CN108079381B - Preparation method of medical titanium alloy surface biological piezoelectric composite coating - Google Patents
Preparation method of medical titanium alloy surface biological piezoelectric composite coating Download PDFInfo
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Abstract
The invention discloses a preparation method of a medical titanium alloy surface bio-piezoelectric composite coating, which comprises the steps of firstly generating a titanium dioxide coating with a compact inner layer and a porous surface layer on the surface of a titanium alloy substrate in situ by adopting a micro-arc oxidation technology, then generating a barium titanate coating on the titanium dioxide coating by adopting a hydrothermal chemical method through in-situ reaction, and finally filling holes on the surface of the polarized coating, namely forming the composite coating with the bio-piezoelectric property on the surface of the medical titanium alloy. The coating prepared by the invention has a compact inner layer, is well combined with a matrix, has high stability, and can effectively prevent harmful metal ions from dissolving out to body fluid; the barium titanate coating with the porous surface layer can generate a piezoelectric effect, promote local blood circulation and further accelerate bone repair; the holes are filled with substances or antibacterial drugs which are beneficial to the growth of early bone tissues, and meanwhile, the rough surface is beneficial to the adhesion and proliferation of cells, so that the metal material has good biocompatibility and bioactivity.
Description
Technical Field
The invention belongs to the technical field of surface modification of biomedical materials, and relates to a preparation method of a biomedical titanium alloy surface bio-piezoelectric composite coating.
Background
Medical titanium alloy is widely applied in the field of medical implantation due to its own high strength, low elastic modulus, non-magnetism, excellent chemical stability and good biocompatibility. However, the medical titanium alloy has great difference with the bone tissue in terms of components and structure, and is only simply and mechanically embedded with the bone tissue after being implanted into a human body, so that strong chemical bonding cannot be formed, and the implant is easy to loosen and fall off. Therefore, the surface modification is very necessary, and the surface modification can not only retain the excellent performance of the titanium alloy, but also solve the problems of lacking bioactivity and the like.
Research shows that the bone tissue is a natural piezoelectric body and can convert the tiny mechanical stress of self movement into electric effect to generate micro current. The micro-current acts on calcium ions and phosphate ions in human body fluid to promote the deposition of the calcium ions and the phosphate ions, provides nutrients for the growth of bone tissues, improves the integration of host bone implant materials, and simultaneously, the electric signal acts on osteocytes and extracellular environment to promote the generation of extracellular interstitial macromolecules, so that the healing of living bones is further accelerated. At present, the piezoelectric ceramics is mainly researched as a bone repair material, and lead-free piezoelectric ceramics barium titanate (BaTiO)3) Its good piezoelectricity and biocompatibility have been widely studied. Therefore, the research on the biological piezoelectric composite coating with excellent piezoelectric performance, high bioactivity, strong binding force between the coating and the substrate and good coating stability is a hotspot and difficulty in the field of surface modification of biomedical materials.
Chinese patent "a method for preparing a hydroxyapatite coating on the surface of a titanium alloy substrate" (application date 2014.11.14, publication No. CN105018924A, publication date 2015.11.04) discloses a method for preparing a hydroxyapatite coating on the surface of a titanium alloy substrate, which comprises spraying mixed titanium powder and hydroxyapatite powder onto the surface of a titanium alloy substrate by using a cold spraying technology, and then preparing a hydroxyapatite coating on the surface of the titanium alloy substrate by using a laser cladding technology. The coating mainly relies on hydroxyapatite to induce new bone formation to improve the bioactivity of the titanium alloy surface, but the hydroxyapatite can be gradually degraded after being implanted into a human body for a long time, a film layer falls off, and the bioactivity is gradually reduced.
Chinese patent application No. 2005.10.14, publication No. CN1785439A, publication No. 2006.06.14 discloses a method for modifying the surface of a titanium material, which is characterized in that a porous oxide film layer is formed by micro-arc oxidation technology, and then a composite coating of fluorhydroxyapatite and barium titanate (FHABT) is prepared on the surface of a sample by electrophoretic deposition technology to improve the biocompatibility and bioactivity. However, after the fluorhydroxyapatite in the coating is degraded, the barium titanate particles can not be degraded in a human body and can be dissociated in the human body, so that potential damage can be caused to the human body, and meanwhile, the bonding force between the electrophoretically deposited film and the oxide film formed by micro-arc oxidation is poor.
