阅读说明：本技术 表面沉积有SiO2多孔的TiO2纳米管阵列的制备方法及应用 (SiO is deposited on the surface2Porous TiO2Preparation method and application of nanotube array ) 是由 宋文 李哲 张玉梅 何奕德 于 2020-03-09 设计创作，主要内容包括：本发明公开了表面沉积有SiO<Sub>2</Sub>多孔的TiO<Sub>2</Sub>纳米管阵列的制备方法及应用。所公开的方法包括：采用油-水两相法在TiO<Sub>2</Sub>纳米管阵列上沉积SiO<Sub>2</Sub>多孔,所述油-水两相法中的油相为含有正硅酸乙酯TEOS的溶液,水相为含有十六烷基三甲基氯化铵CTAC的溶液,所述TiO<Sub>2</Sub>纳米管管径大于50nm。本发明制备的表面沉积有SiO<Sub>2</Sub>多孔的TiO<Sub>2</Sub>纳米管阵列可用于制备口腔种植体。(The invention discloses a method for depositing SiO on the surface 2 Porous TiO 2 A preparation method and application of a nanotube array. The disclosed method comprises: by oil-water two-phase method on TiO 2 Deposition of SiO on nanotube arrays 2 The oil phase in the oil-water two-phase method is a solution containing tetraethyl orthosilicate TEOS, the water phase is a solution containing cetyltrimethylammonium chloride CTAC, and the TiO is porous 2 Nanotube diameterGreater than 50 nm. The surface prepared by the invention is deposited with SiO 2 Porous TiO 2 The nanotube array can be used for preparing oral implants.)

1. SiO is deposited on the surface₂Porous TiO₂The preparation method of the nanotube array is characterized by comprising the following steps: by oil-water two-phase method on TiO₂Deposition of SiO on nanotube arrays₂Porous, oil phase in the oil-water two-phase processIs a TEOS-containing solution, the water phase is a CTAC-containing solution, and the TiO is₂The diameter of the nanotube is larger than 50 nm.

2. The method of claim 1, wherein the TiO is selected from the group consisting of₂The diameter of the nanotube is more than or equal to 80 nm.

3. The method of claim 1, wherein the SiO is₂The porosity is mesoporous.

4. The method of claim 1, wherein the SiO is₂The pore diameter of the porous material is 2-4 nm.

5. The method of claim 1, comprising: will have TiO on the surface₂Placing titanium of the nanotube array in a mixed solution of CTAC, triethylamine and water, adding a mixed solution of TEOS and cyclohexane or a mixed solution of TEOS and decane in the stirring process under a constant temperature condition for reaction, drying and roasting the reaction product after the reaction is finished to obtain the titanium with SiO deposited on the surface₂Porous TiO₂An array of nanotubes.

6. The method of claim 5, wherein the isothermal temperature is 55-65 ℃.

7. The method of claim 5, wherein the drying is carried out at a temperature in the range of 55 to 65 ℃.

8. The method as claimed in claim 5, wherein the suitable temperature range for the calcination is 490-510 ℃.

9. The surface deposited SiO prepared by the method of claim 1₂Porous TiO₂Application of nanotube array in preparing oral implant.

10. MouthThe preparation method of the cavity implant is characterized by comprising the following steps: by oil-water two-phase method on TiO₂Nanotube implant surface deposition of SiO₂The oil phase in the oil-water two-phase method is a solution containing tetraethyl orthosilicate TEOS, and the water phase is a solution containing cetyltrimethylammonium chloride CTAC.

Technical Field

The invention relates to a material with a multi-stage nano-pore structure, in particular to a material with SiO deposited on the surface₂Porous TiO₂A method for preparing a nanotube array and applications thereof.

Background

The superior mechanical and biological functions of the natural tissues of the human body are derived from the fine micro-nano structure in the natural tissues, so from the perspective of bionics, if the complex structures can be constructed, more ideal biological activity can be realized. Although there are many methods available to build ordered nano-array structures on the surface of materials, such as TiO₂The nanotube array, however, lacks gradient change and finer structure in the nanometer scale, and limits the application effect of the bionic material.

