CN116288595B - Ta ion doped titanium dioxide nanotube and preparation method and application thereof - Google Patents
Ta ion doped titanium dioxide nanotube and preparation method and application thereof Download PDFInfo
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- CN116288595B CN116288595B CN202310137826.1A CN202310137826A CN116288595B CN 116288595 B CN116288595 B CN 116288595B CN 202310137826 A CN202310137826 A CN 202310137826A CN 116288595 B CN116288595 B CN 116288595B
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 206
- 239000002071 nanotube Substances 0.000 title claims abstract description 143
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 85
- 150000002500 ions Chemical class 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000010936 titanium Substances 0.000 claims abstract description 90
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 76
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 76
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 45
- 230000003647 oxidation Effects 0.000 claims abstract description 43
- 239000003792 electrolyte Substances 0.000 claims abstract description 40
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims abstract description 34
- 229910052715 tantalum Inorganic materials 0.000 claims abstract description 29
- 239000000758 substrate Substances 0.000 claims abstract description 25
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000001354 calcination Methods 0.000 claims abstract description 13
- 238000005554 pickling Methods 0.000 claims abstract description 13
- 230000010287 polarization Effects 0.000 claims abstract description 12
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 10
- 239000011737 fluorine Substances 0.000 claims abstract description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 7
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- 239000007943 implant Substances 0.000 claims description 11
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 9
- 230000010355 oscillation Effects 0.000 claims description 5
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- 230000011164 ossification Effects 0.000 abstract description 11
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- 239000000243 solution Substances 0.000 description 25
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- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 16
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- 230000008569 process Effects 0.000 description 12
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 10
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- 229910003077 Ti−O Inorganic materials 0.000 description 2
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- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 101100396546 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) tif-6 gene Proteins 0.000 description 1
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Classifications
-
- 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
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/02—Inorganic materials
- A61L27/04—Metals or alloys
- A61L27/06—Titanium or titanium 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
- 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
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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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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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
- A61L2400/00—Materials characterised by their function or physical properties
- A61L2400/12—Nanosized materials, e.g. nanofibres, nanoparticles, nanowires, nanotubes; Nanostructured surfaces
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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
- A61L2400/00—Materials characterised by their function or physical properties
- A61L2400/18—Modification of implant surfaces in order to improve biocompatibility, cell growth, fixation of biomolecules, e.g. plasma treatment
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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
- A61L2420/00—Materials or methods for coatings medical devices
- A61L2420/06—Coatings containing a mixture of two or more compounds
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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
- 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 application provides a Ta ion doped titanium dioxide nanotube and a preparation method and application thereof, belonging to the technical field of biological materials. To solve the problems of the prior TiO 2 The technical problems of insufficient strength and poor osteogenesis performance of the nano tube. The preparation method comprises the following steps: taking a titanium sheet as an anode, and performing anodic oxidation in a fluorine-containing electrolyte to obtain the titanium sheet with the titanium dioxide nanotube array grown on the surface; taking a titanium sheet with a titanium dioxide nanotube array grown on the surface as a cathode and graphite as an anode, and carrying out cathodic polarization pickling in sulfuric acid solution to obtain a titanium substrate template; performing secondary anodic oxidation in a tantalum-containing electrolyte by taking a titanium substrate template as an anode to obtain a titanium sheet with a tantalum-doped titanium dioxide nanotube array grown on the surface; calcining the titanium sheet with the tantalum doped titanium dioxide nanotube array grown on the surface to obtain the Ta ion doped titanium dioxide nanotube.
Description
Technical Field
The application relates to the technical field of biological materials, in particular to a Ta ion doped titanium dioxide nanotube and a preparation method and application thereof.
Background
Implant failure is often due to biological factors (e.g., bacterial infection and insufficient contact of the implant with the bone) and biomechanical factors (e.g., excessive bite load resulting in breakage and/or damage to the implant material). In order to overcome the defects of Ti metal in the osteogenesis capability and complications related to infection, many researches are carried out to realize the functionalization of the titanium implant by changing the morphology, morphology and chemical characteristics of the surface.
