CN116115836A - Surface coating for improving antibacterial property of pure titanium or titanium alloy surface, preparation method and application - Google Patents

Surface coating for improving antibacterial property of pure titanium or titanium alloy surface, preparation method and application Download PDF

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CN116115836A
CN116115836A CN202310052559.8A CN202310052559A CN116115836A CN 116115836 A CN116115836 A CN 116115836A CN 202310052559 A CN202310052559 A CN 202310052559A CN 116115836 A CN116115836 A CN 116115836A
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titanium alloy
coating
titanium
antibacterial
antibacterial property
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张二林
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Yangzhou Tibo Medical Device Technology Co ltd
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Yangzhou Tibo Medical Device Technology Co ltd
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    • 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
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L31/00—Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
    • A61L31/02—Inorganic materials
    • A61L31/022—Metals or alloys
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L31/00—Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
    • A61L31/08—Materials for coatings
    • A61L31/082—Inorganic materials
    • A61L31/088—Other specific inorganic materials not covered by A61L31/084 or A61L31/086
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L31/00—Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
    • A61L31/14—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
    • A61L31/146—Porous materials, e.g. foams or sponges
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L31/00—Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
    • A61L31/14—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
    • A61L31/16—Biologically active materials, e.g. therapeutic substances
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C14/00—Alloys based on titanium
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L2300/00—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
    • A61L2300/10—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices containing or releasing inorganic materials
    • A61L2300/102—Metals or metal compounds, e.g. salts such as bicarbonates, carbonates, oxides, zeolites, silicates
    • A61L2300/104—Silver, e.g. silver sulfadiazine
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L2300/00—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
    • A61L2300/40—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices characterised by a specific therapeutic activity or mode of action
    • A61L2300/404—Biocides, antimicrobial agents, antiseptic agents
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L2420/00—Materials or methods for coatings medical devices
    • A61L2420/02—Methods for coating medical devices
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L2420/00—Materials or methods for coatings medical devices
    • A61L2420/08—Coatings comprising two or more layers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
    • Y02A50/30—Against vector-borne diseases, e.g. mosquito-borne, fly-borne, tick-borne or waterborne diseases whose impact is exacerbated by climate change

Abstract

The invention relates to the field of titanium alloy industry, in particular to a surface coating for improving the antibacterial property of the surface of pure titanium or titanium alloy, a preparation method and application thereof. The coating for improving the antibacterial property of the surface of the pure titanium or titanium alloy mainly comprises an inner layer, a middle transition layer and an outer layer, wherein the inner layer is compact, and the outer layer has submicron and micron pore structures; the coating contains nano-grade AgO and Ag which are uniformly distributed 2 O 3 The method comprises the steps of carrying out a first treatment on the surface of the By the invention is providedThe antibacterial property of the pure titanium or titanium alloy treated by the coating and the preparation method can reach more than or equal to 90 percent, even more than or equal to 99.9 percent; can be applied to titanium alloy foods and medical appliances, and can improve the antibacterial and antibacterial functions of the equipment and the appliances.

Description

Surface coating for improving antibacterial property of pure titanium or titanium alloy surface, preparation method and application
Technical Field
The invention relates to the field of titanium alloy industry, in particular to a surface coating for improving the antibacterial property of the surface of pure titanium or titanium alloy, a preparation method and application thereof.
Background
Pure titanium or titanium alloy has very good specific strength and specific stiffness characteristics, and corrosion resistance, and thus is widely used in various industries. Meanwhile, pure titanium or titanium alloy has good biocompatibility and is also widely applied to medical implantation instruments. However, the surface of pure titanium or titanium alloy is very easy to cause adhesion of bacteria on the surface, further causes propagation of bacteria, causes propagation of bacteria and causes various diseases, so that the antibacterial and antibacterial properties of the pure titanium or titanium alloy are required to be improved, and the service performance of the pure titanium or titanium alloy is required to be improved.
