CN110079849B - Preparation method of antibacterial coating on surface of titanium-based medical instrument - Google Patents

Preparation method of antibacterial coating on surface of titanium-based medical instrument Download PDF

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CN110079849B
CN110079849B CN201910477669.2A CN201910477669A CN110079849B CN 110079849 B CN110079849 B CN 110079849B CN 201910477669 A CN201910477669 A CN 201910477669A CN 110079849 B CN110079849 B CN 110079849B
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titanium
ruthenium
sample
coating
dioxide
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CN110079849A (en
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和祥
刘一菲
程嘉辉
谢维栋
陈震
周睿
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Suzhou Bozhi golden Diamond Technology Co.,Ltd.
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Xian Jiaotong University
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING 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
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C20/00—Chemical coating by decomposition of either solid compounds or suspensions of the coating forming compounds, without leaving reaction products of surface material in the coating
    • C23C20/06—Coating with inorganic material, other than metallic material
    • C23C20/08—Coating with inorganic material, other than metallic material with compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C—CHEMISTRY; METALLURGY
    • C23—COATING 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
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/04—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings of inorganic non-metallic material
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02—Anodisation
    • C25D11/26—Anodisation of refractory metals or alloys based thereon

Abstract

The invention relates to a preparation method of a titanium-based medical instrument surface antibacterial coating, which comprises the steps of taking a pretreated titanium-based material as an anode and a platinum sheet as a cathode, carrying out electrolysis treatment in an electrolyte, and then cleaning and drying to obtain the titanium-based material with a titanium dioxide coating; then soaking the titanium substrate in ruthenium solution, and drying and carrying out heat treatment in sequence to obtain a titanium-based material with a titanium dioxide-ruthenium dioxide coating; and charging the titanium-based material with the titanium dioxide-ruthenium dioxide coating to obtain the titanium-based medical instrument surface antibacterial coating. According to the invention, through two steps of anodic oxidation treatment and ruthenium salt heat treatment, the prepared coating has a nano composite structure and is tightly combined, the specific surface area of titanium is increased, and the antibacterial performance is improved.

Description

Preparation method of antibacterial coating on surface of titanium-based medical instrument
Technical Field
The invention relates to the technical field of metal surface modification, in particular to a preparation method of an antibacterial coating on the surface of a titanium-based medical instrument.
Background
Titanium is widely used in the field of medical implants. By using an anodic oxidation method, an oxide coating can be prepared on the surface of Ti and Ti alloy. By controlling the electrolytic parameters and the components and the content of the electrolyte, the components, the tissues and the structure of the coating can be regulated and controlled to prepare coatings with different functionalities. The mechanism involved in the method is the plasma chemistry principle, the electrochemical reaction principle and the deposition action principle of colloidal particles. According to the requirements of the field of medical implants, the surface of the medical titanium alloy matrix needs to have bioactivity and excellent bacteriostatic ability. In order to meet the requirement, a technology for enhancing the biological activity of the oxidation coating by using a method of doping elements such as copper, silver and the like through electrolysis exists, but the titanium alloy oxidation coating prepared by the existing method is weak in biological activity and not excellent in bacteriostatic performance.
Disclosure of Invention
The invention aims to solve the problems in the prior art and provides a preparation method of an antibacterial coating on the surface of a titanium-based medical instrument.
In order to achieve the purpose, the invention adopts the following technical scheme:
the method comprises the following steps:
(1) material pretreatment: pretreating a titanium-based material;
(2) anodic oxidation: taking the titanium-based material pretreated in the step (1) as an anode and a platinum sheet as a cathode, and carrying out electrolytic treatment in electrolyte to generate a titanium dioxide nanotube array on the surface of the titanium-based material; after the electrolysis is finished, cleaning and drying to obtain a titanium-based material with a titanium dioxide coating;
(3) ruthenium salt heat treatment: soaking the surface of the titanium-based material with the titanium dioxide coating obtained in the step (2) with a ruthenium solution, and then sequentially drying and thermally treating to obtain the titanium-based material with the titanium dioxide-ruthenium dioxide coating;
(4) charging: and (4) charging the titanium-based material with the titanium dioxide-ruthenium dioxide coating obtained in the step (3) to obtain the titanium-based medical instrument surface antibacterial coating.