Preparation of TiO on titanium-based surfaces 2 The nanotube structure can be the same asWhile improving the osseointegration and antibacterial properties of Ti, however, tiO 2 The interface adhesion between the nanotube layer and the Ti substrate is poor, and the self strength of the nanotube is insufficient. Although anodic oxidation can form an oxide dense layer near the bottom of the nanotube, there are still empty bubble regions formed by oxygen vacancies and Ti-H bonds, resulting in TiO 2 The nano tube is easy to be stripped from the base plate or broken from the middle section of the nano tube after being subjected to mechanical external force, so that the stability and the biological binding capacity of the coating are affected. The implant is required to withstand torque friction and external force during and after implantation, and is exposed to corrosive conditions such as blood. If the nanotubes are not firmly bonded to the substrate or are not strong enough, abrasion fragments and corrosion products are released around the implant, causing deleterious biological effects and ultimately resulting in failure of the implant. Therefore, tiO is improved 2 The mechanical strength and osteogenic properties of the nanotubes are critical.
Disclosure of Invention
The application aims to provide a Ta ion doped titanium dioxide nanotube and a preparation method and application thereof, which realize Ta doping under the condition of maintaining the original morphology of the nanotube and solve the problems of insufficient strength and poor osteogenesis performance of the existing nanotube.
In order to achieve the above object, the present application provides the following technical solutions:
a preparation method of a Ta ion doped titanium dioxide nanotube comprises the following steps:
primary anodic oxidation: taking a titanium sheet as an anode, and performing anodic oxidation in a fluorine-containing electrolyte to obtain the titanium sheet with the titanium dioxide nanotube array grown on the surface;
cathode polarization pickling: taking the titanium sheet with the titanium dioxide nanotube array grown on the surface as a cathode and graphite as an anode, and carrying out cathode polarization pickling in sulfuric acid solution to obtain a titanium substrate template;
secondary anodic oxidation: performing secondary anodic oxidation in a tantalum-containing electrolyte by taking a titanium substrate template as an anode to obtain a titanium sheet with a tantalum-doped titanium dioxide nanotube array grown on the surface;
calcining: calcining the titanium sheet with the tantalum doped titanium dioxide nanotube array grown on the surface to obtain a Ta ion doped titanium dioxide nanotube;
wherein the components of the tantalum-containing electrolyte comprise water, ammonium fluoride and tantalum ion solution; the voltage of the secondary anodic oxidation is 40-V-70V, the temperature is 15-25 ℃, and the time is 10-40 min.
In accordance with at least one embodiment of the present disclosure, the tantalum-containing electrolyte comprises 7.5 to 12.5vol% water, 0.1 to 0.5wt% ammonium fluoride, and 0.01 to 1vol% tantalum ion solution in the secondary anodic oxidation step,
the concentration of the tantalum ions in the tantalum-containing electrolyte is 0.001mol/L to 0.02mol/L.
The solvent used in the tantalum ion solution is hydrofluoric acid, and the concentration of tantalum ions in the tantalum ion solution is 1.25 mol/L-5 mol/L.
According to at least one embodiment of the present disclosure, in the step of cathodic polarized pickling, the concentration of the sulfuric acid solution is 0.1mol/L to 5mol/L;
the cathodic polarization pickling time is 10-20 min, and then ultrasonic oscillation washing is carried out in deionized water for 5-30 min.
According to at least one embodiment of the present disclosure, in the step of primary anodic oxidation, the voltage of the primary anodic oxidation is 40V to 70V, the temperature is 15 to 25 ℃, and the time is 10 to 40 minutes.
In accordance with at least one embodiment of the present disclosure, in the step of one anodic oxidation, the fluorine-containing electrolyte comprises ethylene glycol, water, ammonium fluoride, and 1wt% to 40wt% hydrofluoric acid;
the fluorine-containing electrolyte comprises 7.5 to 12.5 percent of water by volume, 0.1 to 0.5 percent of ammonium fluoride by volume and 0.2 to 0.5 percent of hydrofluoric acid by volume.
According to at least one embodiment of the present disclosure, in the calcining step, the calcining temperature is 400 ℃ to 600 ℃, and the heat preservation time is 1h to 6 hours.
Compared with the prior art, the preparation method of the Ta ion doped titanium dioxide nanotube utilizes anodic oxidation to prepare TiO on the surface of pure titanium 2 NanotubeThen, a titanium substrate template with regular nano holes is formed by cathodic polarization acid washing, secondary anodic oxidation is carried out by using tantalum-containing electrolyte, and Ta doped TiO is continuously formed on the titanium substrate template 2 The nano tube is calcined and crystallized to form the TiO material with the same structure as the original TiO material 2 Ta doped TiO with consistent nanotube morphology 2 The nanotube can exert the mechanical advantage of tantalum metal, promote the osteogenesis of the nanotube material, and solve the problem of the existing TiO 2 The problem of insufficient strength and poor osteogenesis performance of the nanotubes can be applied to the surface of an implant to promote osteogenesis.
