阅读说明：本技术 原位制备{001}晶面曝露的锐钛矿型二氧化钛薄膜的方法 (Method for in-situ preparation of {001} crystal face exposed anatase type titanium dioxide film ) 是由 肖帆 周丹 于 2021-08-23 设计创作，主要内容包括：本发明公开了一种原位制备{001}晶面曝露的锐钛矿型二氧化钛薄膜的方法,具体实施方式如下：先对基体进行清洗,然后进行退火预处理,将处理后的基体再进行清洗并晾干备用；将钛源、氟源、酸和异丙醇均匀混合并充分搅拌,配置成反应前驱液备用；将基体与反应前驱液移至不锈钢高压反应釜中,在电热鼓风干燥箱中进行水热反应,反应结束后冷却取出基体,用去离子水进行超声清洗,获得表面有二氧化钛薄膜的基体。通过本发明制备得到的薄膜在基体上原位生长形貌均匀、致密且薄。(The invention discloses a method for in-situ preparation of an anatase titanium dioxide film with exposed {001} crystal face, which comprises the following specific implementation modes: cleaning a substrate, then carrying out annealing pretreatment, cleaning the treated substrate, and airing for later use; uniformly mixing a titanium source, a fluorine source, acid and isopropanol, and fully stirring to prepare a reaction precursor solution for later use; and (3) moving the substrate and the reaction precursor liquid into a stainless steel high-pressure reaction kettle, carrying out hydrothermal reaction in an electrothermal blowing dry box, cooling after the reaction is finished, taking out the substrate, and carrying out ultrasonic cleaning by using deionized water to obtain the substrate with the titanium dioxide film on the surface. The film prepared by the method has uniform, compact and thin in-situ growth appearance on a substrate.)

1. The method for preparing the anatase type titanium dioxide film with the exposed {001} crystal face in situ is characterized by comprising the following steps:

1) cleaning a substrate, then carrying out annealing pretreatment, cleaning the treated substrate, and airing for later use;

2) uniformly mixing a titanium source, a fluorine source, acid and isopropanol, and fully stirring to prepare a reaction precursor solution for later use;

3) and (3) moving the substrate and the reaction precursor liquid into a stainless steel high-pressure reaction kettle, carrying out hydrothermal reaction in an electrothermal blowing dry box, cooling after the reaction is finished, taking out the substrate, and carrying out ultrasonic cleaning by using deionized water to obtain the substrate with the titanium dioxide film on the surface.

2. The method for in-situ preparation of an anatase titanium dioxide film with exposed {001} crystal face according to claim 1, wherein the titanium source in the reaction precursor liquid in the step 2) is at least one of ammonium fluotitanate, fluotitanic acid, titanium trichloride, titanium tetrafluoride and titanium sulfite.

3. The method for in-situ preparation of an anatase titanium dioxide thin film with exposed {001} crystal face according to claim 1, wherein the fluorine source in the reaction precursor liquid in the step 2) is at least one of ammonium fluotitanate, fluotitanic acid, sodium fluoride and titanium tetrafluoride.

4. The method for preparing the anatase titanium dioxide film with exposed {001} crystal face in situ according to claim 1, wherein the matrix in step 1) is at least one of titanium and titanium alloy.

5. The method for in-situ preparation of an anatase titanium dioxide film with exposed {001} crystal face according to claim 1, wherein the acid in the reaction precursor liquid in the step 2) is at least one of hydrochloric acid, sulfuric acid, nitric acid, oxalic acid and acetic acid.

6. The method for in-situ preparation of an anatase titanium dioxide film with exposed {001} crystal planes according to claim 1, wherein the concentration of the titanium source in the reaction precursor liquid in step 2) is 0.20mM to 1.60 mM.

7. The method for in-situ preparation of an anatase titanium dioxide film having exposed {001} crystal planes according to claim 1, wherein the molar ratio of the titanium source to the acid in step 2) is 1: 9-1:100, the molar ratio of the titanium source to the isopropanol being 1: 25-1: 150, the molar ratio of the titanium source to the fluorine source is 1: 2-1: 10.