There are various methods for improving the antibacterial property of pure titanium or titanium alloy, for example, alloying elements having antibacterial property are added to pure titanium or titanium alloy, for example, copper-containing antibacterial titanium alloy (ZL 202010364476.9, CN 202011055146.8), silver-containing antibacterial titanium alloy (ZL 201810085913.6) and iron-containing antibacterial titanium alloy (CN 202111079986.2) have been reported.
Ag element is a broad-spectrum antibacterial metal and has been widely used in high-grade tableware, and antibacterial functions have been known for a long time. The antibacterial paths of Ag element mainly include the following:
(1) Antibacterial and sterilizing Ag ions. Ag ion sterilization has been widely used for bacteriostasis and sterilization in industrial and medical environments. The material can dissolve enough Ag ions to achieve ion antibacterial effect, but the titanium alloy has very good corrosion resistance, and the titanium alloy is very difficult or almost impossible to dissolve enough Ag ions. However, a coating containing Ag ions, such as a salt, polymer or ceramic coating containing Ag ions, is prepared on the surface of the titanium alloy, and when the Ag ions in the coating are dissolved out, a very good antibacterial effect is generated.
(2) Nano Ag is antibacterial. There are many methods for doping elemental nano Ag particles into the surface of titanium alloys, such as plasma implantation, electrochemical techniques, plasma spraying, and magnetron sputtering. Chinese patent CN 113502524A adopts a mode of combining anodic oxidation and hydrothermal treatment, firstly forms nano barium titanate on the surface of titanium, and then immerses the nano barium titanate in AgNO 3 In the solution, nano Ag particles are loaded on the surface of nano barium titanate, so that the nano barium titanate has good antibacterial performance. The patent CN 113463083A adopts a cold spraying method to directly form a coating containing Ag on the surface of titanium, and has good antibacterial property. CN 110302418A and CN 107115559A also provide a method for preparing nano Ag and TiO by hot water method and ion exchange, anodic oxidation and ion reaction 2 Composite coatingHas synergistic antibacterial effect. The preparation of a coating containing Ag ions or nano Ag particles on the surface of a titanium alloy, which achieves an antibacterial effect by dissolved Ag ions or nano Ag particles, is a very effective method for improving the antibacterial performance of the titanium alloy, and has been confirmed by a plurality of examples. The nano silver particles have obvious antibacterial effect, and the research proves that silver can block the electron transfer process of cell membranes and destroy the structure of the cell membranes. However, ag ions and nano silver particles have potential biotoxicity, particularly, the toxicity of nano silver particles is 1000 times that of Ag ions, and free nano silver particles are easy to be phagocytosed by normal cells and cause biotoxicity, so that the biotoxicity of nano silver particles needs to be controlled, and special attention is required in bio-related applications.
(3) A surface potential difference antibacterial mechanism. According to patent ZL202010364476.9, the titanium alloy surface forms enough micro-zone potential difference, and good antibacterial performance can be obtained. In order to obtain a sufficient micro-domain potential difference at the surface, a sufficient second phase must be formed inside the titanium alloy. In the case of Ag-containing titanium alloys, this means that the alloy must have sufficient Ag element to have good antimicrobial properties. For example, the literature reports that only Ag contents exceeding 9% by weight can have an antibacterial rate of > 90%. An increase in Ag content will significantly increase the manufacturing cost of the antimicrobial titanium alloy.
On the premise of not causing biotoxicity, the antibacterial function of Ag is fully utilized, the antibacterial performance of pure titanium or titanium alloy is improved, the application range of titanium and titanium alloy is widened, and the problem to be solved is solved, particularly, the biotoxicity of Ag ions and nano Ag particles is avoided, and the antibacterial performance of Ag element can be fully exerted.
Disclosure of Invention
Aiming at the industrial application of the titanium alloy, the invention provides a coating for improving the antibacterial performance of pure titanium or titanium alloy, a preparation method and application thereof, which can obviously improve the antibacterial and antibacterial performance of the pure titanium or titanium alloy and can be widely applied to the industrial fields of food processing, medical appliances and the like.