Tantalum metal has good biocompatibility and corrosion resistance, and has strong hydrophilicity and surface energy, and excellent osteogenesis induction capability. The application completes doping at the same time of anodic oxidation, so that tantalum element can enter the whole layer of the nanotube, and the shape of the nanotube is not affected. Under biological environment, the cells are in direct contact with the Ta-doped nano tube, so that the tantalum effectively promotes the osteogenic differentiation of bone marrow mesenchymal cells, thereby improving the osteogenic performance.
At present, the method for carrying out Ta ion doping on the nanotube is to deposit metal or metal oxide particles on the surface of the nanotube, which can influence the original morphology of the titanium dioxide nanotube, thereby influencing the osteogenesis performance of the titanium dioxide nanotube. The application adopts a secondary anodic oxidation method to realize Ta doping under the condition of maintaining the original shape of the nanotube, and promotes the osteogenesis performance of the titanium dioxide material.
The application also aims to provide the Ta ion doped titanium dioxide nanotube prepared by the preparation method.
According to at least one embodiment of the present disclosure, the tube diameter of the Ta ion doped titanium dioxide nanotube is 70-120 nm.
The advantages of the Ta ion doped titanium dioxide nanotubes compared with the prior art are the same as those of the above preparation method compared with the prior art, and will not be described in detail herein.
The application also aims to provide an application of the Ta ion doped titanium dioxide nanotube in preparing implant materials.
The advantages of the Ta ion doped titanium dioxide nanotube in preparing the implant material are the same as those of the preparation method in the prior art, and are not described herein.
Drawings
The accompanying drawings, which are included to provide a further understanding of the disclosure and are incorporated in and constitute a part of this specification, illustrate exemplary embodiments of the disclosure and together with the description serve to explain the principles of the disclosure.
FIG. 1 is a topography of a titanium base template prepared in example 1;
FIG. 2 is a topography of a material with an array of tantalum doped titanium dioxide nanotubes formed on the surface thereof prepared in example 1;
FIG. 3 is a side topography of a material with an array of tantalum doped titanium dioxide nanotubes formed on the surface thereof prepared in example 1;
FIG. 4 is a graph of the side morphology and elemental analysis of a transmission electron microscope prepared with tantalum doped titanium dioxide nanotubes formed on the surface prepared in example 1;
FIG. 5 is a graph of the morphology of undoped titania nanotubes prepared in comparative example 1;
FIG. 6 is an XPS plot of O1s for the Ta ion doped titania nanotubes prepared in example 1;
FIG. 7 is an XPS plot of O1s of undoped titanium dioxide nanotubes prepared in comparative example 1;
FIG. 8 is a graph of displacement versus side force loading for different titanium materials;
FIG. 9 is a bar graph of CCK-8 detection results of early adhesion of different titanium materials to bone marrow mesenchymal stem cells; (P<0.05）；
Fig. 10 is a bar graph of ALP activity of different titanium materials on bone marrow mesenchymal stem cells.
Detailed Description
The present disclosure is described in further detail below with reference to the drawings and the embodiments. It is to be understood that the specific embodiments described herein are merely illustrative of the relevant content and not limiting of the present disclosure. It should be further noted that, for convenience of description, only a portion relevant to the present disclosure is shown in the drawings.
In addition, embodiments of the present disclosure and features of the embodiments may be combined with each other without conflict. The present disclosure will be described in detail below with reference to the accompanying drawings in conjunction with embodiments. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
In some embodiments, the titanium flakes are pure titanium, preferably 99.9% pure; before the titanium sheet is used, the titanium sheet can be sequentially subjected to ultrasonic oscillation washing in acetone, ethanol and deionized water for 10-20 min, and then naturally dried. The condition of ultrasonic agitation washing is not particularly limited in the present application, and may be carried out according to the conditions well known in the art.
The platinum electrode is not particularly limited in the present application, and any platinum electrode known in the art may be used.
In some embodiments, a highly ordered titanium dioxide nanotube array is formed on the surface of the titanium sheet in a primary anodic oxidation step, wherein the primary anodic oxidation voltage is preferably 40V-70V, optionally 40V-60V, more preferably 50V, the temperature is preferably 15-25 ℃, the time is optionally 10-40 min, and preferably 15-30 min; the primary anodic oxidation is preferably carried out in an electrolytic cell; the electrolytic cell is not particularly limited, and the electrolytic solution is placed in a corresponding container, for example, a fluorine-containing electrolytic solution is placed in a plastic container, and an acid-containing electrolytic solution is placed in a glass container.