8. the method for in-situ preparation of the anatase titanium dioxide film with exposed {001} crystal face according to claim 1, wherein the annealing pretreatment temperature used in step 1) is 200-700 ℃, and the heat preservation time is more than 0.5 h.

9. The method for preparing the anatase type titanium dioxide film with exposed {001} crystal face in situ according to claim 1, wherein the hydrothermal reaction in the step 3) is carried out for 1-5h at 80-200 ℃, and the cooling mode after the hydrothermal reaction is water cooling.

Technical Field

The invention belongs to the technical field of materials, and particularly relates to a method for in-situ preparation of an anatase titanium dioxide film with exposed {001} crystal face.

Background

Titanium and its alloy have high corrosion resistance, the elastic modulus is close to the advantage of natural bone and its fatigue resistance can be good, used in the surgical implant material nowadays, its surface has not been processed the natural titanium oxide membrane that obtains has no biological activity, it is only simple mechanical bonding, need to carry on surface activation to give its biological activity to it, thus induce the deposition of hydroxyapatite in the human simulated body fluid.

The nano titanium dioxide film has large specific surface area, small size and excellent biocompatibility and photocatalytic performance, and is widely applied to the aspects of electronics, coatings, textiles, sewage treatment, tumor diagnosis, implant modification, antibiosis and the like. Anatase titanium dioxide crystals with different morphologies have different physicochemical properties, and the nano-structure characteristics which have a large influence on the properties of the anatase titanium dioxide crystals have three aspects, namely crystal faces, crystal boundaries and heterostructures. In particular to crystal faces, the surface energy of different crystal faces of the anatase titanium dioxide crystal is ordered according to the first linear Density Functional Theory (DFT): e {001} (0.9J/m)²)>E{100}(0.53 J/m²)>E{101}(0.44 J/m²) According to the principle of minimizing surface energy, the high-energy crystal face is rapidly reduced in the crystal growth process and is replaced by other low-energy crystal faces. Therefore, obtaining the anatase high energy surface {001} is a preferred target for research in various fields.

In 2008, Yang et al used HF as a morphology control agent to synthesize single-crystal anatase titanium dioxide with 47% of {001} crystal face exposure rate by a hydrothermal method. Research into the synthesis of single crystals of anatase titanium dioxide with exposed {001} planes has begun to gain much attention. Then, Yang et al used isopropanol as a synergistic blocking agent and reaction medium for hydrofluoric acid to achieve a {001} surface exposure of 64%. For example, titanium tetrafluoride, hydrofluoric acid and isopropanol proposed in chinese patent CN201510290626.5 are used as precursor liquid, and a hydrothermal method is used to prepare the football-shaped anatase titanium dioxide powder with exposed high-energy crystal face {001}, which has high purity and good crystallinity, but the concentration of the titanium source used is 0.16M to 0.18M, and the concentration is high, and only powder particles can be generated, and a thin film cannot be prepared.

The anatase titanium dioxide with exposed {001} crystal face reported in the literature is generally a powder particle, which is not easy to recover and difficult to fix, making it limited in many applications. In the application direction of biological materials, titanium dioxide powder cannot be effectively combined with a matrix, and in addition, the matrix is seriously corroded due to the addition of HF.

Disclosure of Invention

In order to solve the above problems, the present invention is directed to a method for in-situ preparing an anatase type titanium dioxide thin film with an exposed {001} crystal plane.

