwhile, the characteristic of incomplete and smooth surface is also kept, and the contact area of muscle tissues and the surface of the implant is increased.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that those skilled in the art can make various improvements and modifications without departing from the principle of the present invention, and these improvements and modifications should also be construed as the protection scope of the present invention.

Claims (9)

1. A method for improving the bioactivity of titanium alloy bone is characterized by comprising the following operation steps:
(1) Surface cleaning: soaking and cleaning the surface of the titanium alloy by using an alkaline solution, spraying and brushing alcohol, acetone and clear water in sequence, and drying in a vacuum environment;
(2) Atomization pitting corrosion: quickly placing the dried titanium alloy in the step (1) into an atomization box, vacuumizing, spraying acid mist particles into the atomization box, filling the entire atomization box with acid mist to surround the titanium alloy, performing pitting corrosion on the surface of the titanium alloy by the acid mist, and drying by using nitrogen after the completion;
(3) Spraying metal powder: immersing the titanium alloy into a collagen solution, taking out the titanium alloy, grinding metal powder to a proper particle size before the collagen solution is completely dried, uniformly spraying the metal powder on the surface of the titanium alloy in a vacuum environment, and quickly relieving pressure to embed the metal powder into the collagen solution layer;
(4) Filling the gelatin slow-release ball: soaking gelatin particles into rhBMP-2 solution prepared by PBS to prepare gelatin slow-release balls, placing the gelatin slow-release balls into collagen solution for uniform dispersion, soaking the titanium alloy into the collagen solution containing the gelatin slow-release balls, taking out the titanium alloy, and drying the titanium alloy in a nitrogen environment by adopting nitrogen;
(5) Surface covering: and (4) soaking the titanium alloy treated in the step (4) in a chondroitin sulfate solution, taking out after full soaking, and drying by adopting nitrogen in a nitrogen environment to obtain the treated titanium alloy.
2. The method for improving the bioactivity of titanium alloy bone as claimed in claim 1, wherein: in the step (1), the alkali solution is a sodium hydroxide dilute solution, the soaking and cleaning time is 1-3 hours, and the spray-brushing washing is to uniformly wash the surface of the titanium alloy by sequentially pressurizing and spraying alcohol, acetone and clear water.
3. The method of claim 1, wherein the method comprises: in step (2), the atomization box is a closed box body provided with a switch door, a spraying system is arranged in the atomization box to atomize and spray solution to permeate into the atomization box body, and a vacuum pump is further connected with the atomization box to pump the inner space of the atomization box to be dry.
4. The method of claim 1, wherein the method comprises: in the step (2), the particle size of the acid mist particles is 20-100um, and the acid mist is formed by spraying hydrochloric acid solution.
5. The method of claim 1, wherein the method comprises: in the step (3), the metal powder is magnesium powder and titanium powder, wherein the mass ratio of the magnesium powder to the titanium powder is 1:2, and the titanium powder is sprayed firstly and then the magnesium powder is sprayed when the metal powder is sprayed.
6. The method of claim 1, wherein the method comprises: the collagen solution is formed by dissolving collagen in hexafluoroisopropanol, wherein the mass fraction of the collagen is 3-5%.
7. The method of claim 1, wherein the method comprises: in the step (4), the preparation method of the gelatin slow-release ball is as follows: adding gelatin into water for dissolving and diluting, stirring and drying to form gelatin granules, soaking the gelatin granules into rhBMP-2 solution prepared by PBS, keeping the temperature constant, soaking for 10-24 hours, washing and drying by PBS, adding genipin, standing and curing at room temperature in a dark place for 12-24 hours, washing the genipin by absolute ethyl alcohol, drying in vacuum and sieving to obtain the gelatin sustained-release balls.
8. The method of claim 7, wherein the method comprises: the particle size of the gelatin particles is 0.01-0.2mm, the concentration of the rhBMP-2 solution is 150-200ng/mL, and the addition amount of the genipin is 8-10mL of genipin with the mass concentration of 1% added in every 1g of gelatin.
9. The method of claim 1, wherein the method comprises: in the step (5), the chondroitin sulfate solution contains 3-5% of chondroitin sulfate by mass, and the soaking time in the chondroitin sulfate solution is 1-5min.
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