CN114159626A - Sodium tantalate film with bioactivity and antibacterial property and preparation method thereof - Google Patents

Sodium tantalate film with bioactivity and antibacterial property and preparation method thereof Download PDF

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CN114159626A
CN114159626A CN202111447568.4A CN202111447568A CN114159626A CN 114159626 A CN114159626 A CN 114159626A CN 202111447568 A CN202111447568 A CN 202111447568A CN 114159626 A CN114159626 A CN 114159626A
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film layer
hydrothermal
tantalum
sodium tantalate
doped
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CN114159626B (en
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王翠翠
张意茹
蔡安琦
张于浩
刘轶凡
陈倩
宋颖轩
殷海荣
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Shaanxi University of Science and Technology
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Shaanxi University of Science and Technology
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    • 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
    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
    • A61L27/54—Biologically active materials, e.g. therapeutic substances
    • 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
    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/02—Inorganic materials
    • A61L27/04—Metals or alloys
    • A61L27/047—Other specific metals or alloys not covered by A61L27/042 - A61L27/045 or A61L27/06
    • 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
    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/28—Materials for coating prostheses
    • A61L27/30—Inorganic materials
    • A61L27/306—Other specific inorganic materials not covered by A61L27/303 - A61L27/32
    • 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
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/60—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using alkaline aqueous solutions with pH greater than 8
    • C23C22/64—Treatment of refractory metals or alloys based thereon
    • 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
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/82—After-treatment
    • C23C22/83—Chemical after-treatment
    • 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
    • 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
    • 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
    • A61L2300/412—Tissue-regenerating or healing or proliferative 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
    • A61L2430/00—Materials or treatment for tissue regeneration
    • A61L2430/02—Materials or treatment for tissue regeneration for reconstruction of bones; weight-bearing implants

Abstract

The invention provides a surface modified biological metal material with bone promoting and antibacterial capabilities. The surface modification technology prepares a bioactive film layer codoped with functional elements of calcium and copper on the surface of pure tantalum through the synergistic effect of a hydrothermal-molten salt-hydrothermal method (or a hydrothermal-molten salt method). Firstly, a uniform sodium tantalate film layer is prepared on the surface of metal tantalum by a hydrothermal method, and then Ca is further added by a molten salt growth method2+Is doped on the sodium tantalate film layer and is finally doped with Ca2+Tantalum of the sodium tantalate film layer is doped with Cu through secondary hydrothermal2+So that a Ca-Cu co-doped film layer with bioactivity and antibacterial property is formed on the surface of the pure tantalum. The film layer containing calcium and copper prepared by the method is uniformly distributed on the surface of tantalum, is beneficial to promoting cell differentiation and improving cell activity, has certain antibacterial property, improves the bone-promoting property and the antibacterial property of tantalum metal, and shows good application prospect in the field of medical implant materials.

Description

Sodium tantalate film with bioactivity and antibacterial property and preparation method thereof
Technical Field
The invention belongs to the technical field of surface modification of metal materials, and particularly relates to a sodium tantalate film with bioactivity and antibacterial property and a preparation method thereof.
Background
Due to frequent occurrence of car accidents, collisions and disasters, damaged and fractured or serious injuries of hard tissues of the body such as teeth, bones and the like always occur. Because of its excellent mechanical properties, corrosion resistance, safety and non-toxicity, the medical metal tantalum (Ta) is widely used in the fields of hip joint replacement, knee joint repair and the like. As with most medical metals, pure metallic tantalum is poorly bioactive, poorly able to promote new bone formation and non-antibacterial, and thus limited in clinical use. In addition, in hard tissue implantation surgery, postoperative infection is also one of the problems to be solved urgently. These are the problems that tantalum is needed to solve as hard tissue implant material. The bioactive film layer loaded with functional ions on the surface of tantalum is a main method for improving the biological performance of materials.
Ca2+Is biological apatite (Ca)10(PO4)6(OH)2) One of the main constituent elements plays an important role in bone formation and bone resorption. The mechanism of activation within the cell is based on influencing calcium sensitive receptors in osteoblasts. All the above characteristics allow the doping of Ca2+The implant material of (3) is more fully combined with bone tissues, and the amount of the peripheral new bone is also more. Copper and its ions have long been recognized as having antimicrobial properties, broad spectrum bactericidal ability, being biologically safe to control over a range of concentrations, and being biologically active at a given concentration. In addition, copper ions do not produce bacteriaDrug resistance. Thus, copper and its ions have been incorporated into the surface of a variety of biomaterials.
The existing methods for doping elements comprise a sol-gel method, a wet chemical precipitation method, an electrophoretic deposition method, a melt spinning method, a pulse laser deposition method, a smelting and quenching method, a micro-arc oxidation method, an anodic oxidation method, a hydrothermal method, a molten salt method and the like. Among the above methods, the hydrothermal method is to dissolve and recrystallize insoluble or insoluble substances by adjusting different hydrothermal reaction solutions in a closed high-temperature high-pressure environment and using a relatively high-temperature high-pressure reaction environment, thereby realizing element doping, and has the advantages of safe and simple operation, low reaction temperature and uniform element distribution. The molten salt method generally adopts low-melting-point salts as reaction media, so that the reaction is carried out at an atomic level, a liquid phase appears in the synthesis process, and the diffusion rate of ions is greatly accelerated. The method can realize the diffusion of the doping elements from the molten salt to the surface of the film layer, thereby realizing the doping of the film layer elements. At present, functional elements Ca and Cu are introduced into the surface of tantalum together by a hydrothermal method combined with a molten salt method and are used as medical implant materials.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a sodium tantalate film with bioactivity and antibacterial property and a preparation method thereof.