Chinese patent "alkali liquor water vapor post-treatment method of titanium surface micro-arc oxidation bioactive coating" (application date 2013.07.18, publication No. CN103334144A, publication date 2013.10.02) discloses a method for modifying the surface of a titanium material, which is mainly characterized in that micro-arc oxidation is carried out in mixed electrolyte containing calcium and phosphorus salt to form an oxide film on the surface of the titanium substrate, and then the alkali liquor water vapor treatment is carried out to prepare the bioactive coating on the titanium surface. The coating avoids the problems that the conventional hydrothermal chemical method causes the dissolution of bioactive elements and the generation of apatite is less by the alkali-heat water vapor treatment. However, the bioactive substance of the coating is apatite, and after the bioactive substance is completely degraded, the activity of the matrix is reduced, so that the stability of the coating is insufficient.
Chinese patent (application No. 2004.01.16, publication No. CN1557505A, publication No. 2004.12.29) discloses a biological coating with a gradient metal surface structure, its preparation method and its application. The coating substrate is titanium or titanium alloy, and is structurally characterized in that the gradient structure of compact inner layer and uneven and porous surface layer is adopted. However, the active substances of the coating are mainly calcium and phosphorus elements in the coating, and the bioactivity of the active substances is insufficient.
Hwangbo et al, In-vitro calcium phosphate formation on Electrostatic sprayed–perovskite BaTiO3layer on Ti electrophoretic after polishing treatment, selected from Ceramics International 2015 volume 41, No. 2, No. 2462 and No. 2466, and preparing barium titanate coating on the titanium surface by electrostatic spraying technology. But the binding force between the coating and the substrate is insufficient, and the clinical requirement cannot be met.
Article of the publication by Ho-Jun Song et al, namely, the publication of BaTiO3A barium titanate coating is prepared on the surface of titanium by micro-arc oxidation technique, wherein the coating is selected from Materials Letters, volume 61, No. 16, No. 3473 and No. 3476. However, the content of piezoelectric phase barium titanate in the coating is low, the piezoelectric performance is not high, and meanwhile, the coating contains less bioactive substances and the bioactivity is insufficient.
Disclosure of Invention
The invention aims to provide a preparation method of a medical titanium alloy surface biological piezoelectric composite coating, and solves the problems that a bioactive coating prepared by the existing method is poor in binding force with a substrate and low in surface bioactivity.
The technical scheme adopted by the invention is that the preparation method of the medical titanium alloy surface bio-piezoelectric composite coating comprises the steps of firstly generating a titanium dioxide coating with a compact inner layer and a porous surface layer on the surface of a titanium alloy substrate in situ by adopting a micro-arc oxidation technology, then generating a barium titanate coating by carrying out in-situ reaction on the titanium dioxide coating by adopting a hydrothermal chemical method, and finally filling holes on the surface of the polarized coating, namely forming the composite coating with the bio-piezoelectric property on the surface of the medical titanium alloy.
The present invention is also characterized in that,
the titanium dioxide coating is rich in Ca and P elements.
The method is implemented according to the following steps:
and 4, filling the holes on the surface of the titanium alloy matrix sample coating after the polarization treatment in the step 3, namely obtaining the composite coating with the biological piezoelectric property on the surface of the titanium alloy.
In the step 1, the electrolyte is a mixed aqueous solution containing a complexing agent with the concentration of 0.05-0.2mol/L, calcium ions with the concentration of 0.01-0.5mol/L and phosphate ions with the concentration of 0.05-0.5 mol/L.
The complexing agent is one or a mixture of citric acid and ethylene diamine tetraacetic acid; the calcium ion is selected from calcium acetate, calcium nitrate, and calcium chloride; the phosphate ions are selected from one or more of sodium dihydrogen phosphate, sodium metaaluminate, potassium hydrogen phosphate, potassium dihydrogen phosphate, beta-sodium glycerophosphate or beta-potassium glycerophosphate.