After the primary anodic oxidation is finished, the obtained titanium sheet is preferably washed by ethanol and deionized water in sequence, and electrolyte and impurities are removed to obtain the titanium sheet with the titanium dioxide nanotube array grown on the surface. The specific process of the cleaning is not particularly limited, and may be carried out according to a process well known in the art.
After the titanium sheet with the titanium dioxide nanotube array growing on the surface is obtained, the titanium sheet with the titanium dioxide nanotube array growing on the surface is taken as a cathode, graphite is taken as an anode, and cathode polarization acid washing is carried out in an acid solution to obtain the titanium substrate template.
The graphite is not particularly limited, and commercially available graphite known in the art as an anode may be used.
In the cathodic polarization pickling process, a large number of hydrogen bubbles generated by the nanotube substrate remove the titanium dioxide nanotubes formed in the primary anodic oxidation process, highly ordered equidistant pits are formed on the surface of the titanium sheet, and the pits can be regarded as the residual form after the nanotube layer is integrally removed from the surface of the titanium substrate, and the surface only contains a small amount of oxide layer. Wherein sulfuric acid solution is used for acid washing, and the concentration of the sulfuric acid solution is 0.1mol/L to 5mol/L, alternatively 0.5 mol/L to 2mol/L, and further alternatively 0.8 mol/L to 1.5mol/L. The pickling time is 10 min-20 min, optionally 10 min-15 min.
After the cathodic polarization pickling is completed, the obtained material is preferably placed in water and subjected to ultrasonic washing for 5-30 min, optionally for 5-20 min and optionally for 10min, so that the nanotube layer on the surface of the material is thoroughly removed, and the titanium substrate template is obtained through natural drying.
The application uses the titanium substrate template as the template for the growth of the nanotubes in the secondary anodic oxidation process, so that the growth of the nanotubes is more regular.
After the titanium substrate template is obtained, the titanium substrate template is used as an anode, a platinum electrode is used as a cathode, and secondary anodic oxidation is carried out in tantalum-containing electrolyte to obtain the titanium sheet with the surface being grown with the tantalum-doped titanium dioxide nanotube array.
In the embodiment of the application, the tantalum ion solution is preferably obtained by dissolving tantalum metal in 1-40 wt% of hydrofluoric acid; the concentration of the tantalum ion in the tantalum-containing electrolyte is preferably 0.001 to 0.02mol/L, more preferably 0.01 to 0.015mol/L.
The application preferably fully immerses the titanium substrate template and the platinum electrode in the tantalum-containing electrolyte for secondary anodic oxidation.
In the application, the voltage of the secondary anodic oxidation is 40-70V, optionally 40-60V, preferably 50V; the temperature is 15-25 ℃, preferably 15-20 ℃; the time is optionally 10-40 min, still optionally 15-30 min, preferably 30min.
After the secondary anodic oxidation is completed, the obtained material is preferably washed by ethanol and deionized water in sequence, and electrolyte and impurities are removed, so that the titanium sheet with the tantalum doped titanium dioxide nanotube array grown on the surface is obtained. The specific process of the cleaning is not particularly limited, and may be carried out according to a process well known in the art.
After the titanium sheet with the tantalum-doped titanium dioxide nanotube array grown on the surface is obtained, the titanium sheet with the tantalum-doped titanium dioxide nanotube array grown on the surface is calcined to obtain the Ta ion-doped titanium dioxide nanotube.
Illustratively, the calcination temperature is 400-600 ℃, preferably 500 ℃, the heat preservation time is optionally 1 h-6 h, and further optionally 2-4 h; the rate of temperature rise to the calcination temperature is preferably 5 deg.c/min.
In some embodiments, after calcination is completed, the temperature is reduced to room temperature with a furnace to obtain the Ta ion doped titanium dioxide nanotube.
In the embodiment of the application, in the tantalum ion solution, tantalum metal is dissolved in hydrofluoric acid solution to form a large amount of tantalum fluoride ions (Ta+8HF→ [ TaF) 8 ] 3- +8H + ) The anions are enriched on the surface of the titanium sheet in the anodic oxidation process, and migrate to the deep part of the tube along with the corrosion of the nanotube, and are accumulated on the surface of the nanotube, wherein F-ions volatilize along with the subsequent calcination process, and Ta 5+ Ion radius of ion (64 pm) and Ti 4+ Ions (61 pm) are similar and enter TiO during the formation of anatase titanium dioxide crystals 2 Within the lattice, a portion of the Ti atoms is occupied, thereby completing substitutional doping.