The technical scheme of the invention is as follows: coating for improving antibacterial property of pure titanium or titanium alloy surface and main coatingThe composite material consists of an inner layer, a middle transition layer and an outer layer, wherein the inner layer is compact, and the outer layer has submicron and micron pore structures; the coating contains uniformly distributed nano AgO and nano Ag 2 O 3 And not more than 5% by weight of Ag 2 O; the weight percentage of Ag element in the coating is not more than 8%.
The antibacterial effect of the coating mainly comes from nano AgO and nano Ag in the coating 2 O 3 . AgO and Ag 2 O 3 Has very strong oxidizing power, and when bacteria come into contact with them, oxidation reaction rapidly occurs, electron exchange is performed, bacterial membrane is destroyed, and bacteria are killed, namely AgO and Ag 2 O 3 Contact antibacterial and bactericidal mechanisms. In the antibacterial and bactericidal processes, no Ag ions or nano Ag particles are dissolved out, so that good antibacterial effect is ensured, and the biotoxicity of the Ag ions or nano Ag particles is avoided. AgO and Ag 2 O 3 Is dependent on AgO and Ag for its antibacterial effect 2 O 3 The greater the number of contacts and the greater the contact area with bacteria, the better the antibacterial effect. AgO and Ag 2 O 3 Exists in the coating in nano scale, can obviously improve AgO and Ag 2 O 3 The contact area with bacteria can obtain better antibacterial effect.
The compact inner layer of the coating can ensure that the coating and the matrix titanium have very high bonding strength, and simultaneously the corrosion resistance of the titanium alloy is improved. The submicron and micron pore structure of the outer layer enlarges the surface area of the coating, can improve the contact area between bacteria and the coating, and fully plays the roles of nano AgO and nano Ag in the coating 2 O 3 Is effective in inhibiting bacteria.
Coating preparation is to ensure that: 1) Ag element is formed by AgO and Ag 2 O 3 Is present in the form of (c). Part of Ag is inevitably formed in the preparation process 2 O, as long as the weight percentage is not more than 5%, will not influence the antibacterial performance of the coating; 2) AgO and Ag 2 O 3 Is of the size of nanometers, 3) the coating has a three-layer composite structure, particularly a submicron and micron-sized pore structure of the outer layer, captures more bacteria, increases the bacteria and AgO and Ag 2 O 3 Is provided.
Electrolytic oxidation of solutions to AgO and Ag 2 O 3 There are two problems with coatings: 1) Ag (silver) + Is a cation and is therefore easily deposited on the cathode during electrolytic oxidation, so that a coating layer containing Ag cannot be formed on the surface of the anode titanium. 2) AgO and Ag 2 O 3 Is an unstable oxide, and can be converted into Ag during the preparation process and the subsequent use process 2 O, reduces the antimicrobial properties of the coating. This requires control of process parameters during the preparation and subsequent stabilization to form Ag 2 The weight percentage of O is not more than 5%.
A preparation method of a coating for improving the antibacterial property of the surface of pure titanium or titanium alloy comprises the following steps: 1) And (5) surface pretreatment. Removing oil and oxide skin on the surface of the titanium alloy in a physical, chemical or electrochemical mode; on one hand, the oil and oxide skin on the surface are removed, the interface bonding strength of the coating and the matrix is improved, the service life is prolonged, and on the other hand, the fresh titanium matrix is leaked out to fully react with electrolyte solution, so that the designed coating is formed. 2) And (5) solution plasma oxidation treatment. The pretreated titanium alloy is subjected to voltage treatment in electrolyte solution for no less than 1min, plasma is generated, oxidation treatment is carried out, and a coating is formed on the surface of the pretreated titanium alloy; 3) And (5) stabilizing treatment. The titanium alloy after oxidation treatment is kept at the temperature of 80-750 ℃ for not more than 10 hours, so that the stabilization of the chemical components and chemical properties of the surface is realized. Because the gas is released in the oxidation process of the step 1) and the step 2), the formed coating has a loose structure, the surface of the titanium alloy forms a porous coating, and the coating contains a large amount of nano-scale AgO and Ag 2 O 3 . However, both of these compounds are unstable phases and are liable to decompose, and thus require stabilization treatment to be stably present in the coating layer.