The micro-arc oxidation parameters in the step 1 are as follows: the micro-arc oxidation adopts pulse direct current voltage, the voltage is 200-500V, the pulse frequency is 300-900Hz, the duty ratio is 10-50%, the temperature of the electrolyte is below 60 ℃, and the oxidation time is 4-20 min.
In the step 2, the concentration of the barium hydroxide aqueous solution is 0.1-0.3 mol/L, and the addition amount is 50-70% of the total volume of the reaction kettle; the hydrothermal reaction temperature is 140 ℃ and 220 ℃, and the heat preservation is carried out for 6-16 h.
In the step 3, the polarization medium is any one of air, methyl silicone oil and transformer oil; the polarization voltage is 1-5kV, the polarization temperature is 30-150 ℃, and the polarization time is 1-5 h.
And 4, filling the holes with a bioactive substance or an antibacterial substance.
And the filling method in the step 4 is an impregnation method or a nano air spraying method.
The invention has the beneficial effects that firstly, micro-arc oxidation technology is adopted to carry out in-situ reaction on the surface of the medical titanium alloy to form an oxide layer with a compact and firm inner layer and a porous surface, on the basis, a hydrothermal chemical method is adopted to carry out in-situ reaction on the porous oxide layer to generate a barium titanate coating, then polarization treatment is carried out to ensure that the composite coating has piezoelectric property, finally, the technologies such as dipping, spraying and the like are adopted to fill substances for promoting cell growth in holes, and a coating structure with bio-piezoelectric property of 'compact inner layer + porous surface layer + filler in holes' is formed on the surface of the medical titanium alloy. The inner layer of the coating is compact, the coating is well combined with the matrix, the stability is high, and meanwhile, harmful metal ions can be effectively prevented from being dissolved out to body fluid; the piezoelectric effect of the piezoelectric bionic human bone of the barium titanate coating with the porous surface layer can transmit the force applied to the bone tissue to the material to generate the piezoelectric effect by depending on the activity of the human body, and the appropriate electrical stimulation can improve the deposition of hydroxyapatite, promote local blood circulation and further accelerate the repair of the bone; the holes are filled with calcium phosphate bone cement, hydroxyapatite, silver particles, gentamicin, chitosan and other substances or antibacterial drugs which are beneficial to the growth of early bone tissues, and meanwhile, the rough surface is beneficial to the adhesion and proliferation of cells, so that the metal material has good biocompatibility and bioactivity.
Drawings
FIG. 1 is a schematic structural diagram of a titanium dioxide coating with a dense inner layer and a porous surface prepared on the surface of a titanium alloy substrate in step 1 of the invention;
FIG. 2 is a schematic structural diagram of a bio-piezoelectric composite coating prepared by the present invention.
In the figure, 1 is a titanium alloy matrix, 2 is a porous oxidation layer, and 3 is a bioactive substance.
Detailed Description
The present invention will be described in detail below with reference to the accompanying drawings and specific embodiments.
The invention provides a preparation method of a medical titanium alloy surface bio-piezoelectric composite coating, which comprises the steps of firstly, generating a titanium dioxide coating which is rich in Ca and P elements, compact in inner layer and porous in surface layer on the surface of a substrate in situ by adopting a micro-arc oxidation technology; then, barium ions enter the titanium dioxide coating by using a hydrothermal chemical method under the alkali-heat condition, and the barium ions react with the titanium dioxide in situ to generate a barium titanate coating; and finally, filling holes on the surface of the polarized coating to obtain the composite coating with the surface having the biological piezoelectric property.
The method is implemented by the following steps:
Placing the pretreated titanium alloy matrix sample in a stainless steel tank containing electrolyte, and carrying out micro-arc oxidation treatment by using a titanium sample as an anode and a stainless steel tank as a cathode, wherein the micro-arc oxidation treatment adopts pulse direct current voltage, the voltage is 200 plus-voltage and 500V, the pulse frequency is 300 plus-voltage and 900Hz, the duty ratio is 10-50%, the temperature of the electrolyte is below 60 ℃, and the oxidation time is 4-20min, so that the titanium dioxide coating with a compact inner layer and a porous surface layer is obtained, as shown in figure 1.