Further, in the step (1), the titanium-based material is Ti-6Al-4V alloy, TC4 titanium alloy, TA2 industrial pure titanium or TA3 industrial pure titanium; the pretreatment is to polish, clean and dry by sand paper.
Further, the sand paper is one or more of 240 meshes, 400 meshes, 600 meshes and 1000 meshes.
Further, in the step (2), the electrolyte is ethylene glycol and NH4The solution F is formed by mixing and melting in water, and the volume ratio of the ethylene glycol to the water is (0.5-1.5): NH in electrolyte solution4The concentration of F is 0.1-1.5 mol/L.
Further, in the step (2), during the electrolysis treatment, the anode voltage is 10-80V, and the electrolysis time is 1-8 h.
Further, in the step (3), the ruthenium solution is prepared by adding ruthenium salt into water, and the concentration of the ruthenium solution is 5 mg/mL-50 mg/mL.
Further, the ruthenium salt is ruthenium acetate, ruthenium chloride or ruthenium sulfate.
Further, in the step (3), the titanium-based material with the titanium dioxide coating is subjected to surface infiltration of the ruthenium solution by pulling for 2-5 times through a pulling method.
Further, in the step (3), the temperature of the heat treatment is 200-550 ℃, and the time is 0.5-4 h.
Further, in the step (4), the charging time is 1 h-4.5 h, and the charging voltage is 0.2 v-1.8 v.
Compared with the prior art, the invention has the beneficial effects that:
(1) the coating prepared by the method has a nano composite structure through two steps of anodic oxidation treatment and ruthenium salt heat treatment, and a titanium dioxide nano-rod-shaped structure layer generated by an anodic oxidation method is tightly combined with a ruthenium dioxide nano-structure generated by ruthenium salt heat treatment.
(2) According to the invention, because of anodic oxidation treatment and ruthenium salt heat treatment, a firm titanium dioxide ruthenium dioxide nanostructure coating is grown on the titanium surface, the specific surface area of titanium is effectively increased, and the specific capacitance is up to 1.86F/m measured by experiments2The method can prove that the specific surface area of the titanium is greatly increased, and the antibacterial performance is improved.
(3) Because the titanium dioxide and ruthenium dioxide coating prepared by the method has excellent electrical property, the bacteriostatic ability of the treated sample after being charged is obviously improved, and a good bacteriostatic effect is shown, and experiments show that the killing rate of staphylococcus aureus can reach 90%. When positive charging is carried out, in the experimental range, the longer the charging time is, the larger the charging voltage is, and the stronger the bacteriostasis capacity is, the bacteriostasis capacity can be controlled by controlling the charging time and the charging voltage.
(4) The invention has simple process and low cost, and the prepared coating has no discontinuous interface with the substrate and has good biological activity. And the excellent electrical property is represented in an electrical property test, and the excellent effect is shown in various antibacterial activity tests. Therefore, the product is expected to be widely applied in the medical field.
Drawings
FIG. 1 is a schematic view of an anodizing apparatus according to the present invention;
FIG. 2 is a schematic view of the nanostructure of the titanium dioxide ruthenium dioxide prepared by the present invention;
in the figure, 1 is a titanium sample, 2 is titanium dioxide, and 3 is tin dioxide.
FIG. 3 is a diagram showing the bacteriostatic effect of the antibacterial coating on the surface of the titanium-based medical device prepared by the present invention before charging;
FIG. 4 is a diagram showing the antibacterial effect of the titanium-based medical device surface antibacterial coating prepared by the present invention after charging;
Detailed Description
The present invention will be described in detail with reference to the accompanying drawings.
The invention relates to a preparation method of a titanium-based medical instrument surface antibacterial coating, which comprises the following steps:
1) material pretreatment: and (3) sanding the titanium sample to be treated to be smooth in surface without obvious scratches and defects, wherein the sandpaper is one or more of 240 meshes, 400 meshes, 600 meshes and 1000 meshes. Ultrasonically cleaning the polished sample for 2-3 min by absolute ethyl alcohol and deionized water in sequence; and putting the sample subjected to ultrasonic cleaning into a drying oven to be dried at 40 ℃. The titanium test sample is Ti-6Al-4V alloy, TC4 titanium alloy, TA2 industrial pure titanium or TA3 industrial pure titanium.