The invention is realized by the following technical scheme:
a method for preparing a sodium tantalate film with bioactivity and antibacterial property comprises the following steps:
adding the tantalum sheet into a NaOH hydrothermal solution for carrying out a hydrothermal reaction, and preparing the tantalum sheet covered with the sodium tantalate film layer;
placing the tantalum sheet covered with the sodium tantalate film layer in CaCl2Carrying out molten salt treatment in the powder to prepare a tantalum sheet of the calcium-doped sodium tantalate film layer;
adding CuCl into the tantalum sheet of the calcium-doped sodium tantalate film layer prepared in the above step2And carrying out secondary hydrothermal reaction in the hydrothermal solution, and preparing the calcium-copper co-doped sodium tantalate film layer with bioactivity and antibacterial property on the surface of the tantalum sheet.
Alternatively, the first and second electrodes may be,
a method for preparing a sodium tantalate film with bioactivity and antibacterial property comprises the following steps:
adding the tantalum sheet into a NaOH hydrothermal solution for carrying out a hydrothermal reaction, and preparing the tantalum sheet covered with the sodium tantalate film layer;
adding CuCl into the tantalum sheet covered with the sodium tantalate film layer obtained by the preparation method2Carrying out secondary hydrothermal reaction in the hydrothermal solution to prepare a tantalum sheet with a copper-doped sodium tantalate film layer;
placing the tantalum sheet of the copper-doped sodium tantalate film layer prepared in the CaCl2And performing molten salt treatment in the powder to prepare the calcium-copper co-doped sodium tantalate film layer with bioactivity and antibacterial property on the surface of the tantalum sheet.
Preferably, the concentration of the NaOH hydrothermal solution is 2 mol/L; the CuCl2The concentration of the hydrothermal solution is 0.0001-0.1 mol/L.
Preferably, the first hydrothermal reaction is carried out in a hydrothermal reaction kettle, and the filling degree of the NaOH hydrothermal solution in the hydrothermal reaction kettle is 30-40%.
Preferably, the temperature of the first hydrothermal reaction is 220 ℃, and the reaction time is 24 hours; the temperature of the secondary hydrothermal reaction is 200 ℃, and the reaction time is 2 hours.
Preferably, the temperature of molten salt treatment is 550 ℃, the temperature rise time is 90min, and the heat preservation time is 3 h.
Preferably, the molten salt treatment is carried out in a crucible, the CaCl2The filling degree of the powder in the crucible is 90-99 percent, and the CaCl is2Is anhydrous calcium chloride.
Preferably, the secondary hydrothermal reaction is carried out in a hydrothermal reaction kettle, and the CuCl is2The filling degree of the hydrothermal solution in the hydrothermal reaction kettle is 30-40%.
The microstructure of the calcium-copper co-doped sodium tantalate film with the bioactivity and the antibacterial property is cubic or spherical.
Compared with the prior art, the invention has the following beneficial technical effects:
the invention aims to provide a simple and rapid preparation method, namely a method for preparing a functional element calcium (Ca) copper (Cu) codoped bioactive film on the surface of tantalum by a hydrothermal-molten salt-hydrothermal method (or a hydrothermal-molten salt method). The material is beneficial to increasing the proliferation and differentiation of osteoblasts and has good biological activity and antibacterial property. The method can not only conveniently and rapidly prepare the sodium tantalate film on the tantalum surface, but also adjust the temperature of the molten salt method and CuCl in the subsequent functional ion doping process2The conditions of concentration, time, temperature and the like of hydrothermal doping improve the bone-promoting performance and antibacterial property of the material, and the material has good application in the aspects of surface biological modification of medical materials and the like.
The sodium tantalate film with biological activity and antibacterial property prepared by the method disclosed by the invention has the advantages that the calcium element and the copper element are uniformly distributed on the surface of the tantalum, so that the biological activity and the biological antibacterial property of the tantalum are improved, and the proliferation of osteoblasts and the killing of bacteria are promoted. The preparation condition is mild, the cost is low, and the large-scale preparation is convenient. Through the comparative analysis of the doping content of the calcium element and the copper element and the bone-promoting effect and the antibacterial effect, the optimal content of the calcium ions and the copper ions which are most beneficial to organisms is found. Further, by analyzing the antibacterial effect of the calcium-copper co-doped sodium tantalate film, it is determined that the doping sequence of doping Ca first and then doping Cu can further improve the biological activity and antibacterial property of the film.