In order to achieve the purpose, the following technical scheme is provided:

the method for preparing the anatase type titanium dioxide film with the exposed {001} crystal face in situ comprises the following steps:

1) cleaning a substrate, then carrying out annealing pretreatment, cleaning the treated substrate, and airing for later use;

2) uniformly mixing a titanium source, a fluorine source, acid and isopropanol, and fully stirring to prepare a reaction precursor solution for later use;

3) and (3) moving the substrate and the reaction precursor liquid into a stainless steel high-pressure reaction kettle, carrying out hydrothermal reaction in an electrothermal blowing dry box, cooling after the reaction is finished, taking out the substrate, and carrying out ultrasonic cleaning by using deionized water to obtain the substrate with the titanium dioxide film on the surface.

Further, the titanium source in the reaction precursor liquid in the step 2) is at least one of ammonium fluotitanate, fluotitanic acid, titanium trichloride, titanium tetrafluoride and titanium sulfite.

Further, the fluorine source in the reaction precursor liquid in the step 2) is at least one of ammonium fluotitanate, fluotitanic acid, sodium fluoride and titanium tetrafluoride.

Further, the matrix in the step 1) is at least one of titanium and titanium alloy.

Further, the acid in the reaction precursor liquid in the step 2) is at least one of hydrochloric acid, sulfuric acid, nitric acid, oxalic acid and acetic acid.

Further, the concentration of the titanium source in the reaction precursor liquid in the step 2) is 0.20mM-1.60 mM.

Further, the molar ratio of the titanium source to the acid in the step 2) is 1: 9-1:100, the molar ratio of the titanium source to the isopropanol being 1: 25-1: 150, the molar ratio of the titanium source to the fluorine source is 1: 2-1: 10.

further, in order to avoid collapse corrosion of the 3D printed titanium alloy substrate, hydrogen peroxide can be added into the solution obtained in the step (2), and the molar ratio of the concentration of the titanium source to the molar ratio of the hydrogen peroxide is 1: 15.

further, the annealing pretreatment temperature adopted in the step 1) is 200-700 ℃, and the heat preservation time is more than 0.5 h.

Further, the reaction time used in the hydrothermal reaction in the step 3) is 1-5h, the temperature of the hydrothermal reaction is 80-200 ℃, and the cooling mode after the hydrothermal reaction is water cooling.

The invention has the beneficial effects that:

1) generally, hydrofluoric acid is selected as a capping reagent for exposing the high-energy crystal face, but the hydrofluoric acid corrodes the surface of a substrate and cannot form a uniform titanium dioxide film, fluotitanic acid and isopropanol are adopted as precursor liquid, and the synergistic effect between the fluotitanic acid and the isopropanol can effectively control the grain size and expose the {001} high-energy crystal face, so that the corrosion effect of the hydrofluoric acid is effectively avoided, and a proper amount of fluorine content can effectively resist bacteria;

2) the prepared titanium dioxide film has small crystal grains, the general size is between 15nm and 60nm, the size is small, the number of crystal boundaries is large, and the surface energy is high;

3) the method can obtain the uniform and thin anatase titanium dioxide film with the exposed {001} crystal face at low temperature by a hydrothermal method, the film is formed in a liquid phase at one time, subsequent treatment is not needed, the reaction repeatability is good, the film is not limited by a substrate and the size, and the roughness of the substrate is not influenced later.

Drawings

FIG. 1 is a field emission scanning electron micrograph of an anatase type titanium dioxide thin film obtained in example 1;

FIG. 2 is a field emission scanning electron micrograph of an anatase type titanium dioxide thin film obtained in example 3;

FIG. 3 is a field emission scanning electron micrograph of an anatase titania thin film obtained by the production in example 4;

FIG. 4 is a field emission scanning electron micrograph of an anatase titania thin film obtained by the production in example 7;

FIG. 5 is a scanning electron micrograph of anatase titania thin films prepared in example 8;

FIG. 6 is a scanning electron micrograph of anatase titania thin films produced in example 9;

FIG. 7 is a scanning electron micrograph of anatase titania thin film produced in example 10;

FIG. 8 is a scanning electron micrograph of anatase titania thin film produced in example 12;

FIG. 9 is a scanning electron micrograph of anatase titania thin film produced in example 13;