2) Anodic oxidation: taking the titanium sample treated in the step 1) as an anode, taking a platinum sheet as a cathode, and using ethylene glycol and NH4And mixing and melting the solution F in water to form a mixed solution, wherein the volume ratio of the ethylene glycol to the water is 0.5: 1-1.5: 1, NH in the mixed solution4The concentration of F is 0.1-1.5 mol/L, and the mixed solution is used as electrolyte for electrolysis treatment. Setting the anode voltage to be 10-80V and the electrolysis time to be 1-8 h. And after the electrolysis is finished, generating a titanium dioxide nanotube array on the titanium surface. After the electrolysis, the sample was washed with deionized water and then dried at 40 ℃ to obtain a titanium oxide sample.
3) Ruthenium salt heat treatment: dissolving ruthenium salt in water to form 5-50 mg/mL ruthenium salt solution, and pulling for 2-5 times by using a pulling method to soak the surface of the titanium oxide sample obtained after drying in the step 2) with the prepared ruthenium salt solution; putting the sample soaked with ruthenium acetate into an oven to be dried at 40 ℃; and (3) putting the dried sample into a muffle furnace, and carrying out heat treatment for 0.5-4 h at 200-550 ℃ to obtain the sample with the bioactive micro-arc titanium oxide surface tin dioxide-ruthenium dioxide coating. The ruthenium salt is ruthenium acetate, ruthenium chloride or ruthenium sulfate.
4) Charging: and (3) charging the sample with the titanium dioxide ruthenium dioxide coating obtained after cleaning and drying in the step 3) to obtain the titanium-based surface tin dioxide-ruthenium dioxide antibacterial coating with electrical activity, biological activity and good antibacterial activity. Wherein the charging time is 1 h-4.5 h, and the charging voltage is 0.2 v-1.8 v.
The following are specific examples of the present invention.
Example 1
1) Material pretreatment: the titanium sample to be treated is polished by 240-mesh sand paper until the surface is smooth and has no obvious scratch and defect. Ultrasonically cleaning the polished sample for 2min by absolute ethyl alcohol and deionized water in sequence; and putting the sample subjected to ultrasonic cleaning into a drying oven to be dried at 40 ℃. Wherein, the titanium sample is TA2 industrial pure titanium;
2) anodic oxidation: taking the titanium sample treated in the step 1) as an anode, taking a platinum sheet as a cathode, and using ethylene glycol and NH4Mixing the solution F with water to form a mixed solution, wherein the ratio of ethylene glycol to water is 0.5:1, and NH is contained in the mixed solution4The concentration of F is 0.1mol/L, and the mixed solution is used as electrolyte for electrolytic treatment. The anode voltage was set at 10V and the electrolysis time was 1 h. And after the electrolysis is finished, generating a titanium dioxide nanotube array on the titanium surface. After the electrolysis, the sample was washed with deionized water and then dried at 40 ℃ to obtain a titanium oxide sample.
3) Ruthenium salt heat treatment: dissolving ruthenium acetate in water to form 5mg/mL ruthenium acetate solution, and pulling for 2 times by using a pulling method to soak the surface of the titanium oxide sample dried in the step 2) with the prepared ruthenium acetate solution; putting the sample soaked with ruthenium acetate into an oven to be dried at 40 ℃; and (3) putting the dried sample into a muffle furnace, and carrying out heat treatment for 0.5h at 200 ℃ to obtain the sample with the bioactive micro-arc titanium oxide surface tin dioxide-ruthenium dioxide coating.
4) Charging: and (3) charging the sample with the titanium dioxide ruthenium dioxide coating obtained after cleaning and drying in the step 3) to obtain the titanium-based surface tin dioxide-ruthenium dioxide antibacterial coating with electrical activity, biological activity and good antibacterial activity. Wherein the charging time is 1.5h, and the charging voltage is 0.2 v.
Example 2
1) Material pretreatment: the titanium sample to be treated is polished by 400-mesh sand paper until the surface is smooth and has no obvious scratch and defect. Ultrasonically cleaning the polished sample for 3min by absolute ethyl alcohol and deionized water in sequence; and putting the sample subjected to ultrasonic cleaning into a drying oven to be dried at 40 ℃. Wherein the titanium sample is TC4 titanium alloy;
2) anodic oxidation: taking the titanium sample treated in the step 1) as an anode, taking a platinum sheet as a cathode, and using ethylene glycol and NH4Mixing the solution F with water to form a mixed solution, wherein the ratio of ethylene glycol to water is 0.8:1, and NH is contained in the mixed solution4The concentration of F is 0.5mol/L, and the mixed solution is used as electrolyte for electrolytic treatment. The anode voltage was set at 20V and the electrolysis time was 1.5 h. And after the electrolysis is finished, generating a titanium dioxide nanotube array on the titanium surface. After the electrolysis, the sample was washed with deionized water and then dried at 40 ℃ to obtain a titanium oxide sample.