Drawings
FIG. 1 is an SEM image of the Ca-Cu co-doped Na-tantalate film layers prepared in examples 1-4, a: calcium-copper co-doped sodium tantalate film layer prepared in example 1, b: calcium-copper co-doped sodium tantalate film layer prepared in example 2, c: calcium copper co-doped sodium tantalate film layer prepared in example 3, d: the calcium-copper co-doped sodium tantalate film layer prepared in example 4;
FIG. 2 is an SEM image of the Ca-Cu co-doped Na-tantalate film layers prepared in examples 5-8, a: calcium copper co-doped sodium tantalate film layer prepared in example 5, b: calcium copper co-doped sodium tantalate film layer prepared in example 6, c: calcium copper co-doped sodium tantalate film layer prepared in example 7, d: the calcium copper co-doped sodium tantalate film layer prepared in example 8;
fig. 3 is a TEM image of the calcium copper co-doped sodium tantalate film layers prepared in example 3 and example 7, a: NaTaO as received3TEM image of (b: NaTaO as received3HRTEM of (g), c: TEM image of the film prepared in example 7, d: HRTEM of film layer prepared in example 7, e: TEM image of the film prepared in example 3, f: HRTEM of the film layer prepared in example 3;
FIG. 4 is a surface XRD pattern of the calcium copper co-doped sodium tantalate film prepared in examples 1-4;
FIG. 5 is an AFM image of the surface of the calcium copper co-doped sodium tantalate film layer prepared in examples 1-4, a: as-is Ta, a: NaTaO as received3C, c: calcium-copper co-doped sodium tantalate film layer prepared in example 1, d: the calcium-copper co-doped sodium tantalate film prepared in example 2, e: calcium-copper co-doped sodium tantalate film prepared in example 3, f: the calcium-copper co-doped sodium tantalate film layer prepared in example 4;
fig. 6 is an ICP diagram of the calcium copper co-doped sodium tantalate film layer prepared in examples 2-4, a: cu2+B: ca2 +Ion elution map of (a);
fig. 7 is an XPS chart of the surface of the calcium-copper co-doped sodium tantalate film prepared in example 3, a: XPS total spectrum, b: high resolution spectrogram of Cu2p, c: high resolution spectrogram of Ca2 p;
FIG. 8 is a sample of the Ca-Cu co-doped sodium tantalate film prepared in examples 1-4 co-cultured with E.coli; a: as-is Ta, a: NaTaO as received3C, c: calcium-copper co-doped sodium tantalate film layer prepared in example 1, d: the calcium-copper co-doped sodium tantalate film prepared in example 2, e: calcium-copper co-doped sodium tantalate film prepared in example 3, f: the calcium copper co-doped sodium tantalate film layer prepared in example 4.
Detailed Description
The present invention will now be described in further detail with reference to specific examples, which are intended to be illustrative, but not limiting, of the invention.
NaTaO with both biological activity and antibacterial property3The film layer and the preparation method thereof are characterized in that: raw materials comprise metal tantalum sheets, NaOH and anhydrous CaCl2And CuCl2；
The concentration of the NaOH is 2 mol/L;
the preparation process of the biomedical metal material comprises the following steps:
the method comprises the following steps: putting the tantalum sheet and NaOH hydrothermal solution into a hydrothermal reaction kettle together for hydrothermal reaction, namely forming uniform NaTaO on the surface of the tantalum3A film layer;
step two: will be covered with NaTaO3Placing the tantalum sheet of the film layer in CaCl2The powder is subjected to molten salt treatment, namely Ca is formed on the surface of tantalum in a doped mode2+NaTaO (NaTaO)3And (5) film layer.
Step three: will be doped with Ca2+NaTaO3Tantalum flakes and CuCl of film layer2Putting the hydrothermal solution into a hydrothermal reaction kettle together for hydrothermal reaction, namely forming Ca doped on the surface of the tantalum2+And Cu2+NaTaO (NaTaO)3And (5) film layer.
CuCl in step three2The concentration of the solution is 0.0001-0.1 mol/L.
The reaction steps of the second step and the third step can be replaced, and Cu is doped firstly2+Re-doping with Ca2+。
The present invention will be described in detail with reference to examples. It should be noted that the embodiments and features of the embodiments in the present application may be combined with each other without conflict.
The following detailed description is illustrative of the embodiments and is intended to provide further details of the invention. Unless otherwise defined, all technical terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of exemplary embodiments according to the invention.
Example 1
A bioactive and antibacterial agentSodium tantalate (sodium tantalate) NaTaO3The film layer and the preparation method thereof, the raw materials comprise metal tantalum sheets, NaOH and anhydrous CaCl2And CuCl2；
The concentration of the NaOH is 2 mol/L;
the preparation process of the biomedical metal material comprises the following steps:
the method comprises the following steps: and putting the tantalum sheet and the NaOH hydrothermal solution into a hydrothermal reaction kettle together for hydrothermal reaction at 220 ℃ for 24 hours. Wherein, when the hydrothermal solution is injected into a hydrothermal reaction kettle, the filling degree of the solution is 30 percent, and then Ca is doped2+The tantalum sample is soaked into a hydrothermal solution for hydrothermal reaction, namely uniform NaTaO is formed on the surface of the tantalum3A film layer;
step two: will be covered with NaTaO3Placing the tantalum sheet of the film layer in CaCl2The powder is subjected to molten salt treatment in a crucible, the treatment temperature is 550 ℃, the temperature rise time is 90min, the heat preservation time is 3h, and the filling degree of the powder in the crucible is 99%. That is, Ca is doped on the surface of tantalum2+NaTaO (NaTaO)3And (5) film layer.