In some embodiments, in a single anodization step, F in a fluorine-containing electrolyte - Ions are enriched near the titanium sheet under the action of an electric field, and meanwhile, a layer of compact TiO is formed on the surface of the titanium 2 Oxide layer (formula 1), and the oxide layer becomes thicker. Then under the action of electric field, the oxide layer close to the fluorine-containing electrolyte is started to be F - Ion corrosion (formula 2) occursLocally dissolving to form a large number of holes on the surface of the oxide layer; subsequently F - The ions continuously corrode the compact oxide layer downwards under the action of an electric field, and after the oxide layer at the bottom of the hole is dissolved, the deep titanium is oxidized again, so that the oxide layer grows to the deep part, and finally the titanium dioxide nanotube is formed. The reaction is as follows:
Ti+2H 2 O→TiO 2 +4H + （1）
TiO 2 +6F - +4H + →[TiF 6 ] 2- +2H 2 O （2）
[TiF6] 2- +6H 2 O→[Ti(OH)6] 2- + 6F - +6H + （3）
[Ti(OH)6] 2- →TiO 2 + 2H 2 O + 2OH - （4）
in some embodiments, ta is reacted with hydrofluoric acid in the tantalum ion solution to form TaF in a secondary anodization step 8 3- Electrolyte is added, and the mixture is doped into TiO along with the secondary anodic oxidation process 2 In the nano tube, during the process of anodic oxidation to form the titanium dioxide nano tube, the F-ion corrodes the titanium dioxide compact oxide layer to generate an intermediate TiF 6 2- The method comprises the steps of carrying out a first treatment on the surface of the These products are concentrated on the walls of the nanotubes and form anatase crystals with the titanium dioxide in the walls during the final heat treatment. And [ TaF 8 ] 3- Structure of (2) and TiF 6 2- Similarly, the negative charges carried by the titanium dioxide nano tube are easy to gather on the surface of the titanium sheet of the anode and are gathered on the wall of the titanium dioxide nano tube together, and finally enter the crystal lattice of the titanium dioxide in the heat treatment process, thereby obtaining the morphology structure and the original TiO 2 Ta doped TiO with nanotube diameter and length basically consistent 2 Nanotube arrays, react as follows:
Ta+8HF→[TaF 8 ] 3- +8H + （5）
[TaF 8 ] 3- +8H 2 O→[Ta(OH) 8 ] 3- + 8F - +8H + （6）
2[Ta(OH) 8 ] 3- →Ta 2 O 5 + 5H 2 O + 6OH - （7）
according to another aspect of the application, a Ta ion doped titania nanotube prepared by the above preparation method is provided. In the Ta ion doped titanium dioxide nanotube, ta is loaded on the wall of the titanium dioxide nanotube in an oxide form.
In some embodiments, the diameter of the Ta ion doped titanium dioxide nanotube is 70-120 nm, optionally 100nm; the tube length is 1000+ -100 nm.
According to still another aspect of the present application, there is provided an application of the Ta ion doped titanium dioxide nanotube described above in preparing implant materials. The method of application of the present application is not particularly limited, and may be applied according to methods well known in the art.
Examples of several methods for preparing Ta ion doped titania nanotubes are given below, and representative Ta ion doped titania nanotubes were selected for performance analysis.
Example 1
The method for preparing the Ta ion doped titanium dioxide nanotube provided by the embodiment specifically comprises the following steps:
(1) Sequentially ultrasonic washing smooth high-purity (99.9%) titanium sheet in acetone, ethanol and deionized water for 10min, and naturally drying for standby;
(2) The titanium sheet after cleaning and drying is used as an anode, the platinum electrode is used as a cathode, the titanium sheet and the platinum electrode are completely immersed in electrolyte, the electrolyte solvent is ethylene glycol, and the electrolyte contains 10vol% of deionized water, 0.3wt% of ammonium fluoride and 0.4vol% of 40wt% of hydrofluoric acid; in an electrolytic cell, carrying out primary anodic oxidation for 30min at the room temperature with the voltage of 50V, cleaning the surface of a material by using ethanol and deionized water, removing electrolyte and impurities, and forming a highly ordered titanium dioxide nanotube array on the surface of a titanium sheet;
(3) Taking a titanium sheet with a titanium dioxide nanotube array formed on the surface as a cathode, taking graphite as an anode, pickling for 10min in a sulfuric acid solution with the concentration of 1mol/L, putting the obtained material into deionized water, ultrasonic washing for 10min, and naturally drying to obtain a titanium substrate template;
(4) The method comprises the steps of taking a titanium substrate template as an anode and a platinum electrode as a cathode, immersing the titanium substrate template and the platinum electrode in electrolyte completely, wherein an electrolyte solvent is ethylene glycol, the electrolyte contains 10vol% of deionized water, 0.3wt% of ammonium fluoride and 0.4vol% of tantalum ion solution, the tantalum ion solution is obtained by dissolving tantalum metal in 40wt% of HF, the concentration of tantalum ions in the tantalum ion solution is 5mol/L, so that the concentration of Ta ions in the electrolyte is 0.02mol/L, performing secondary anodic oxidation for 30min under the condition of constant-temperature water bath with the voltage of 50V and the temperature of 20 ℃, cleaning the surface of a material by sequentially using ethanol and deionized water, and forming a highly ordered tantalum-doped titanium dioxide nanotube array on the surface of a titanium sheet;
(5) And (3) heating the material with the tantalum doped titanium dioxide nanotube array formed on the surface to 500 ℃ at a speed of 5 ℃ per minute in a tube furnace, preserving heat for 4 hours, cooling to room temperature along with the furnace, and obtaining the Ta ion doped titanium dioxide nanotube with the tube diameter of 100nm, which is recorded as 2.0-Ta.