3) Ruthenium salt heat treatment: dissolving ruthenium chloride in water to form a ruthenium chloride solution of 15mg/mL, and carrying out lifting and pulling for 3 times by using a pulling method to soak the surface of the titanium oxide sample obtained after drying in the step 2) with the prepared ruthenium chloride solution; putting the sample soaked with ruthenium chloride into an oven to be dried at 50 ℃; and (3) putting the dried sample into a muffle furnace to carry out heat treatment for 2 hours at 350 ℃, thus obtaining the sample with the microarc titanium oxide surface tin dioxide-ruthenium dioxide coating with bioactivity.
4) Charging: and (3) charging the sample with the titanium dioxide ruthenium dioxide coating obtained after cleaning and drying in the step 3) to obtain the titanium-based surface tin dioxide-ruthenium dioxide antibacterial coating with electrical activity, biological activity and good antibacterial activity. Wherein the charging time is 1h, and the charging voltage is 0.3 v.
Example 3
1) Material pretreatment: the titanium sample to be treated is polished by 1000-mesh abrasive paper until the surface is smooth and has no obvious scratch and defect. Ultrasonically cleaning the polished sample for 2.5min by absolute ethyl alcohol and deionized water in sequence; and putting the sample subjected to ultrasonic cleaning into a drying oven to be dried at 40 ℃. Wherein, the titanium sample is TA2 industrial pure titanium;
2) anodic oxidation: taking the titanium sample treated in the step 1) as an anode, taking a platinum sheet as a cathode, and using ethylene glycol and NH4Mixing the solution F with water to form a mixed solution, wherein the ratio of ethylene glycol to water is 1:1, and NH is contained in the mixed solution4The concentration of F is 0.5mol/L, and the mixed solution is used as electrolyte for electrolytic treatment. The anode voltage was set at 30V and the electrolysis time was set at 5 h. And after the electrolysis is finished, generating a titanium dioxide nanotube array on the titanium surface. After the electrolysis, the sample was washed with deionized water and then dried at 40 ℃ to obtain a titanium oxide sample.
3) Ruthenium salt heat treatment: dissolving ruthenium sulfate in water to form a ruthenium sulfate solution of 35mg/mL, and carrying out lifting and pulling for 4 times by using a pulling method to soak the surface of the titanium oxide sample dried in the step 2) with the prepared ruthenium sulfate solution; putting the sample soaked with ruthenium acetate into an oven to be dried at 40 ℃; and (3) putting the dried sample into a muffle furnace, and carrying out heat treatment for 2.5h at 450 ℃ to obtain the sample with the bioactive micro-arc titanium oxide surface tin dioxide-ruthenium dioxide coating.
4) Charging: and (3) charging the sample with the titanium dioxide ruthenium dioxide coating obtained after cleaning and drying in the step 3) to obtain the titanium-based surface tin dioxide-ruthenium dioxide antibacterial coating with electrical activity, biological activity and good antibacterial activity. Wherein the charging time is 1.5h, and the charging voltage is 0.5 v.
Example 4
1) Material pretreatment: the titanium sample to be treated is polished by 600-mesh sand paper until the surface is smooth and has no obvious scratch and defect. Ultrasonically cleaning the polished sample for 3min by absolute ethyl alcohol and deionized water in sequence; and putting the sample subjected to ultrasonic cleaning into a drying oven to be dried at 40 ℃. Wherein the titanium sample is Ti-6Al-4V alloy;
2) anodic oxidation: taking the titanium sample treated in the step 1) as an anode, taking a platinum sheet as a cathode, and using ethylene glycol and NH4Mixing the solution F with water to form a mixed solution, wherein the ratio of ethylene glycol to water is 1.5:1, and NH is contained in the mixed solution4F concentration is 1mol/L, and the mixed solution is used as electrolyte to carry out electrolysisAnd (6) processing. The anode voltage was set at 40V and the electrolysis time was 3 h. And after the electrolysis is finished, generating a titanium dioxide nanotube array on the titanium surface. After the electrolysis, the sample was washed with deionized water and then dried at 40 ℃ to obtain a titanium oxide sample.