Disclosure of Invention

The invention aims to provide a preparation method and application of a TiO2 nanotube array with SiO2 porous deposited on the surface.

The surface provided by the invention is deposited with SiO₂Porous TiO₂The preparation method of the nanotube array comprises the following steps: by oil-water two-phase method on TiO₂Deposition of SiO on nanotube arrays₂The oil phase in the oil-water two-phase method is a solution containing tetraethyl orthosilicate TEOS, the water phase is a solution containing cetyltrimethylammonium chloride CTAC, and the TiO is porous₂The diameter of the nanotube is larger than 50 nm.

Further, the TiO₂The diameter of the nanotube is more than or equal to 80 nm. Specifically, it may be 80-100 nm.

Further, the SiO₂The porosity is mesoporous.

Further, the SiO₂The pore diameter of the porous material is 2-4 nm.

Further, the method comprises providing the surface with TiO₂Placing titanium of the nanotube array in mixed solution of CTAC, triethylamine and water, adding mixed solution of TEOS and cyclohexane or mixed solution of TEOS and decane during stirring at constant temperature for reaction, drying and roasting to obtain the product with SiO deposited on the surface₂Porous TiO₂An array of nanotubes.

Preferably, the constant temperature is 55-65 ℃.

Preferably, the suitable temperature range for drying is 55-65 ℃.

Preferably, the suitable temperature range for the calcination is 490-510 ℃.

The surface prepared by the invention is deposited with SiO₂Porous TiO₂The nanotube array can be used for preparing oral implants.

The invention is in TiO₂Silicon dioxide sodium (MSTF) is further deposited on the surface of The Nanotube (TNT), and a multi-stage nano-pore structure MSTF @ TNT is formed, so that biological effects (specifically, hydrophilicity, cell adhesion, viability of inoculated cells, expression level of osteogenic genes, and osteogenic differentiation characteristics of cells) are further improved, and the method is specifically shown in fig. 1 to 14. The preparation method is simple, uniform and complete, and can be practically applied to the surface of the implant.

Drawings

FIG. 1(a) is an SEM image of a micron-scale pit formed in a titanium plate after hydrofluoric acid etching, representing a micron-scale morphology; (b) is TiO₂A nanotube SEM image representing a nanotopography with dimensions of about 100 nm; the next two SEM images in column (c) are the low power and high power SEM images of the nanotube of the present invention (after 4h deposition), which illustrate the formation of multi-level nano-pore structure on the surface of the titanium substrate;

FIG. 2 shows porous (mesoporous) SiO on the material prepared in example 1₂An aperture distribution map; the illustration shows that the surface aperture of the material is uniform, the aperture size is 3.74 +/-0.98 nm, and the material is in the mesoporous category, so that the adsorption or filtration effect has better specificity;

FIG. 3 shows ATR-FTIR results for the surface of a multi-stage nanotube array (MSTF @ TNT) prepared according to the present invention; the results of this figure illustrate that: SiO at 1080, 793, 473 wavenumbers₂Three characteristic peaks of tetrahedron, which prove SiO₂Generating; the results shown in FIGS. 1 and 2 illustrate TiO₂SiO is formed on the surface of the nanotube₂A secondary nano structure with the aperture about 4nm is formed, and the secondary nano structure is also called a mesoporous structure;

FIG. 4 shows the adhesion results of MC3T3-E1 cells cultured on TNT (a) and MSTF @ TNT (b), respectively, for 1 day, which shows that: the cell extension on the surface of the material prepared by the invention is more obvious, and the cell adhesion quantity is increased;

FIG. 5 shows the results of water contact angle measurements on the surfaces of different samples, showing: pure Titanium (PT) surface water contact angle was about 37.75 °, TNT was 21.37 °, whereas MSTF @ TNT surface could reach 7.08 ° and rapidly wet the entire surface within one second, exhibiting superhydrophilicity, <0.05, <0.01, < 0.001;