FIG. 10 is a scanning electron micrograph of anatase titania thin film produced in example 14;

FIG. 11 is a scanning electron micrograph of anatase titania thin films produced according to example 15;

FIG. 12 is a scanning electron micrograph of anatase titania thin film produced in example 16;

FIG. 13 is a scanning electron micrograph of anatase titanium dioxide thin film produced according to example 17;

FIG. 14 is a scanning electron micrograph of anatase titania thin film obtained by production in example 18;

FIG. 15 is a scanning electron micrograph of an anatase titania thin film obtained by production in example 29;

fig. 16 is an XRD test result and a pure titanium XRD result of the anatase type titanium dioxide thin film prepared in example 1 of the present invention.

Detailed Description

The invention will be further described with reference to the following examples and the accompanying drawings, but the scope of the invention is not limited thereto. Such as reaction equipment and reaction temperature, reaction time, and the kind and concentration of the reaction precursor liquid are not limited to those exemplified in the examples. The invention takes pure titanium, titanium alloy and the like as the matrix of the in-situ grown titanium dioxide film, and is suitable for medical implants. Implants include, but are not limited to, implants that are implanted in humans as a human replacement or support, implants that are implanted in animals as a replacement for bone, and the like. Substitutes for implantation into the human body include, but are not limited to, dental implants, bone substitutes, implants that support or attach to bone, such as steel nails, plates, and the like. The invention researches the bioactivity of the method, but not only the bioactivity, but also other properties.

Example 1

The method for preparing the anatase titanium dioxide film with the exposed {001} crystal face in situ provided by the embodiment comprises the following steps:

1) annealing pretreatment of the titanium sheet: shearing to 25' 10 mm²The titanium substrate is alternately cleaned by acetone and ethanol, each cleaning is carried out for 5min, the circulation is carried out for 3 times, and then the titanium substrate is cleaned by deionized water for 3 times. Then, annealing the titanium sheet in a muffle furnace at 450 ℃ for 1.5h, cleaning in the same way after taking out, and airing at normal temperature for later use;

2) preparing 250mL of reaction precursor liquid, taking fluotitanic acid as a titanium source and a fluorine source, wherein the concentration of the fluotitanic acid is 0.885mM, the concentration of hydrochloric acid is 13mM, and the concentration of isopropanol is 33 mM;

3) simultaneously putting the precursor solution and the titanium sheet into a stainless steel high-pressure reaction kettle, carrying out hydrothermal reaction in an electrothermal blowing dry box at the reaction temperature and the reaction time of 160 ℃ and 2 hours respectively, carrying out ultrasonic cleaning on a sample taken out after water cooling in deionized water, and airing at normal temperature;

as can be seen from FIG. 1, the titanium dioxide film with the exposed flaky {001} crystal face appears on the substrate, the surface appearance of the film is uniform, the film completely covers the surface of the substrate, and a layer of dense hydroxyapatite is formed on the surface of the titanium dioxide film after soaking for 24 hours by 1.5 times of SBF. FIG. 1 (a) is a micrograph at 500 nm; FIG. 1 (b) is a microscopic image of a titanium sheet after being soaked in a constant temperature incubator at 36.5 ℃ for 24 hours with 1.5 times of SBF; as can be seen from FIG. 16, the XRD pattern of standard anatase titanium dioxide has a peak at 37.5 deg. corresponding to the (004) crystal plane, and a significant exposure of the (004) crystal plane occurs. Therefore, the method can prepare the anatase titanium dioxide film exposed by the high-energy {001} crystal face family in situ.