In the pretreatment, naOH aqueous alkali containing not less than 5g/L is adopted to remove oil stains on the surface of the silver-containing titanium alloy, and then acid solution containing hydrofluoric acid with the concentration not more than 5% is adopted to remove oxide skin on the surface.
The electrolyte is soluble inThe liquid contains free PO 4 -1 、SO 4 -2 、SiO 3 -2 One or two or more of them; containing free PO 4 -1 Free PO at the time 4 -1 The concentration of (2) is not less than 0.05mol/L; containing free SO 4 -2 Free SO 4 -2 The concentration of (2) is not less than 0.05mol/L; containing free SiO 3 -2 Free SiO 3 -2 The concentration of (2) is not less than 0.05mol/L;
for pure titanium and non-silver-containing titanium alloys, the electrolyte solution also contains chelates of Ag, complexes of Ag, or Ag 2 At least one of the O particles has Ag content not less than 0.1g/L.
When the titanium alloy is a silver-containing titanium alloy, the electrolyte solution may be free of chelates of Ag, complexes of Ag, and Ag 2 O particles, good antibacterial properties can also be obtained. Because Ag exists in the silver-containing titanium alloy, the silver-containing titanium alloy can participate in oxidation reaction to form silver oxide.
Chelate or complex of Ag, including but not limited to EDTa-Ag/Na. The Ag content in the solution is not less than 0.1g/L.
Ag by Ag 2 When present in the form of O particles, some dispersant and suspending agent may be added.
The voltage value of the applied voltage is as follows: 10V-450V.
The voltage value of the applied voltage is as follows: 20V-350V.
The voltage value of the applied voltage is as follows: 121V-200V.
The stabilization treatment temperature is 100-400 ℃, and the stabilization treatment time is not more than 6 hours.
The application of the coating for improving the antibacterial property of the surface of the pure titanium or titanium alloy in the antibacterial property of the surface of the silver-containing titanium alloy comprises the following components in percentage by weight: 0.1-20%.
The silver element in the silver-containing titanium alloy comprises the following components in percentage by weight: 0.4-4.9%.
The coating may also contain trace elements such as Ca, ce, sr, K, P and O.
The invention has the beneficial effects that: the antibacterial property of the pure titanium or titanium alloy treated by the coating and the preparation method can reach more than or equal to 90 percent, even more than or equal to 99.9 percent; the antibacterial performance of the surface of the silver-containing titanium alloy with low silver content is obviously improved, and 90% of antibacterial effect can be realized by the method as long as the silver content in the silver-containing titanium alloy is not less than 0.1%.
Detailed Description
Selecting commercial pure titanium and TC4 titanium alloy as samples, placing the samples into the electrolyte solution, applying voltage, treating for different time, taking out the samples, ultrasonically cleaning chemical reagents remained on the surface by clean water, airing the samples, preserving the heat for a certain time at the temperature of 80-750 ℃, and then detecting the antibacterial property.
The embodiment selects pure titanium, TC4 and Ti-Ag alloy for relevant experiments, and the application effect of the titanium alloy on the surfaces of other titanium alloys is not affected.
The antibacterial test is specified according to the standards of JIS Z2801-2000 antibacterial processed products-antibacterial test method and antibacterial effect, and the like, and specifically comprises the following steps: 0.3mL of the test bacterial liquid is respectively taken and added to a control sample (pure titanium) and an iron-containing titanium alloy sample in a dropwise manner. The cover films are respectively covered on the samples by using sterilizing forceps, so that bacterial liquid is uniformly contacted with the samples, and the samples are placed in a sterilizing plate and are placed in a constant temperature incubator for culturing for 24 hours under the conditions of 37 ℃ and the relative humidity of more than 90 percent. Taking out the cultured samples for 24 hours, respectively adding 15mL of eluent, repeatedly cleaning the samples and the cover film, shaking uniformly, respectively taking 0.1mL of the samples which are dripped into the plate nutrient agar medium, making three parallel samples for each sample, uniformly coating the samples by using a sterilization triangular rake, culturing the samples in a constant temperature oven at 37 ℃ for 48 hours, and counting viable bacteria according to the method of GB/T4789.2.