FIG. 6 is a confocal microscope observation of MC3T3-E1 cells after 2h inoculation, illustrating that: the MSTF @ TNT surface had a greater number of MC3T3-E1 cell adhesions, demonstrating that the surface can promote osteoblast early adhesion, on a scale of 200 μm, <0.05, <0.01, < 0.001;

FIG. 7 is a graph showing the results of the CCK8 method for identifying the viability levels of cells after 1d and 3d inoculation: MSTF @ TNT surface showed the highest cell viability at each time node p <0.05, > p <0.01, > p < 0.001;

FIG. 8 shows the expression levels of the surface osteogenesis related genes of the different samples inoculated with 3d and 7d cells, and the graphical results show that the expression levels of MSTF @ TNT are basically significantly higher than those of the control group at different times for the four most common osteogenesis related genes A L P, RUNX2, OPN and OCN, p <0.05, > p <0.01, > p < 0.001;

FIG. 9 shows the results of A L P staining and alizarin red staining, which show that MSTF @ TNT surface A L P staining and alizarin red staining are both darker, indicating that MSTF @ TNT surface alkaline phosphatase activity is stronger and extracellular calcium deposition is more obvious, which means that surface cell osteogenic differentiation is more obvious.

FIGS. 10a and b are TiO with small tube diameter of comparative example₂Macroscopic and macroscopic results plot of nanotube (30nm) array surface;

FIGS. 11a and b are graphs showing the macroscopic and macroscopic results of the multi-stage nano-pore structure synthesized in example 2 using decane as an oil phase component, respectively;

FIG. 12 is a porous SiO solid on the material synthesized in example 2₂The pore size distribution of the film;

FIGS. 13a and b are graphs of the macroscopic and macroscopic results of the multi-stage nano-pore structure synthesized in example 3, respectively;

FIG. 14 shows porous SiO on the synthesized material of example 3₂Membrane pore size distribution.

Detailed Description

The invention adopts an oil-water two-phase method, takes solution containing tetraethyl orthosilicate TEOS (silicon source: silicon element provided in the reaction process) as an oil phase and solution containing hexadecyl trimethyl ammonium chloride CTAC (template agent: which plays a role in synthesizing and guiding a porous and mesoporous structure in the reaction process) as a water phase, and takes the solution as the water phase to perform the TiO synthesis in large pipe diameter (more than 50nm)₂The surface of the nanotube array is reacted, dried and roasted to obtain the product with SiO deposited on the surface₂The structure of the multi-stage nano-tube with a porous structure. The preparation method of the invention can combine the small pore-scale nano structure and the large pore-scale nano structure together to construct the multi-level nano pore structure.

The composition of the respective solvents of the solution containing tetraethyl orthosilicate TEOS and the solution containing cetyltrimethylammonium chloride CTAC is based on the purpose of realizing the invention. Specifically, a mixed solution of CTAC, triethylamine and water can be used as an aqueous phase, wherein the triethylamine provides but is not limited to an alkaline catalytic environment, the toxicity and side effects of the triethylamine are low, and the water is used as a diluent. The mixed solution of tetraethoxysilane TEOS and cyclohexane is an oil phase, wherein the cyclohexane is used as but not limited to a constituent component of the oil phase in an oil-water two-phase method, plays a certain expansion role on micelles, and can be replaced by decane or other carbon alkanes.

The drying in the process of the present invention is not limited to removing the solvent on the surface of the material after the reaction, and the material surface solvent can be removed by cleaning before the drying, and the drying process can be selected but not limited to being performed in an oven. Wherein the calcination temperature is higher or much higher than the temperature during drying, optionally but not limited to, in a muffle furnace.

It should be noted that, when the reaction materials provided by the present invention are used to prepare materials under the conditions defined by the present invention, reasonable material usage amounts are within the protection scope of the present invention.

In order to make the present invention more comprehensible, the technical solutions of the present invention are further described below with reference to specific embodiments, but the present invention is not limited thereto.