Step three: will be doped with Ca2+NaTaO (NaTaO)3Tantalum flakes and CuCl of film layer2Putting the hydrothermal solution into a hydrothermal reaction kettle for hydrothermal reaction, wherein the filling degree of the solution is 30% when the hydrothermal solution is injected into the hydrothermal reaction kettle, and then doping Ca2+NaTaO (NaTaO)3Soaking the tantalum sheet in the film layer into a hydrothermal solution for hydrothermal reaction, and CuCl2The concentration is 0.0001mol/L, the hydrothermal temperature is 200 ℃, the hydrothermal time is 2h, namely Ca is doped on the tantalum surface2+And Cu2+NaTaO (NaTaO)3And (5) film layer.
Example 2
NaTaO with bioactivity and antibacterial property3The film layer and the preparation method thereof, the raw materials comprise metal tantalum sheets, NaOH and anhydrous CaCl2And CuCl2；
The concentration of the NaOH is 2 mol/L;
the preparation process of the biomedical metal material comprises the following steps:
the method comprises the following steps: and putting the tantalum sheet and the NaOH hydrothermal solution into a hydrothermal reaction kettle together for hydrothermal reaction at 220 ℃ for 24 hours. Wherein, when the hydrothermal solution is injected into a hydrothermal reaction kettle, the filling degree of the solution is 30 percent, and then Ca is doped2+The tantalum sample is soaked into a hydrothermal solution for hydrothermal reaction, namely uniform NaTaO is formed on the surface of the tantalum3A film layer;
step two: will be covered with NaTaO3Placing the tantalum sheet of the film layer in CaCl2The powder is subjected to molten salt treatment in a crucible, the treatment temperature is 550 ℃, the temperature rise time is 90min, the heat preservation time is 3h, and the filling degree of the powder in the crucible is 99%. That is, Ca is doped on the surface of tantalum2+NaTaO (NaTaO)3And (5) film layer.
Step three: will be doped with Ca2+NaTaO (NaTaO)3Tantalum flakes and CuCl of film layer2Putting the hydrothermal solution into a hydrothermal reaction kettle for hydrothermal reaction, wherein the filling degree of the solution is 30% when the hydrothermal solution is injected into the hydrothermal reaction kettle, and then doping Ca2+NaTaO (NaTaO)3Soaking the tantalum sheet of the film layer into a hydrothermal solution for carrying out hydrothermal reaction CuCl2The concentration is 0.001mol/L, the hydrothermal temperature is 200 ℃, the hydrothermal time is 2h, namely Ca is doped on the surface of the tantalum2+And Cu2+NaTaO (NaTaO)3And (5) film layer.
Example 3
NaTaO with bioactivity and antibacterial property3The film layer and the preparation method thereof, the raw materials comprise metal tantalum sheets, NaOH and anhydrous CaCl2And CuCl2；
The concentration of the NaOH is 2 mol/L;
the preparation process of the biomedical metal material comprises the following steps:
the method comprises the following steps: and putting the tantalum sheet and the NaOH hydrothermal solution into a hydrothermal reaction kettle together for hydrothermal reaction at 220 ℃ for 24 hours. Wherein, when the hydrothermal solution is injected into a hydrothermal reaction kettle, the filling degree of the solution is 30 percent, and then Ca is doped2+The tantalum sample is soaked into a hydrothermal solution for hydrothermal reaction, namely, the tantalum sample is soaked on the surface of the tantalumHomogeneous NaTaO is formed3A film layer;
step two: will be covered with NaTaO3Placing the tantalum sheet of the film layer in CaCl2The powder is subjected to molten salt treatment in a crucible, the treatment temperature is 550 ℃, the temperature rise time is 90min, the heat preservation time is 3h, and the filling degree of the powder in the crucible is 99%. That is, Ca is doped on the surface of tantalum2+NaTaO (NaTaO)3And (5) film layer.
Step three: will be doped with Ca2+NaTaO (NaTaO)3Tantalum flakes and CuCl of film layer2Putting the hydrothermal solution into a hydrothermal reaction kettle for hydrothermal reaction, wherein the filling degree of the solution is 30% when the hydrothermal solution is injected into the hydrothermal reaction kettle, and then doping Ca2+NaTaO (NaTaO)3Soaking the tantalum sheet in the film layer into a hydrothermal solution for hydrothermal reaction, and CuCl2The concentration is 0.01mol/L, the hydrothermal temperature is 200 ℃, the hydrothermal time is 2h, namely Ca is doped on the tantalum surface2+And Cu2+NaTaO (NaTaO)3And (5) film layer.
Example 4
NaTaO with bioactivity and antibacterial property3The film layer and the preparation method thereof, the raw materials comprise metal tantalum sheets, NaOH and anhydrous CaCl2And CuCl2；
The concentration of the NaOH is 2 mol/L;
the preparation process of the biomedical metal material comprises the following steps:
the method comprises the following steps: and putting the tantalum sheet and the NaOH hydrothermal solution into a hydrothermal reaction kettle together for hydrothermal reaction at 220 ℃ for 24 hours. Wherein, when the hydrothermal solution is injected into the hydrothermal reaction kettle, the filling degree of the solution is 30 percent, and then the tantalum sample is soaked into the hydrothermal solution for hydrothermal reaction, namely uniform NaTaO is formed on the surface of the tantalum3A film layer;
step two: will be covered with NaTaO3Placing the tantalum sheet of the film layer in CaCl2The powder is subjected to molten salt treatment in a crucible, the treatment temperature is 550 ℃, the temperature rise time is 90min, the heat preservation time is 3h, and the filling degree of the powder in the crucible is 99%. That is, Ca is doped on the surface of tantalum2+NaTaO (NaTaO)3And (5) film layer.