The sterilization rate of the iron-containing titanium alloy after the iron-containing titanium alloy acts on common bacteria (such as escherichia coli, staphylococcus aureus and the like) is calculated according to the following formula:
the sterilization rate (%) = [ (number of viable bacteria of culture dish sample-number of viable bacteria of treated sample)/number of viable bacteria of culture dish product ] ×100%.
Table one is an example of an implementation of pure titanium and an Ag-free titanium alloy.
Examples 1 and 2 are commercially available pure titanium and TC4 titanium alloys, respectively, which were treated with conventional mechanical polishing, alkali treatment and acid treatment to remove oil stains and scale from the surface, with an antibacterial rate of 0% and no antibacterial properties.
The same pure titanium and TC4 alloy have good antibacterial performance after the preparation method of the coating, such as other implementation examples in the table I, and the antibacterial rate reaches more than 90 percent.
Comparing examples 3, 5 and 6, it can be seen that either the free PO is contained 4 -1 、SiO 3 -2 Or SO 4 -2 The antibacterial rate is higher than 98%, and very good antibacterial performance can be obtained.
As a result of comparing examples 6 and 7, it can be found that as long as the electrolyte solution contains Ag 2 O particles or chelates of Ag and complexes of Ag, such as EDTa-Ag/Na, can obtain very good antibacterial performance through the preparation method route of the invention.
Comparing examples 7, 8 and 9, it was found that very good antibacterial properties can be obtained by the route of the preparation method according to the present invention as long as the Ag content in the electrolyte solution is not less than 0.1g/L.
Comparing examples 6, 10 and 11, it was found that very good antibacterial properties can be obtained by the route of the preparation method according to the present invention as long as the Ag content in the electrolyte solution is not less than 0.1g/L.
The antibacterial property of the titanium alloy surface depends on the relative content of Ag on the surface, and as the content of Ag in the coating layer increases, the antibacterial property increases stepwise, and comparative examples 1, 10, 11, 12, 13, 14 and 15 are conducted. When the Ag content in the coating reaches 8%, the antibacterial rate reaches more than 99.9%, and the manufacturing cost is increased by continuously increasing the Ag content in the coating.
Free PO in electrolyte solution 4 -1 、SiO 3 -2 、SO 4 -2 The content must be not less than 0.05mol/L, otherwise the oxidation reaction cannot be achieved, the desired antibacterial effect cannot be achieved, for example, embodiment example 16, because of free PO 4 -1 The content is less than 0.05mol/L, resulting in failure to effect oxidation reaction, ag formed 2 The O content is more, agO and Ag 2 O 3 Is less in content, ultimately resulting in a coating antibacterial rate<10% without antimicrobial properties. But free PO in the electrolyte solution 4 -1 、SiO 3 -2 、SO 4 -2 At concentrations above 0.05mol/L, there is no effect on the antimicrobial properties, for example, examples 17 and 18.
The voltage of the oxidation process determines the thickness of the oxidized coating and the size of the surface pore structure. The higher the voltage, the larger the pore size formed and the thicker the coating thickness. The voltage is low, the surface cannot form sufficient plasma oxidation reaction, and Ag is formed 2 The O content is more than 5 percent, and AgO and Ag 2 O 3 The content of (2) is small, so that the surface antibacterial property is poor. However, the voltage is too large, the surface of the sample is damaged greatly, the surface morphology is damaged, a perfect coating cannot be formed, and the overall antibacterial effect is not ideal. Very good antibacterial properties can be obtained at voltages ranging from 10 to 450V, for example, in comparative examples 19, 20, 21, 22, 23, 24, 25.