3) Ruthenium salt heat treatment: dissolving ruthenium acetate in water to form a ruthenium acetate solution of 10mg/mL, and carrying out lifting and pulling for 5 times by using a pulling method to soak the surface of the titanium oxide sample obtained after drying in the step 2) with the prepared ruthenium acetate solution; putting the sample soaked with ruthenium acetate into an oven to be dried at 40 ℃; and (3) putting the dried sample into a muffle furnace, and carrying out heat treatment for 3h at 550 ℃ to obtain the sample with the microarc titanium oxide surface tin dioxide-ruthenium dioxide coating with bioactivity.
4) Charging: and (3) charging the sample with the titanium dioxide ruthenium dioxide coating obtained after cleaning and drying in the step 3) to obtain the titanium-based surface tin dioxide-ruthenium dioxide antibacterial coating with electrical activity, biological activity and good antibacterial activity. Wherein the charging time is 2h and the charging voltage is 1.2 v.
Example 5
1) Material pretreatment: the titanium sample to be treated is sequentially polished by 240-mesh and 600-mesh sandpaper until the surface is smooth and has no obvious scratch or defect. Ultrasonically cleaning the polished sample for 2-3 min by absolute ethyl alcohol and deionized water in sequence; and putting the sample subjected to ultrasonic cleaning into a drying oven to be dried at 40 ℃. Wherein, the titanium sample is TA3 industrial pure titanium;
2) anodic oxidation: taking the titanium sample treated in the step 1) as an anode, taking a platinum sheet as a cathode, and using ethylene glycol and NH4Mixing the solution F with water to form a mixed solution, wherein the ratio of ethylene glycol to water is 1:1, and NH is contained in the mixed solution4The concentration of F is 1.4mol/L, and the mixed solution is used as electrolyte for electrolytic treatment. The anode voltage was set at 50V and the electrolysis time was 2 h. And after the electrolysis is finished, generating a titanium dioxide nanotube array on the titanium surface. After the electrolysis, the sample was washed with deionized water and then dried at 40 ℃ to obtain a titanium oxide sample.
3) Ruthenium salt heat treatment: dissolving ruthenium sulfate in water to form 5mg/mL ruthenium sulfate solution, and pulling for 2 times by using a pulling method to soak the surface of the titanium oxide sample dried in the step 2) with the prepared ruthenium sulfate solution; putting the sample soaked with ruthenium sulfate into an oven to be dried at 40 ℃; and (3) putting the dried sample into a muffle furnace to carry out heat treatment for 4 hours at the temperature of 200 ℃, thus obtaining the sample with the microarc titanium oxide surface tin dioxide-ruthenium dioxide coating with bioactivity.
4) Charging: and (3) charging the sample with the titanium dioxide ruthenium dioxide coating obtained after cleaning and drying in the step 3) to obtain the titanium-based surface tin dioxide-ruthenium dioxide antibacterial coating with electrical activity, biological activity and good antibacterial activity. Wherein the charging time is 2.5h and the charging voltage is 1.2 v.
Example 6
1) Material pretreatment: the titanium sample to be treated is sequentially polished by 400-mesh and 600-mesh sandpaper until the surface is smooth and has no obvious scratch or defect. Ultrasonically cleaning the polished sample for 3min by absolute ethyl alcohol and deionized water in sequence; and putting the sample subjected to ultrasonic cleaning into a drying oven to be dried at 40 ℃. Wherein, the titanium sample is TA2 industrial pure titanium;
2) anodic oxidation: taking the titanium sample treated in the step 1) as an anode, taking a platinum sheet as a cathode, and using ethylene glycol and NH4Mixing the solution F with water to form a mixed solution, wherein the ratio of ethylene glycol to water is 1.2:1, and NH is contained in the mixed solution4The concentration of the solution F is 1.5mol/L, and the mixed solution is used as electrolyte for electrolytic treatment. The anode voltage was set at 60V and the electrolysis time was 2 h. And after the electrolysis is finished, generating a titanium dioxide nanotube array on the titanium surface. After the electrolysis, the sample was washed with deionized water and then dried at 40 ℃ to obtain a titanium oxide sample.