Example 2
The Ta ion doped titania nanotube preparation method provided in this embodiment is different from that of embodiment 1 only in that:
in the step (4), the concentration of tantalum ions in the tantalum ion solution was 1.25mol/L, so that the concentration of Ta ions in the electrolyte was 0.005mol/L, which was denoted as 0.5-Ta.
Example 3
The Ta ion doped titania nanotube preparation method provided in this embodiment is different from that of embodiment 1 only in that:
in the step (4), the concentration of tantalum ions in the tantalum ion solution was 2.5mol/L, so that the concentration of Ta ions in the electrolyte was 0.01mol/L, which was designated as 1.0-Ta.
Example 4
The Ta ion doped titania nanotube preparation method provided in this embodiment is different from that of embodiment 1 only in that:
in the step (4), the concentration of tantalum ions in the tantalum ion solution was 3.75mol/L, so that the concentration of Ta ions in the electrolyte was 0.015mol/L, which was designated as 1.5-Ta.
Comparative example 1
The preparation method of the titanium dioxide nanotubes provided in this comparative example is different from that of example 1 only in that:
in step (4), 0.4vol% tantalum ion solution in the electrolyte is replaced with 0.4% vol 40wt% hydrofluoric acid;
and (3) obtaining the titanium dioxide nanotube (TNT) without the step (5).
Characterization and performance testing:
1) Referring to fig. 1, fig. 1 is a morphology diagram of a titanium substrate template prepared in example 1, wherein the upper right corner is the bottom of the stripped nanotube layer, and the left side is the titanium substrate; pit-like structures uniformly distributed on the titanium substrate correspond to the bottom of the nanotube. The titanium substrate with the morphology enables the formation of the nanotubes to start from the bottom of the uniform pit during secondary anodic oxidation, so that the morphology of the formed nanotubes is more uniform. The uniform morphology increases the mechanical strength of the nanotubes.
2) Referring to fig. 2 to 3, fig. 2 is a morphology diagram of a material with a tantalum doped titania nanotube array formed on the surface prepared in example 1; FIG. 3 is a side topography of a material with an array of tantalum doped titanium dioxide nanotubes formed on the surface thereof prepared in example 1; it can be seen that after secondary anodic oxidation, highly ordered tantalum doped titanium dioxide nanotubes are formed on the surface of the material, the tube diameter is uniform and is about 100nm, and the tube length is 1000 nm +/-100 nm.
3) FIG. 4 shows the side morphology and elemental analysis of a transmission electron microscope prepared with tantalum doped titanium dioxide nanotubes formed on the surface prepared in example 1; as shown in fig. 4, tantalum was uniformly distributed over the entire length of the nanotube and had no effect on the morphology of the titania nanotubes.
4) Referring to fig. 5, fig. 5 is a morphology diagram of an undoped titanium dioxide nanotube prepared in comparative example 1; because the solution containing Ta is added into the secondary anodic oxidation electrolyte, the ion concentration in the electrolyte can be increased, so that the anodic oxidation reaction is aggravated, thermodynamics and dynamics of the anodic oxidation reaction are interfered, and compared with undoped titanium dioxide nanotubes, the diameter of the nanotubes can be reduced by carrying out Ta doping in the anodic oxidation electrolyte.