Step three: will be doped with Ca2+NaTaO (NaTaO)3Tantalum flakes and CuCl of film layer2Putting the hydrothermal solution into a hydrothermal reaction kettle for hydrothermal reaction, wherein the filling degree of the solution is 30% when the hydrothermal solution is injected into the hydrothermal reaction kettle, and then doping Ca2+NaTaO (NaTaO)3Soaking the tantalum sheet in the film layer into a hydrothermal solution for hydrothermal reaction, and CuCl2The concentration is 0.1mol/L, the hydrothermal temperature is 200 ℃, the hydrothermal time is 2h, namely Ca is doped on the tantalum surface2+And Cu2+NaTaO (NaTaO)3And (5) film layer.
Example 5
NaTaO with bioactivity and antibacterial property3The film layer and the preparation method thereof, the raw materials comprise metal tantalum sheets, NaOH and anhydrous CaCl2And CuCl2；
The concentration of the NaOH is 2 mol/L;
the preparation process of the biomedical metal material comprises the following steps:
the method comprises the following steps: and putting the tantalum sheet and the NaOH hydrothermal solution into a hydrothermal reaction kettle together for hydrothermal reaction at 220 ℃ for 24 hours. Wherein, when the hydrothermal solution is injected into the hydrothermal reaction kettle, the filling degree of the solution is 30 percent, and then the tantalum sample is soaked into the hydrothermal solution for hydrothermal reaction, namely uniform NaTaO is formed on the surface of the tantalum3A film layer;
step two: will be covered with NaTaO3Tantalum flakes and CuCl of film layer2Putting the hydrothermal solution into a hydrothermal reaction kettle together for hydrothermal reaction, and adding CuCl2When the hydrothermal solution is injected into the hydrothermal reaction kettle, CuCl2The hydrothermal solution had a degree of filling of 30% and was then covered with NaTaO3Soaking the tantalum sheet in the film layer into a hydrothermal solution for hydrothermal reaction, and CuCl2The concentration is 0.0001mol/L, the hydrothermal temperature is 200 ℃, the hydrothermal time is 2h, namely Cu is doped on the tantalum surface2+NaTaO (NaTaO)3And (5) film layer.
Step three: will be doped with Cu2+NaTaO (NaTaO)3Placing the tantalum sheet of the film layer in CaCl2Crucible in powderCarrying out molten salt treatment at 550 ℃, heating for 90min, keeping the temperature for 3h, and filling the powder in a crucible to 99%. Namely, Cu is doped on the surface of tantalum2+And Ca2+NaTaO (NaTaO)3And (5) film layer.
Example 6
NaTaO with bioactivity and antibacterial property3The film layer and the preparation method thereof, the raw materials comprise metal tantalum sheets, NaOH and anhydrous CaCl2And CuCl2；
The concentration of the NaOH is 2 mol/L;
the preparation process of the biomedical metal material comprises the following steps:
the method comprises the following steps: and putting the tantalum sheet and the NaOH hydrothermal solution into a hydrothermal reaction kettle together for hydrothermal reaction at 220 ℃ for 24 hours. Wherein, when the hydrothermal solution is injected into the hydrothermal reaction kettle, the filling degree of the solution is 30 percent, and then the tantalum sample is soaked into the hydrothermal solution for hydrothermal reaction, namely uniform NaTaO is formed on the surface of the tantalum3A film layer;
step two: will be covered with NaTaO3Tantalum flakes and CuCl of film layer2Putting the hydrothermal solution into a hydrothermal reaction kettle together for hydrothermal reaction, and adding CuCl2When the hydrothermal solution is injected into the hydrothermal reaction kettle, CuCl2The hydrothermal solution had a degree of filling of 30% and was then covered with NaTaO3Soaking the tantalum sheet in the film layer into a hydrothermal solution for hydrothermal reaction, and CuCl2The concentration is 0.001mol/L, the hydrothermal temperature is 200 ℃, the hydrothermal time is 2h, namely Cu is doped on the tantalum surface2+NaTaO (NaTaO)3And (5) film layer.
Step three: will be doped with Cu2+NaTaO3Placing the tantalum sheet of the film layer in CaCl2The powder is subjected to molten salt treatment in a crucible, the treatment temperature is 550 ℃, the temperature rise time is 90min, the heat preservation time is 3h, and the filling degree of the powder in the crucible is 99%. Namely, Cu is doped on the surface of tantalum2+And Ca2+NaTaO (NaTaO)3And (5) film layer.