3) Ruthenium salt heat treatment: dissolving ruthenium chloride in water to form 5mg/mL ruthenium chloride solution, and carrying out lifting and pulling for 4 times by using a pulling method to soak the surface of the titanium oxide sample obtained after drying in the step 2) with the prepared ruthenium chloride solution; putting the sample soaked with ruthenium chloride into an oven to be dried at 40 ℃; and (3) putting the dried sample into a muffle furnace, and carrying out heat treatment for 3h at 300 ℃ to obtain the sample with the bioactive micro-arc titanium oxide surface tin dioxide-ruthenium dioxide coating.
4) Charging: and (3) charging the sample with the titanium dioxide ruthenium dioxide coating obtained after cleaning and drying in the step 3) to obtain the titanium-based surface tin dioxide-ruthenium dioxide antibacterial coating with electrical activity, biological activity and good antibacterial activity. Wherein the charging time is 2h and the charging voltage is 1.5 v.
Example 7
1) Material pretreatment: the titanium sample to be treated is sequentially polished by 400-mesh, 600-mesh and 1000-mesh sand paper until the surface is smooth and has no obvious scratch and defect. Ultrasonically cleaning the polished sample for 3min by absolute ethyl alcohol and deionized water in sequence; and putting the sample subjected to ultrasonic cleaning into a drying oven to be dried at 40 ℃. Wherein the titanium sample is TC4 titanium alloy;
2) anodic oxidation: taking the titanium sample treated in the step 1) as an anode, taking a platinum sheet as a cathode, and using ethylene glycol and NH4Mixing the solution F with water to form a mixed solution, wherein the ratio of ethylene glycol to water is 1:1, and NH is contained in the mixed solution4The concentration of F is 0.5mol/L, and the mixed solution is used as electrolyte for electrolytic treatment. The anode voltage was set at 60V and the electrolysis time was 2 h. And after the electrolysis is finished, generating a titanium dioxide nanotube array on the titanium surface. After the electrolysis, the sample was washed with deionized water and then dried at 40 ℃ to obtain a titanium oxide sample.
3) Ruthenium salt heat treatment: dissolving ruthenium chloride in water to form a ruthenium chloride solution of 25mg/mL, and carrying out lifting and pulling for 5 times by using a pulling method to soak the surface of the titanium oxide sample obtained after drying in the step 2) with the prepared ruthenium chloride solution; putting the sample soaked with ruthenium chloride into an oven to be dried at 40 ℃; and (3) putting the dried sample into a muffle furnace, and carrying out heat treatment for 2h at 500 ℃ to obtain the sample with the microarc titanium oxide surface tin dioxide-ruthenium dioxide coating with bioactivity.
4) Charging: and (3) charging the sample with the titanium dioxide ruthenium dioxide coating obtained after cleaning and drying in the step 3) to obtain the titanium-based surface tin dioxide-ruthenium dioxide antibacterial coating with electrical activity, biological activity and good antibacterial activity. Wherein the charging time is 4h and the charging voltage is 1.6 v.
Example 8
1) Material pretreatment: the titanium sample to be treated is sequentially polished by 240 meshes of sand paper, 600 meshes of sand paper and 1000 meshes of sand paper until the surface is smooth, and no obvious scratch or defect exists. Ultrasonically cleaning the polished sample for 2min by absolute ethyl alcohol and deionized water in sequence; and putting the sample subjected to ultrasonic cleaning into a drying oven to be dried at 40 ℃. Wherein, the titanium sample is TA2 industrial pure titanium;
2) anodic oxidation: taking the titanium sample treated in the step 1) as an anode, taking a platinum sheet as a cathode, and using ethylene glycol and NH4Mixing the solution F with water to form a mixed solution, wherein the ratio of ethylene glycol to water is 1:1, and NH is contained in the mixed solution4The concentration of F was 0.14mol/L, and the mixed solution was used as an electrolyte to conduct electrolysis. The anode voltage was set at 80V and the electrolysis time was set at 5 h. And after the electrolysis is finished, generating a titanium dioxide nanotube array on the titanium surface. After the electrolysis, the sample was washed with deionized water and then dried at 40 ℃ to obtain a titanium oxide sample.