The application reduces the reaction temperature by controlling the content of F ions in the electrolyte, and controls the pipe diameter of the nano-tube, so that the pipe diameter of the Ta doped nano-tube is consistent with the shape of the undoped nano-tube (comparing figure 2 with figure 5), the pipe diameters are all 100nm, and the pipe length is 1000 nm +/-100 nm.
5) FIG. 6 is an XPS plot of O1s of the Ta ion doped titania nanotubes prepared in example 1, as shown in FIG. 6, in the Ta doped nanotubes, ta-O (530.8 eV) peaks formed in addition to the Ti-O characteristic peaks (529.8 eV) and-OH (532.0 eV) due to Ta substituting for Ti in the lattice;
FIG. 7 is an XPS plot of O1s of undoped titanium dioxide nanotubes prepared in comparative example 1, the main peak of the undoped Ta titanium dioxide nanotubes O1s being divided into Ti-O (Ti 4+ :529.8 eV，Ti 3+ 530.4 eV) and-OH (532.0 eV).
It can be seen from a comparison of fig. 6 and fig. 7 that: due to the doping of Ta element, ti in titanium dioxide 3+ Conversion of ions to Ti 4+ Ions, and Ti 3+ The too large ionic radius of the ions can lead to the expansion of crystal lattices, so that the mechanical strength of the titanium dioxide nanotube is weakened; doping of Ta element removes Ti 3+ The defects caused by the ions enhance the mechanical strength of the titanium dioxide nanotubes, and the mechanical strength of the nanotubes increases with the increase of the Ta concentration, as shown in FIG. 8, and FIG. 8 shows graphs of displacement versus lateral force loading of different titanium materials.
5) In vitro cell adhesion assay
Test materials: pure titanium sheet, titanium dioxide nanotube (TNT) prepared in comparative example 1, ta ion doped titanium dioxide nanotube prepared in examples 1-4;
s1, extracting and separating rat bone marrow mesenchymal stem cells (BMSCs) at 37 ℃ and 5vol% CO 2 Culturing in an incubator for 3 days, changing liquid, growing cells until 70-80% of passages, and culturing primary cells until the cells grow full when the primary cells grow to the second generationThe method is used for testing cell adhesion and osteogenic performance;
s2, respectively placing a pure titanium sheet, a titanium dioxide nanotube and a tantalum doped titanium dioxide nanotube which are subjected to ultrasonic oscillation washing and high-temperature high-pressure sterilization into a 24-pore plate, and inoculating 2.5 multiplied by 10 into each pore 4 Individual cells were cultured in an incubator.
S3, respectively at 1h and 12h of inoculated cells, discarding culture solution in the holes, adding culture solution containing 10vol% of CCK-8 reagent, incubating at 37 ℃ for 2h, and reading OD by using an enzyme-labeled instrument 450nm Numerical values, and the obtained results are shown in FIG. 9.
FIG. 9 is a bar graph showing the results of CCK-8 detection of early adhesion of different titanium materials to bone marrow mesenchymal stem cells; p < 0.05), where a high OD value indicates a high number of cells adhering to the surface of the material. As shown in fig. 9, compared with the titanium dioxide nanotube without Ta, the titanium dioxide nanotube with Ta doped with Ta has the effect of bone formation differentiation, which is more early than the undoped nanotube, and indirectly promotes early bone formation on the surface of the material.
6) In vitro cell osteogenic Activity test
Test materials: pure titanium sheet, titanium dioxide nanotube (TNT) prepared in comparative example 1, ta ion doped titanium dioxide nanotube prepared in examples 1-4;
s10, respectively placing a pure titanium sheet, a titanium dioxide nanotube and a tantalum doped titanium dioxide nanotube which are subjected to ultrasonic oscillation washing and high-temperature high-pressure sterilization into a 24-pore plate, and inoculating 1X 10 into each pore 5 Individual cells, cultured in an incubator;
s20, when the proliferation of cells reaches 70% of the bottom of a 24-pore plate, changing the cells into an osteoinductive medium, and then carrying out 5% CO at 37 DEG C 2 Culturing in an incubator for 3 days, and changing liquid;
s30, when the cells of each group are cultured to 3, 5, 7 and 14 days, the culture medium in the holes is discarded, and the lysate is added for lysis on ice. Then using alkaline phosphatase (ALP) detection kit to detect, setting 3 multiple holes in each hole, and using enzyme-labeled instrument to detectOD measurement 405nm The results were converted to enzyme activities and divided by the total protein amount of the group to obtain alkaline phosphatase relative activities, and the results are shown in FIG. 8.