The electrolyte is a mixed aqueous solution containing 0.05-0.2mol/L of complexing agent, 0.01-0.5mol/L of calcium ion and 0.05-0.5mol/L of phosphate radical ion. The electrolyte for providing calcium ions is calcium acetate, calcium nitrate and calcium chloride; the electrolyte providing phosphate ions is sodium dihydrogen phosphate, sodium metaaluminate, potassium hydrogen phosphate, potassium dihydrogen phosphate, beta-sodium glycerophosphate or beta-potassium glycerophosphate; the complexing agent is one or a mixture of citric acid and disodium ethylene diamine tetraacetate.
And (2) adding a barium hydroxide aqueous solution with the concentration of 0.1-0.3 mol/L, which accounts for 50-70% of the total volume of the reaction kettle, into the reaction kettle, placing the titanium sample subjected to micro-arc oxidation treatment in the step (1) into the hydrothermal reaction kettle, and preserving heat for 6-16h at the temperature of 140-220 ℃, namely generating the barium titanate coating on the surface of the titanium dioxide coating in situ.
In the hydrothermal reaction process, barium ions in the hydrothermal solution enter the titanium dioxide coating, and the barium ions and the titanium dioxide undergo a chemical reaction in situ under the alkali-heat condition, so that the barium titanate coating is generated.
Polarizing the titanium alloy sample obtained in the step 2 in a medium, wherein the polarizing voltage is 1-5kV, the polarizing temperature is 30-150 ℃, and the polarizing time is 1-5 h; and taking out the sample after the polarization is finished, sequentially ultrasonically cleaning the sample for 10min by using absolute ethyl alcohol and deionized water, and drying the sample.
The medium is any one of air, methyl silicone oil and transformer oil.
Step 4, hole filling treatment
And (3) filling substances which are beneficial to bone or cell growth into the holes on the surface of the titanium alloy sample coating subjected to the polarization treatment in the step (3) by adopting an immersion method or a nano air spraying method, and thus obtaining the composite coating with the surface having the bio-piezoelectric property, as shown in fig. 2.
Substances that contribute to bone or cell growth include biologically active substances and antibacterial substances. Wherein the bioactive substances are Hydroxyapatite (HA), calcium phosphate bone cement, etc.; the antibacterial substances include nano silver, chitosan, gentamicin, etc.
Filling by an immersion method, specifically:
preparing a substance to be filled into an aqueous solution, immersing the titanium alloy sample subjected to polarization treatment into the aqueous solution for full immersion, taking out and air-drying, repeating the above operation for a plurality of times, wherein the number of times of repeated operation is more than or equal to 5, and filling the holes.
Filling by a nano air spraying method, specifically: firstly, ultrasonically cleaning a sample by absolute ethyl alcohol, drying, then spraying filler particles with the particle size of less than 10 mu m on the surface of a titanium alloy sample subjected to polarization treatment by utilizing high-pressure air, quickly and uniformly coating a smooth surface of non-absorbent foam, and lightly polishing by using clean and dry soft superfine fiber cloth; and then wiping the surface of the sample once by using absolute ethyl alcohol, repeatedly and repeatedly spraying for a plurality of times, wherein the repeated times are more than or equal to 5 until the filler powder exists in the holes, and then spraying water vapor on the surface of the sample for 5-30 min.
The method forms a coating structure with the bio-piezoelectric performance, namely compact inner layer, porous surface layer and filler in pores, in the medical titanium alloy. The inner layer of the coating is compact, the coating is well combined with the matrix, the stability is high, and meanwhile, harmful metal ions can be effectively prevented from being dissolved out to body fluid; the piezoelectric effect of the piezoelectric bionic human bone of the barium titanate coating with the porous surface layer can transmit the force applied to the bone tissue to the material to generate the piezoelectric effect by depending on the activity of the human body, and the appropriate electrical stimulation can improve the deposition of hydroxyapatite, promote local blood circulation and further accelerate the repair of the bone; the holes are filled with substances which are beneficial to the growth of early bone tissues, such as calcium phosphate, hydroxyapatite, silver-carrying, drug-carrying and the like, and the rough surface is beneficial to the adhesion and proliferation of cells, so that the metal material has good biocompatibility and bioactivity.