3) Ruthenium salt heat treatment: dissolving ruthenium acetate in water to form 45mg/mL ruthenium acetate solution, and pulling for 2 times by using a pulling method to soak the surface of the titanium oxide sample dried in the step 2) with the prepared ruthenium acetate solution; putting the sample soaked with ruthenium acetate into an oven to be dried at 40 ℃; and (3) putting the dried sample into a muffle furnace, and carrying out heat treatment for 4h at 400 ℃ to obtain the sample with the microarc titanium oxide surface tin dioxide-ruthenium dioxide coating with bioactivity.
4) Charging: and (3) charging the sample with the titanium dioxide ruthenium dioxide coating obtained after cleaning and drying in the step 3) to obtain the titanium-based surface tin dioxide-ruthenium dioxide antibacterial coating with electrical activity, biological activity and good antibacterial activity. Wherein the charging time is 4.5h and the charging voltage is 1.8 v.
Example 9
1) Material pretreatment: the titanium sample to be treated is sequentially polished by 400-mesh, 600-mesh and 1000-mesh sand paper until the surface is smooth and has no obvious scratch and defect. Ultrasonically cleaning the polished sample for 2.5min by absolute ethyl alcohol and deionized water in sequence; and putting the sample subjected to ultrasonic cleaning into a drying oven to be dried at 40 ℃. Wherein, the titanium sample is TA3 industrial pure titanium;
2) anodic oxidation: taking the titanium sample treated in the step 1) as an anode, taking a platinum sheet as a cathode, and using ethylene glycol and NH4Mixing the solution FMixing and melting in water to form a mixed solution, wherein the ratio of ethylene glycol to water is 1:1, and NH is contained in the mixed solution4The concentration of F is 0.15mol/L, and the mixed solution is used as electrolyte for electrolytic treatment. The anode voltage was set at 70V and the electrolysis time was set at 8 h. And after the electrolysis is finished, generating a titanium dioxide nanotube array on the titanium surface. After the electrolysis, the sample was washed with deionized water and then dried at 40 ℃ to obtain a titanium oxide sample.
3) Ruthenium salt heat treatment: dissolving ruthenium sulfate in water to form 50mg/mL ruthenium sulfate solution, and carrying out lifting and pulling for 3 times by using a pulling method to soak the surface of the sample with the titanium oxide nano-structure coating obtained after drying in the step 2) with the prepared ruthenium sulfate solution; putting the sample soaked with ruthenium sulfate into an oven to be dried at 40 ℃; and (3) putting the dried sample into a muffle furnace, and carrying out heat treatment for 4 hours at 300 ℃ to obtain the sample with the bioactive micro-arc titanium oxide surface tin dioxide-ruthenium dioxide coating.
4) Charging: and (3) charging the titanium oxide sample obtained after cleaning and drying in the step 3) to obtain the titanium-based surface tin dioxide-ruthenium dioxide antibacterial coating with electrical activity, biological activity and good antibacterial activity. Wherein the charging time is 4h and the charging voltage is 1.5 v.
Referring to FIG. 1, the anodizing apparatus of the present invention is shown in FIG. 1, using a treated titanium sample as an anode, a platinum sheet as a cathode, and ethylene glycol and NH4And mixing and melting the solution F in water to form a mixed solution, and performing electrolysis treatment by using the mixed solution as an electrolyte.
Referring to fig. 2, the titanium dioxide ruthenium dioxide coating prepared by the present invention includes titanium dioxide 2 firmly grown on a titanium sample 1, and ruthenium dioxide 3 grown on the titanium dioxide 2, the prepared coating has a nano composite structure, and a titanium dioxide nano-column rod-shaped structure layer generated by an anodic oxidation method is tightly combined with a ruthenium dioxide nano-structure generated by ruthenium salt heat treatment.
Referring to fig. 3, it can be seen from fig. 3 that the titanium-based medical device prepared by the present invention has no bacteriostatic effect before the antibacterial coating is charged, the spots in the test are viable bacteria, and a large number of spots are visible in the test. The uncharged sample has poor bacteriostatic ability.
Referring to fig. 4, it can be seen from fig. 4 that the titanium-based medical treatment prepared by the invention shows that the antibacterial coating is tested for bacteriostatic performance after being positively charged, spots in the figure are viable bacteria, the spots in the figure are greatly reduced, and the killing rate of staphylococcus aureus can reach 90%, thus proving that the titanium-based medical equipment prepared by the invention shows that the antibacterial coating has excellent bacteriostatic effect after being charged. The charge sample has good bacteriostatic ability.