Example 7
NaTa with bioactivity and antibacterial propertyO3The film layer and the preparation method thereof, the raw materials comprise metal tantalum sheets, NaOH and anhydrous CaCl2And CuCl2；
The concentration of the NaOH is 2 mol/L;
the preparation process of the biomedical metal material comprises the following steps:
the method comprises the following steps: and putting the tantalum sheet and the NaOH hydrothermal solution into a hydrothermal reaction kettle together for hydrothermal reaction at 220 ℃ for 24 hours. Wherein, when the hydrothermal solution is injected into the hydrothermal reaction kettle, the filling degree of the solution is 30 percent, and then the tantalum sample is soaked into the hydrothermal solution for hydrothermal reaction, namely uniform NaTaO is formed on the surface of the tantalum3A film layer;
step two: will be covered with NaTaO3Tantalum flakes and CuCl of film layer2Putting the hydrothermal solution into a hydrothermal reaction kettle together for hydrothermal reaction, and adding CuCl2When the hydrothermal solution is injected into the hydrothermal reaction kettle, CuCl2The hydrothermal solution had a degree of filling of 30% and was then covered with NaTaO3Soaking the tantalum sheet in the film layer into a hydrothermal solution for hydrothermal reaction, and CuCl2The concentration is 0.01mol/L, the hydrothermal temperature is 200 ℃, the hydrothermal time is 2h, namely Cu is doped on the tantalum surface2+NaTaO (NaTaO)3And (5) film layer.
Step three: will be doped with Cu2+NaTaO (NaTaO)3Placing the tantalum sheet of the film layer in CaCl2The powder is subjected to molten salt treatment in a crucible, the treatment temperature is 550 ℃, the temperature rise time is 90min, the heat preservation time is 3h, and the filling degree of the powder in the crucible is 99%. Namely, Cu is doped on the surface of tantalum2+And Ca2+NaTaO (NaTaO)3And (5) film layer.
Example 8
NaTaO with bioactivity and antibacterial property3The film layer and the preparation method thereof, the raw materials comprise metal tantalum sheets, NaOH and anhydrous CaCl2And CuCl2；
The concentration of the NaOH is 2 mol/L;
the preparation process of the biomedical metal material comprises the following steps:
the method comprises the following steps: mixing tantalumThe slices and NaOH hydrothermal solution are put into a hydrothermal reaction kettle together for hydrothermal reaction at 220 ℃ for 24 hours. Wherein, when the hydrothermal solution is injected into the hydrothermal reaction kettle, the filling degree of the solution is 30 percent, and then the tantalum sample is soaked into the hydrothermal solution for hydrothermal reaction, namely uniform NaTaO is formed on the surface of the tantalum3A film layer;
step two: will be covered with NaTaO3Tantalum flakes and CuCl of film layer2Putting the hydrothermal solution into a hydrothermal reaction kettle together for hydrothermal reaction, and adding CuCl2When the hydrothermal solution is injected into the hydrothermal reaction kettle, CuCl2The hydrothermal solution had a degree of filling of 30% and was then covered with NaTaO3Soaking the tantalum sheet in the film layer into a hydrothermal solution for hydrothermal reaction, and CuCl2The concentration is 0.1mol/L, the hydrothermal temperature is 200 ℃, the hydrothermal time is 2h, namely Cu is doped on the tantalum surface2+NaTaO (NaTaO)3And (5) film layer.
Step three: will be doped with Cu2+NaTaO (NaTaO)3Placing the tantalum sheet of the film layer in CaCl2The powder is subjected to molten salt treatment in a crucible, the treatment temperature is 550 ℃, the temperature rise time is 90min, the heat preservation time is 3h, and the filling degree of the powder in the crucible is 99%. Namely, Cu is doped on the surface of tantalum2+And Ca2+NaTaO (NaTaO)3And (5) film layer.
Example 9
NaTaO with bioactivity and antibacterial property3The film layer and the preparation method thereof, the raw materials comprise metal tantalum sheets, NaOH and anhydrous CaCl2And CuCl2；
The concentration of the NaOH is 2 mol/L;
the preparation process of the biomedical metal material comprises the following steps:
the method comprises the following steps: and putting the tantalum sheet and the NaOH hydrothermal solution into a hydrothermal reaction kettle together for hydrothermal reaction at 220 ℃ for 24 hours. Wherein, when the hydrothermal solution is injected into the hydrothermal reaction kettle, the filling degree of the solution is 35 percent, and then the tantalum sample is soaked into the hydrothermal solution for hydrothermal reaction, namely uniform NaTaO is formed on the surface of the tantalum3A film layer;
step two: will be covered with NaTaO3Tantalum flakes and CuCl of film layer2Putting the hydrothermal solution into a hydrothermal reaction kettle together for hydrothermal reaction, and adding CuCl2When the hydrothermal solution is injected into the hydrothermal reaction kettle, CuCl2The hydrothermal solution had a degree of filling of 35% and was then covered with NaTaO3Soaking the tantalum sheet in the film layer into a hydrothermal solution for hydrothermal reaction, and CuCl2The concentration is 0.1mol/L, the hydrothermal temperature is 200 ℃, the hydrothermal time is 2h, namely Cu is doped on the tantalum surface2+NaTaO (NaTaO)3And (5) film layer.
Step three: will be doped with Cu2+NaTaO (NaTaO)3Placing the tantalum sheet of the film layer in CaCl2The powder is subjected to molten salt treatment in a crucible, the treatment temperature is 550 ℃, the temperature rise time is 90min, the heat preservation time is 3h, and the filling degree of the powder in the crucible is 95%. Namely, Cu is doped on the surface of tantalum2+And Ca2+NaTaO (NaTaO)3And (5) film layer.