Fig. 10 is a bar graph of ALP activity of different titanium materials on bone marrow mesenchymal stem cells (statistical differences between different groups of letters). As can be seen from fig. 10, the tantalum-doped titania nanotubes have more excellent osteogenic properties than undoped titania nanotubes, and such properties have a dose dependency.
In the description of the present specification, reference to the terms "one embodiment/manner," "some embodiments/manner," "example," "a particular example," "some examples," etc., means that a particular feature, structure, material, or characteristic described in connection with the embodiment/manner or example is included in at least one embodiment/manner or example of the application. In this specification, the schematic representations of the above terms are not necessarily for the same embodiment/manner or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments/modes or examples. Furthermore, the various embodiments/modes or examples described in this specification and the features of the various embodiments/modes or examples can be combined and combined by persons skilled in the art without contradiction.
Furthermore, the terms "first," "second," and the like, are used for descriptive purposes only and are not to be construed as indicating or implying a relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defining "a first" or "a second" may explicitly or implicitly include at least one such feature. In the description of the present application, the meaning of "plurality" means at least two, for example, two, three, etc., unless specifically defined otherwise.
It will be appreciated by those skilled in the art that the above-described embodiments are merely for clarity of illustration of the disclosure, and are not intended to limit the scope of the disclosure. Other variations or modifications will be apparent to persons skilled in the art from the foregoing disclosure, and such variations or modifications are intended to be within the scope of the present disclosure.
Claims (8)
1. The preparation method of the Ta ion doped titanium dioxide nanotube is characterized by comprising the following steps of:
primary anodic oxidation: taking a titanium sheet as an anode, and performing anodic oxidation in a fluorine-containing electrolyte to obtain the titanium sheet with the titanium dioxide nanotube array grown on the surface;
cathode polarization pickling: taking the titanium sheet with the titanium dioxide nanotube array grown on the surface as a cathode and graphite as an anode, and carrying out cathode polarization pickling in sulfuric acid solution to obtain a titanium substrate template;
secondary anodic oxidation: performing secondary anodic oxidation in a tantalum-containing electrolyte by taking a titanium substrate template as an anode to obtain a titanium sheet with a tantalum-doped titanium dioxide nanotube array grown on the surface;
calcining: calcining the titanium sheet with the tantalum doped titanium dioxide nanotube array grown on the surface to obtain a Ta ion doped titanium dioxide nanotube;
wherein the tantalum-containing electrolyte comprises 7.5 to 12.5vol% of water, 0.1 to 0.5wt% of ammonium fluoride and 0.01 to 1vol% of tantalum ion solution,
the concentration of the tantalum ions in the tantalum-containing electrolyte is 0.001mol/L to 0.02mol/L; the voltage of the secondary anodic oxidation is 40V-70V, the temperature is 15-25 ℃ and the time is 10-40 min; the solvent used in the tantalum ion solution is hydrofluoric acid, and the concentration of tantalum ions in the tantalum ion solution is 1.25 mol/L-5 mol/L.
2. The method according to claim 1, wherein in the step of cathodic polarization pickling, the concentration of the sulfuric acid solution is 0.1mol/L to 5mol/L;
the cathodic polarization pickling time is 10-20 min, and then ultrasonic oscillation washing is carried out in deionized water for 5-30 min.
3. The method according to claim 1, wherein in the step of primary anodic oxidation, the primary anodic oxidation is performed at a voltage of 40V to 70V, a temperature of 15 ℃ to 25 ℃ and a time of 10min to 40min.
4. The method according to claim 1, wherein in the step of one-time anodic oxidation, the fluorine-containing electrolyte comprises ethylene glycol, water, ammonium fluoride and 1 to 40wt% hydrofluoric acid;
the fluorine-containing electrolyte comprises 7.5 to 12.5 percent of water by volume, 0.1 to 0.5 percent of ammonium fluoride by volume and 0.2 to 0.5 percent of hydrofluoric acid by volume.
5. The method according to claim 1, wherein in the calcining step, the calcining temperature is 400 to 600 ℃ and the holding time is 1 to 6 hours.
6. The Ta ion doped titania nanotube prepared by the method of any one of claims 1 to 5.
7. The Ta ion doped titania nanotube of claim 6, wherein the Ta ion doped titania nanotube has a pipe diameter of 70nm to 120nm.
8. Use of the Ta ion doped titania nanotubes of claim 6 or 7 in the preparation of implant materials.
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| CN109989089A (en) * | 2018-01-03 | 2019-07-09 | 中国科学院上海硅酸盐研究所 | External Osteoblast Differentiation tantalum base coating of a kind of rush with micro-nano structure and preparation method thereof |
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