The specific capacitance of the coating prepared by the invention is up to 1.86F/m through experimental measurement2It is sufficient to demonstrate a large increase in the specific surface area of titanium.
The preparation method comprises the steps of polishing and ultrasonically cleaning a sample for pretreatment, then taking the treated titanium sample as an anode, taking a platinum sheet as a cathode, and using ethylene glycol and NH4And F, dissolving the mixed solution in water to form a mixed solution, and performing electrolysis treatment by using the mixed solution as an electrolyte to generate a titanium dioxide nanotube array on the surface of the titanium. And cleaning and drying after the electrolysis is finished. Soaking the surface of the obtained sample with ruthenium solution, and drying; and carrying out heat treatment on the dried sample to obtain the titanium dioxide ruthenium dioxide coating with bioactivity. And charging the obtained titanium sample to obtain the titanium-based medical instrument surface antibacterial coating. The coating has excellent electrical property in an electrical property test and has good antibacterial property in an antibacterial property test.

Claims (7)

1. A preparation method of an antibacterial coating on the surface of a titanium-based medical instrument is characterized by comprising the following steps:
(1) material pretreatment: pretreating a titanium-based material;
in the step (1), the titanium-based material is Ti-6Al-4V alloy, TC4 titanium alloy, TA2 industrial pure titanium or TA3 industrial pure titanium; the pretreatment is to polish, clean and dry by sand paper;
(2) anodic oxidation: taking the titanium-based material pretreated in the step (1) as an anode and a platinum sheet as a cathode, and carrying out electrolytic treatment in electrolyte to generate a titanium dioxide nanotube array on the surface of the titanium-based material; after the electrolysis is finished, cleaning and drying to obtain a titanium-based material with a titanium dioxide coating;
(3) ruthenium salt heat treatment: soaking the surface of the titanium-based material with the titanium dioxide coating obtained in the step (2) with a ruthenium solution, and then sequentially drying and thermally treating to obtain the titanium-based material with the titanium dioxide-ruthenium dioxide coating;
in the step (3), the titanium-based material with the titanium dioxide coating is subjected to surface infiltration of a ruthenium solution by pulling for 2-5 times through a pulling method; in the step (3), the temperature of the heat treatment is 200-550 ℃, and the time is 0.5-4 h;
through anodic oxidation treatment and ruthenium salt heat treatment, a coating with a titanium dioxide ruthenium dioxide nanostructure is grown on the titanium surface, so that the specific surface area of the titanium is increased;
(4) charging: and (4) charging the titanium-based material with the titanium dioxide-ruthenium dioxide coating obtained in the step (3) to obtain the titanium-based medical instrument surface antibacterial coating.
2. The method for preparing the antibacterial coating on the surface of the titanium-based medical device as claimed in claim 1, wherein the sandpaper is one or more of 240 meshes, 400 meshes, 600 meshes and 1000 meshes.
3. The method for preparing the antibacterial coating on the surface of the titanium-based medical instrument as claimed in claim 1, wherein in the step (2), the electrolyte is ethylene glycol and NH4The solution F is formed by mixing and melting in water, and the volume ratio of the ethylene glycol to the water is (0.5-1.5): NH in electrolyte solution4The concentration of F is 0.1-1.5 mol/L.
4. The preparation method of the antibacterial coating on the surface of the titanium-based medical instrument as claimed in claim 1, wherein in the step (2), during the electrolysis treatment, the anode voltage is 10-80V, and the electrolysis time is 1-8 h.
5. The method of claim 1, wherein in the step (3), the ruthenium solution is prepared by adding ruthenium salt into water, and the concentration of the ruthenium solution is 5 mg/mL-50 mg/mL.
6. The method for preparing the antibacterial coating on the surface of the titanium-based medical instrument as claimed in claim 5, wherein the ruthenium salt is ruthenium acetate, ruthenium chloride or ruthenium sulfate.
7. The method for preparing the antibacterial coating on the surface of the titanium-based medical instrument as claimed in claim 1, wherein in the step (4), the charging time is 1 h-4.5 h, and the charging voltage is 0.2 v-1.8 v.
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