Example 1
Placing the pretreated titanium substrate sample in a stainless steel tank body containing electrolyte, taking the titanium sample as an anode and the stainless steel tank body as a cathode, adopting pulse direct current voltage, the voltage being 200V, the pulse frequency being 700Hz, the duty ratio being 10%, the oxidation time being 4min, and the electrolyte temperature being 60 ℃. The electrolyte is formed by mixing a solvent which is deionized water, a solute which is disodium ethylene diamine tetraacetate with the concentration of 0.05mol/L, calcium acetate with the concentration of 0.01mol/L and sodium dihydrogen phosphate with the concentration of 0.05 mol/L;
adding a barium hydroxide aqueous solution with the concentration of 0.1mol/L accounting for 50% of the total volume of the reaction kettle into the reaction kettle, placing the titanium sample subjected to micro-arc oxidation treatment into a hydrothermal reaction kettle, and then preserving heat for 6 hours at the temperature of 140 ℃;
polarizing the sample treated in the step in an air medium, wherein the polarizing voltage is 1kV, the temperature is 150 ℃, the time is 1h, taking out the sample after the polarization is finished, carrying out ultrasonic cleaning for 10min by using absolute ethyl alcohol and deionized water in sequence, and drying;
preparing a certain amount of Simulated Body Fluid (SBF), just contacting the coating surface of the sample with the SBF liquid level, enabling the SBF liquid to enter holes on the coating surface by utilizing the capillary force action of the liquid, keeping for 10min, taking out the sample, naturally drying, and repeating the operation for 5 times. The composite coating with the bio-piezoelectric performance can be prepared on the surface of the medical titanium alloy.
Example 2
Placing the pretreated titanium substrate sample in a stainless steel tank body containing electrolyte, taking the titanium sample as an anode and the stainless steel tank body as a cathode, adopting pulse direct current voltage, voltage of 500V, pulse frequency of 300Hz, duty ratio of 20%, oxidation time of 8min, and electrolyte temperature of 60 ℃. The electrolyte is formed by mixing a solvent which is deionized water, a solute which is disodium ethylene diamine tetraacetate with the concentration of 0.1mol/L, calcium acetate with the concentration of 0.1mol/L and sodium dihydrogen phosphate with the concentration of 0.07 mol/L;
adding a barium hydroxide aqueous solution with the concentration of 0.2mol/L accounting for 70% of the total volume of the reaction kettle into the reaction kettle, placing the titanium sample subjected to micro-arc oxidation treatment into a hydrothermal reaction kettle, and then preserving heat for 8 hours at the temperature of 180 ℃;
polarizing the sample treated in the step in an air medium, wherein the polarizing voltage is 3kV, the temperature is 100 ℃, the time is 3h, taking out the sample after the polarization is finished, carrying out ultrasonic cleaning for 10min by using absolute ethyl alcohol and deionized water in sequence, and drying;
preparing chitosan into an aqueous solution, immersing the titanium alloy sample subjected to polarization treatment into the aqueous solution for full immersion, taking out and air-drying, and repeating the operation for 10 times till the holes are filled. The composite coating with the bio-piezoelectric performance can be prepared on the surface of the medical titanium alloy.