Example 10
NaTaO with bioactivity and antibacterial property3The film layer and the preparation method thereof, the raw materials comprise metal tantalum sheets, NaOH and anhydrous CaCl2And CuCl2；
The concentration of the NaOH is 2 mol/L;
the preparation process of the biomedical metal material comprises the following steps:
the method comprises the following steps: and putting the tantalum sheet and the NaOH hydrothermal solution into a hydrothermal reaction kettle together for hydrothermal reaction at 220 ℃ for 24 hours. Wherein, when the hydrothermal solution is injected into the hydrothermal reaction kettle, the filling degree of the solution is 40 percent, and then the tantalum sample is soaked into the hydrothermal solution for hydrothermal reaction, namely uniform NaTaO is formed on the surface of the tantalum3A film layer;
step two: will be covered with NaTaO3Placing the tantalum sheet of the film layer in CaCl2The powder is subjected to molten salt treatment in a crucible, the treatment temperature is 550 ℃, the temperature rise time is 90min, the heat preservation time is 3h, and the filling degree of the powder in the crucible is 90%. That is, Ca is doped on the surface of tantalum2+NaTaO (NaTaO)3And (5) film layer.
Step three: will be doped with Ca2+NaTaO (NaTaO)3Tantalum flakes and CuCl of film layer2Putting the hydrothermal solution into a hydrothermal reaction kettle for hydrothermal reaction, wherein the filling degree of the solution is 40% when the hydrothermal solution is injected into the hydrothermal reaction kettle, and then doping Ca2+NaTaO (NaTaO)3Soaking the tantalum sheet in the film layer into a hydrothermal solution for hydrothermal reaction, and CuCl2The concentration is 0.1mol/L, the hydrothermal temperature is 200 ℃, the hydrothermal time is 2h, namely Ca is doped on the tantalum surface2+And Cu2+NaTaO (NaTaO)3And (5) film layer.
Experimental example 1
Table 1 is a table of EDS test data for the calcium copper co-doped sodium tantalate film layers of examples 1-8.
Figure BDA0003384305380000121
Figure BDA0003384305380000131
The results show that the Ca-first doping used in examples 1 to 42+Re-doping of Cu2+Ca of the sample prepared by the hydrothermal-molten salt-hydrothermal method2+And Cu2+The atomic contents of the components were higher than those of the Cu-first-doped components used in examples 5 to 82+Further doping with Ca2+The hydrothermal-molten salt method.
Experimental example 2
SEM tests were conducted on the materials obtained in examples 1 to 8.
FIG. 1 is an SEM image of the Ca-Cu co-doped Na-tantalate film layers prepared in examples 1-4, a: calcium-copper co-doped sodium tantalate film layer prepared in example 1, b: calcium-copper co-doped sodium tantalate film layer prepared in example 2, c: calcium copper co-doped sodium tantalate film layer prepared in example 3, d: the calcium-copper co-doped sodium tantalate film layer prepared in example 4; FIG. 2 is an SEM image of the Ca-Cu co-doped Na-tantalate film layers prepared in examples 5-8, a: calcium copper co-doped sodium tantalate film layer prepared in example 5, b: calcium copper co-doped sodium tantalate film layer prepared in example 6, c: calcium copper co-doped sodium tantalate film layer prepared in example 7, d: the calcium copper co-doped sodium tantalate film layer prepared in example 8;
the results show that the morphology of the samples obtained in examples 1 to 4 gradually changed from a cubic shape to a spherical shape. The morphology of the samples obtained in examples 5-8 did not change much and remained cubic.
Experimental example 3
The materials obtained in examples 1 to 8 were subjected to TEM testing. FIG. 3 is a TEM image of the calcium copper co-doped sodium tantalate film layer prepared in example 3 and example 7; a: NaTaO as received3TEM image of (b: NaTaO as received3HRTEM of (g), c: TEM image of the film prepared in example 7, d: HRTEM of film layer prepared in example 7, e: TEM image of the film prepared in example 3, f: HRTEM of the film layer prepared in example 3;
the results show that the samples obtained in examples 1 to 4 had a interplanar spacing of 0.296nm and NaTaO3The interplanar spacing of 0.389nm is obviously changed. The interplanar spacing of the samples obtained in examples 5-8 was still 0.387nm and no significant change occurred.
Experimental example 4
The materials obtained in examples 1 to 4 were subjected to XRD measurement. FIG. 4 is a surface XRD pattern of the calcium copper co-doped sodium tantalate film prepared in examples 1-4;
the results showed that the phase of the sample obtained in examples 1 to 4 was Ca2Ta2O7，NaTaO3And Ta.
Experimental example 5
AFM testing was performed on the materials obtained in examples 1-4. FIG. 5 is an AFM image of the surface of a calcium copper co-doped sodium tantalate film layer prepared in examples 1-4; a: as-is Ta, a: NaTaO as received3C, c: calcium-copper co-doped sodium tantalate film layer prepared in example 1, d: the calcium-copper co-doped sodium tantalate film prepared in example 2, e: calcium-copper co-doped sodium tantalate film prepared in example 3, f: the calcium-copper co-doped sodium tantalate film layer prepared in example 4;
the results show that the samples obtained in examples 1 to 4 had surface roughness of relatively pure Ta and NaTaO3Compared with the prior art, the method is greatly improved.