Stabilization ensures that Ag is formed by AgO and Ag 2 O 3 Stabilized, if no stabilization is carried out, or the stabilization temperature is below 80 ℃, agO and Ag 2 O 3 Unstable, turns into other substances, and loses antibacterial properties, such as example 26. The stabilization treatment temperature was as high as 80-750℃to obtain a very good antibacterial effect, and comparative examples 23, 27, 28, 29 and 30. Treatment at a temperature exceeding 750 ℃ seriously reduces the mechanical properties of the alloy, and the use of the alloy is not recommended.
The stabilization treatment time was controlled to be within 10 hours, so that the coating could be stabilized to achieve the desired antibacterial effect, as compared with examples 25, 31, 32 and 33. Extending the stabilization treatment time can seriously affect the mechanical properties of the titanium alloy and waste energy, and is not recommended.
Table-comparison of the antimicrobial properties of samples under different treatment conditions.
Figure BDA0004058872670000081
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Figure BDA0004058872670000091
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Figure BDA0004058872670000101
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Figure BDA0004058872670000111
The second table lists several silver-containing titanium alloys with different Ag contents, and the present embodiment uses a Ti-Ag binary alloy as an example for convenience of description, so that the method designed by the present invention is not affected and the same application effect is obtained when the method is applied to other silver-containing titanium alloys.
The Ti-Ag alloy not surface-treated had an antibacterial rate of 0% and no antibacterial property when the silver content was less than 4.9 wt%. The antibacterial rate increases with the increase of the silver content in the silver-containing titanium alloy, but at silver contents of less than 13wt%, the antibacterial rate is still less than 90%, which is also called no antibacterial material. When the silver content reached and exceeded 13 wt.%, the antibacterial rate reached 90%, which is an antibacterial material, examples 1 to 9 were carried out as in Table II. Compared with Ti-Ag alloy treated by the method, the antibacterial performance of the silver-containing titanium alloy is greatly improved by implementing examples 10-18 in the second table, and the antibacterial performance of the original non-antibacterial Ti-Ag alloy is improved remarkably, and the antibacterial performance is improved obviously. For Ti-Ag alloy with higher Ag content, the antibacterial performance is greatly improved, and the antibacterial rate of the Ti-13Ag alloy is improved from 90% to 99.9%.
Examples 13, 19, 20, 21, 22, 23 and 24 in comparative table two show that the antibacterial performance of the treated silver-containing titanium alloy can reach an antibacterial rate of >90% and the antibacterial rate is not greatly affected, regardless of whether the solution contains one, two or three of free phosphate, free silicate and free sulfuric acid.
Examples 14, 25 and 26 in Table II were compared to find that a good antibacterial effect could be achieved as long as the concentration of free phosphate in the solution was not less than 0.05mol/L, without a large difference, but when the concentration of free phosphate in the solution was less than 0.05mol/L, the antibacterial rate was only 50%, and the same effect was not achieved for other free silicate and free sulfuric acid, for example, example 27.
Comparison of examples 14, 28, 29, 30, 31, 32 and 33 in Table II shows that the applied voltage has a certain effect on the antimicrobial properties, and that the antimicrobial properties at low voltages are slightly lower than those at high voltages, but the difference is very small when the voltage exceeds 100V, and particularly when the voltage exceeds 121V, a stable 99.9% antimicrobial ratio is maintained.
As can be seen from comparison of examples 32, 34, 35, 36, 37 and 38 in Table II, the stabilization effect can be achieved at 80-750deg.C, the temperature and time changes have little effect on the antibacterial property, the energy consumption is large, and the long-term stabilization treatment is not recommended. However, when the stabilization temperature is lower than 80 ℃, the stabilization treatment cannot be achieved, and the desired antibacterial effect cannot be achieved, for example, embodiment 39.
When the Ag-containing compounds in the solutions were compared with examples 10, 11, 40, 41 in table two, the antibacterial properties of the alloys were further improved from 90% to 99.9%, and the other several alloys showed the same effects, for example, examples 42, 43, and 44 in table two.