Example 3
Placing the pretreated titanium substrate sample in a stainless steel tank body containing electrolyte, taking the titanium sample as an anode and the stainless steel tank body as a cathode, adopting pulse direct current voltage, the voltage being 400V, the pulse frequency being 500Hz, the duty ratio being 30%, the oxidation time being 10min, and the temperature of the electrolyte being 60 ℃. The electrolyte is formed by mixing a solvent which is deionized water, and solutes which are disodium ethylene diamine tetraacetate with the concentration of 0.2mol/L, calcium acetate with the concentration of 0.15mol/L and sodium dihydrogen phosphate with the concentration of 0.3 mol/L;
adding a barium hydroxide aqueous solution with the concentration of 0.3mol/L accounting for 60 percent of the total volume of the reaction kettle into the reaction kettle, placing the titanium sample subjected to micro-arc oxidation treatment into a hydrothermal reaction kettle, and then preserving heat for 10 hours at the temperature of 200 ℃;
polarizing the sample treated in the step in an air medium, wherein the polarizing voltage is 4kV, the temperature is 60 ℃, the time is 2 hours, taking out the sample after the polarization is finished, carrying out ultrasonic cleaning for 10min by using absolute ethyl alcohol and deionized water in sequence, and drying;
firstly, ultrasonically cleaning a sample by absolute ethyl alcohol, drying, then mixing one or two kinds of nano powder of calcium hydrophosphate, anhydrous calcium phosphate, calcium dihydrogen phosphate, tricalcium phosphate or tetracalcium phosphate according to the molar ratio of Ca/P of 1.3-2, spraying the nano powder on the surface of the sample by utilizing high-pressure air, quickly and uniformly coating a flat surface which does not absorb water foam, lightly polishing by using clean and dry soft superfine fiber cloth, then wiping the surface of the sample by using absolute ethyl alcohol once, repeating the operation for 10 times until mixed powder exists in holes, then spraying water vapor on the surface of the sample, and spraying for 5-20min to generate the calcium phosphate cement.
Example 4
Placing the pretreated titanium substrate sample in a stainless steel tank body containing electrolyte, taking the titanium sample as an anode and the stainless steel tank body as a cathode, adopting pulse direct current voltage, the voltage being 300V, the pulse frequency being 900Hz, the duty ratio being 50%, the oxidation time being 20min, and the temperature of the electrolyte being 60 ℃. The electrolyte is formed by mixing a solvent which is deionized water, solutes which are disodium ethylene diamine tetraacetate with the concentration of 0.5mol/L, calcium acetate with the concentration of 0.5mol/L and sodium dihydrogen phosphate with the concentration of 0.5 mol/L;
adding a barium hydroxide aqueous solution with the concentration of 0.1mol/L accounting for 65 percent of the total volume of the reaction kettle into the reaction kettle, placing the titanium sample subjected to micro-arc oxidation treatment into a hydrothermal reaction kettle, and then preserving heat for 16 hours at the temperature of 220 ℃;
polarizing the sample treated in the step in an air medium, wherein the polarizing voltage is 5kV, the temperature is 30 ℃, the time is 4 hours, taking out the sample after the polarization is finished, carrying out ultrasonic cleaning for 10min by using absolute ethyl alcohol and deionized water in sequence, and drying;
firstly, ultrasonically cleaning a sample by absolute ethyl alcohol, drying, then spraying nano silver particles on the surface of the sample by utilizing high-pressure air, quickly and uniformly coating a flat surface which does not absorb water foam, lightly polishing by using clean and dry soft superfine fiber cloth, then wiping the surface of the sample by absolute ethyl alcohol once, repeating the operation for 5 times until mixed powder exists in holes, then spraying water vapor on the surface of the sample, and spraying for 15-30 min.