Experimental example 6
The materials obtained in examples 2 to 4 were subjected to the ICP test.FIG. 6 is the ICP diagram of the Ca/Cu co-doped Na-tantalate film prepared in examples 2-4, wherein a is the Cu diagram2+Is shown in figure b is Ca2+Ion elution map of (a);
the results show that in the co-doped series, the deposition of both Ca ions and Cu ions is relatively high in example 3.
Experimental example 7
The material obtained in example 3 was subjected to XPS testing. Fig. 7 is an XPS chart of the surface of the calcium-copper co-doped sodium tantalate film prepared in example 3, a: XPS total spectrum, b: high resolution spectrogram of Cu2p, c: high resolution spectrogram of Ca2 p;
the results show that the sample surface contains Ca and Cu, and the valence states are 2.
Experimental example 8
The materials obtained in examples 1 to 4 were subjected to a bacterial experiment. FIG. 8 is a plate count picture of calcium-copper co-doped sodium tantalate film samples prepared in examples 1-4 after 24h co-culture with E.coli, a: as-is Ta, a: NaTaO as received3C, c: calcium-copper co-doped sodium tantalate film layer prepared in example 1, d: the calcium-copper co-doped sodium tantalate film prepared in example 2, e: calcium-copper co-doped sodium tantalate film prepared in example 3, f: the calcium-copper co-doped sodium tantalate film layer prepared in example 4;
the result shows that the antibacterial rate of the prepared calcium-copper co-doped sodium tantalate film layer can reach 68-92%; among them, the antibacterial ratio of example 3 is preferably 92%.

Claims (10)

1. A method for preparing a sodium tantalate film with bioactivity and antibacterial property is characterized by comprising the following steps:
adding the tantalum sheet into a NaOH hydrothermal solution for carrying out a hydrothermal reaction, and preparing the tantalum sheet covered with the sodium tantalate film layer;
placing the tantalum sheet covered with the sodium tantalate film layer in CaCl2Carrying out molten salt treatment in the powder to prepare a tantalum sheet of the calcium-doped sodium tantalate film layer;
adding CuCl into the tantalum sheet of the calcium-doped sodium tantalate film layer prepared in the above step2Carrying out a second hydrothermal reaction in the hydrothermal solutionAnd preparing the calcium-copper co-doped sodium tantalate film with bioactivity and antibacterial property on the surface of the tantalum sheet.
2. A method for preparing a sodium tantalate film with bioactivity and antibacterial property is characterized by comprising the following steps:
adding the tantalum sheet into a NaOH hydrothermal solution for carrying out a hydrothermal reaction, and preparing the tantalum sheet covered with the sodium tantalate film layer;
adding CuCl into the tantalum sheet covered with the sodium tantalate film layer obtained by the preparation method2Carrying out secondary hydrothermal reaction in the hydrothermal solution to prepare a tantalum sheet with a copper-doped sodium tantalate film layer;
placing the tantalum sheet of the copper-doped sodium tantalate film layer prepared in the CaCl2And carrying out molten salt treatment in the powder, and preparing the calcium-copper co-doped sodium tantalate film layer with bioactivity and antibacterial property on the surface of the tantalum sheet.
3. The method for preparing the sodium tantalate film with bioactivity and antibacterial property as claimed in claim 1 or 2, wherein the concentration of the NaOH hydrothermal solution is 2 mol/L; the CuCl2The concentration of the hydrothermal solution is 0.0001-0.1 mol/L.
4. The method for preparing the sodium tantalate film with bioactivity and antibacterial property as claimed in claim 1 or 2, wherein the first hydrothermal reaction is performed in a hydrothermal reaction kettle, and the filling degree of the NaOH hydrothermal solution in the hydrothermal reaction kettle is 30-40%.
5. The method for preparing the sodium tantalate film with bioactivity and antibacterial property as claimed in claim 1 or 2, wherein the temperature of the first hydrothermal reaction is 220 ℃ and the reaction time is 24 hours; the temperature of the secondary hydrothermal reaction is 200 ℃, and the reaction time is 2 hours.
6. The method for preparing the sodium tantalate film with bioactivity and antibacterial property as claimed in claim 1 or 2, wherein the temperature of molten salt treatment is 550 ℃, the temperature rise time is 90min, and the heat preservation time is 3 h.
7. The method for preparing the sodium tantalate film with bioactivity and antibacterial property as claimed in claim 1 or 2, wherein the molten salt treatment is performed in a crucible, and the CaCl is treated2The filling degree of the powder in the crucible is 90-99 percent, and the CaCl is2Is anhydrous calcium chloride.
8. The method for preparing the sodium tantalate film with bioactivity and antibacterial property as claimed in claim 1 or 2, wherein the second hydrothermal reaction is performed in a hydrothermal reaction kettle, and the CuCl is added2The filling degree of the hydrothermal solution in the hydrothermal reaction kettle is 30-40%.
9. A bioactive and antibacterial sodium tantalate film layer, prepared by the method of any one of claims 1-8.
10. The bioactive and antimicrobial sodium tantalate film layer of claim 9, wherein the microstructure of the bioactive and antimicrobial sodium tantalate film layer is cubic or spherical.
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