The antibacterial properties of the alloys before and after the treatment are compared, and the treatment method provided by the invention not only remarkably improves the antibacterial properties of the silver-containing titanium alloy, but also reduces the minimum silver content in the antibacterial titanium alloy, and is hopeful to reduce the cost of the alloy while not reducing the antibacterial properties.
Table two comparison of antibacterial properties of Ti-Ag alloys under different treatment conditions
Figure BDA0004058872670000131
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Figure BDA0004058872670000141
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Figure BDA0004058872670000151
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Figure BDA0004058872670000161
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Figure BDA0004058872670000171
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Claims (10)

1. The coating for improving the antibacterial property of the surface of the pure titanium or the titanium alloy is characterized by mainly comprising an inner layer, a middle transition layer and an outer layer, wherein the inner layer is compact, and the outer layer has submicron and micron pore structures; the coating contains uniformly distributed nano AgO and nano Ag 2 O 3 And not more than 5% by weight of Ag 2 O; the weight percentage of Ag element in the coating is not more than 8%.
2. The preparation method of the coating for improving the antibacterial property of the surface of the pure titanium or titanium alloy is characterized by comprising the following steps of: 1) Surface pretreatment; removing oil and oxide skin on the surface of pure titanium or titanium alloy in a physical, chemical or electrochemical mode; 2) Solution plasma oxidation treatment: the pretreated pure titanium or titanium alloy is placed in electrolyte solution, voltage treatment is applied for no less than 1min, plasma is generated, solution plasma oxidation treatment is carried out, and a coating is formed on the surface of the pretreated pure titanium or titanium alloy; 3) Stabilizing treatment; the pure titanium or titanium alloy after oxidation treatment is kept at 80-750 ℃ for not more than 10 hours for stabilizing the chemical components and chemical properties of the surface.
3. The method for preparing a coating for improving the antibacterial property of a pure titanium or titanium alloy surface according to claim 2, wherein the electrolyte solution contains free PO 4 -1 、SO 4 -2 、SiO 3 -2 One or two or more of them; containing free PO 4 -1 Free PO at the time 4 -1 The concentration of (2) is not less than 0.05mol/L; containing free SO 4 -2 Free SO 4 -2 The concentration of (2) is not less than 0.05mol/L; containing free SiO 3 -2 Free SiO 3 -2 The concentration of (2) is not less than 0.05mol/L; the electrolyte solution also contains chelate of Ag, complex of Ag and Ag 2 One of the O particles has Ag content not less than 0.1g/L.
4. The method for preparing a coating for improving the antibacterial property of a pure titanium or titanium alloy surface according to claim 3, wherein when the titanium alloy is a silver-containing titanium alloy, the electrolyte solution does not contain chelates of Ag, complexes of Ag and Ag 2 And O particles.
5. The method for preparing a coating for improving the antibacterial property of a pure titanium or titanium alloy surface according to claim 2, 3 or 4, wherein the voltage value of the applied voltage is: 10V-450V.
6. The method for preparing a coating for improving the antibacterial property of a pure titanium or titanium alloy surface according to claim 5, wherein the voltage value of the applied voltage is: 20V-350V.
7. The method for preparing a coating for improving the antibacterial property of a pure titanium or titanium alloy surface according to claim 2 or 6, wherein the voltage value of the applied voltage is: 121V-200V.
8. The method for preparing a coating for improving the antibacterial property of a pure titanium or titanium alloy surface according to claim 2, wherein the stabilization treatment temperature is 100-400 ℃ and the stabilization treatment time is not more than 6 hours.
9. Use of the coating for improving the antibacterial property of the surface of pure titanium or titanium alloy according to claim 1, wherein the silver element in the silver-containing titanium alloy is in weight percentage: 0.1-20%.
10. The use according to claim 9, wherein the silver element in the silver-containing titanium alloy comprises the following weight percentages: 0.4-4.9%.
CN202310052559.8A 2023-02-02 2023-02-02 Surface coating for improving antibacterial property of pure titanium or titanium alloy surface, preparation method and application Pending CN116115836A (en)

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