Claims (7)
1. A preparation method of a medical titanium alloy surface bio-piezoelectric composite coating is characterized by firstly adopting a micro-arc oxidation technology to generate a titanium dioxide coating with a compact inner layer and a porous surface layer on the surface of a titanium alloy substrate in situ, then adopting a hydrothermal chemical method to make the titanium dioxide coating react in situ to generate a barium titanate coating, and finally filling holes on the surface of the polarized coating, namely forming the composite coating with the bio-piezoelectric property on the surface of the medical titanium alloy, wherein the titanium dioxide coating is rich in Ca and P elements;
the method is implemented according to the following steps:
step 1, placing a pretreated titanium alloy matrix sample into a stainless steel tank body containing electrolyte, taking the titanium alloy matrix sample as an anode and the stainless steel tank body as a cathode, and generating a titanium dioxide coating with a compact inner layer and a porous surface layer on the surface of the titanium alloy matrix sample in situ by adopting a micro-arc oxidation technology;
step 2, adding a barium hydroxide aqueous solution into a reaction kettle, placing the titanium alloy matrix sample subjected to micro-arc oxidation treatment in the step 1 into the reaction kettle for hydrothermal reaction, and generating a barium titanate coating on the surface of the titanium dioxide coating in situ;
step 3, carrying out polarization treatment on the titanium alloy matrix sample treated in the step 2;
step 4, filling the holes on the surface of the titanium alloy matrix sample coating after polarization treatment in the step 3, namely obtaining a composite coating with the biological piezoelectric property on the surface of the titanium alloy;
the electrolyte in the step 1 is a mixed aqueous solution containing a complexing agent with the concentration of 0.05-0.2mol/L, calcium ions with the concentration of 0.01-0.5mol/L and phosphate ions with the concentration of 0.05-0.5 mol/L.
2. The method for preparing the medical titanium alloy surface bio-piezoelectric composite coating according to claim 1, wherein the complexing agent is one or a mixture of citric acid and disodium ethylene diamine tetraacetate; the calcium ion is selected from calcium acetate, calcium nitrate, and calcium chloride; the phosphate ions are selected from one or more of sodium dihydrogen phosphate, sodium metaaluminate, potassium hydrogen phosphate, potassium dihydrogen phosphate, beta-sodium glycerophosphate or beta-potassium glycerophosphate.
3. The method for preparing the medical titanium alloy surface bio-piezoelectric composite coating according to claim 1, wherein the micro-arc oxidation parameters in the step 1 are as follows: the micro-arc oxidation adopts pulse direct current voltage, the voltage is 200-500V, the pulse frequency is 300-900Hz, the duty ratio is 10-50%, the temperature of the electrolyte is below 60 ℃, and the oxidation time is 4-20 min.
4. The preparation method of the medical titanium alloy surface bio-piezoelectric composite coating according to claim 1, wherein the concentration of the barium hydroxide aqueous solution in the step 2 is 0.1mol/L-0.3mol/L, and the addition amount is 50% -70% of the total volume of the reaction kettle; the hydrothermal reaction temperature is 140 ℃ and 220 ℃, and the heat preservation is carried out for 6-16 h.
5. The method for preparing the medical titanium alloy surface bio-piezoelectric composite coating according to claim 1, wherein the polarizing medium in the step 3 is any one of air, methyl silicone oil and transformer oil; the polarization voltage is 1-5kV, the polarization temperature is 30-150 ℃, and the polarization time is 1-5 h.
6. The method for preparing the medical titanium alloy surface bio-piezoelectric composite coating according to claim 1, wherein the material for filling the pores in the step 4 is a bioactive substance or an antibacterial substance.
7. The method for preparing the medical titanium alloy surface bio-piezoelectric composite coating according to claim 1, wherein the filling method in the step 4 is a dipping method or a nano air spraying method.
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| CN110013565A (en) * | 2019-03-29 | 2019-07-16 | 西安理工大学 | A kind of preparation method of titanium alloy surface biology Piezoelectric coating |
| CN110200727A (en) * | 2019-07-01 | 2019-09-06 | 中国人民解放军第四军医大学 | A kind of 3D printing tubular porous titanium prosthesis and preparation method thereof for four limbs large segmental bone defect |
| CN113005497B (en) * | 2021-02-05 | 2022-10-21 | 中山大学 | Composite coating for preventing fouling on titanium alloy surface and preparation method and application thereof |
| CN113445102B (en) * | 2021-06-01 | 2022-09-02 | 西安理工大学 | Preparation method of biological piezoelectric coating on surface of titanium-based material |
| CN113502524B (en) * | 2021-07-07 | 2022-08-26 | 西安理工大学 | Preparation method of medical titanium alloy surface biological piezoelectric antibacterial coating |
| CN116043205B (en) * | 2023-03-31 | 2023-06-27 | 上海交通大学医学院附属第九人民医院 | Copper barium titanate piezoelectric ceramic coating and preparation method and application thereof |
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