Example 2

The method for preparing the anatase titanium dioxide film with the exposed {001} crystal face in situ provided by the embodiment comprises the following steps:

1) annealing pretreatment of the titanium sheet: shearing to 25' 10 mm²Titanium substrate of, use ofAnd alternately cleaning with acetone and ethanol for 5min each time, circulating for 3 times, and cleaning with deionized water for 3 times. Then, annealing the titanium sheet in a muffle furnace at 450 ℃ for 1.5h, cleaning in the same way after taking out, and airing at normal temperature for later use;

2) preparing 200mL of reaction precursor liquid, taking fluotitanic acid as a titanium source and a fluorine source, wherein the concentration of the fluotitanic acid is 0.885mM, the concentration of hydrochloric acid is 13mM, and the concentration of isopropanol is 33 mM;

3) simultaneously putting the precursor solution and the titanium sheet into a stainless steel high-pressure reaction kettle, carrying out hydrothermal reaction in an electrothermal blowing dry box at the reaction temperature of 160 ℃ for 1h, carrying out ultrasonic cleaning on a sample taken out after water cooling in deionized water, and airing at normal temperature;

the titanium dioxide film exposed to the {001} crystal face of the sheet appears on the substrate. The surface appearance of the film is uniform, the film completely covers the surface of the substrate, and a layer of compact hydroxyapatite is formed on the surface of the titanium dioxide film after the film is soaked for 24 hours by 1.5 times of SBF.

Example 3

The method for preparing the anatase titanium dioxide film with the exposed {001} crystal face in situ provided by the embodiment comprises the following steps:

1) annealing pretreatment of the titanium sheet: shearing to 25' 10 mm²The titanium substrate is alternately cleaned by acetone and ethanol, each cleaning is carried out for 5min, the circulation is carried out for 3 times, and then the titanium substrate is cleaned by deionized water for 3 times. Then, annealing the titanium sheet in a muffle furnace at 450 ℃ for 1.5h, cleaning in the same way after taking out, and airing at normal temperature for later use;

2) preparing 250mL of reaction precursor liquid, taking fluotitanic acid as a titanium source and a fluorine source, wherein the concentration of the fluotitanic acid is 0.885mM, the concentration of hydrochloric acid is 13mM, and the concentration of isopropanol is 33 mM;

3) simultaneously putting the precursor solution and the titanium sheet into a stainless steel high-pressure reaction kettle, carrying out hydrothermal reaction in an electrothermal blowing dry box at the reaction temperature and the reaction time of 160 ℃ and 3 hours respectively, carrying out ultrasonic cleaning on a sample taken out after water cooling in deionized water, and airing at normal temperature;

as can be seen from fig. 2, a flaky titanium dioxide film exposed on the {001} crystal face appears on the substrate, the surface appearance of the film is uniform, the film completely covers the surface of the substrate, and a layer of dense hydroxyapatite is formed on the surface of the titanium dioxide film after soaking for 24 hours by 1.5 times of SBF, and fig. 2 (a) is a microscopic appearance image with a scale of 500 nm; FIG. 2 (b) is a micrograph of a titanium sheet after soaking in a constant temperature incubator at 36.5 ℃ with 1.5 times of SBF for 24 hours.

Example 4

The method for preparing the anatase titanium dioxide film with the exposed {001} crystal face in situ provided by the embodiment comprises the following steps:

1) annealing pretreatment of the titanium sheet: shearing to 25' 10 mm²The titanium substrate is alternately cleaned by acetone and ethanol, each cleaning is carried out for 5min, the circulation is carried out for 3 times, and then the titanium substrate is cleaned by deionized water for 3 times. Then, annealing the titanium sheet in a muffle furnace at 450 ℃ for 1.5h, cleaning in the same way after taking out, and airing at normal temperature for later use;

2) preparing 250mL of reaction precursor liquid, taking fluotitanic acid as a titanium source and a fluorine source, wherein the concentration of the fluotitanic acid is 0.885mM, the concentration of hydrochloric acid is 13mM, and the concentration of isopropanol is 33 mM;

3) simultaneously putting the precursor solution and the titanium sheet into a stainless steel high-pressure reaction kettle, carrying out hydrothermal reaction in an electrothermal blowing dry box at the reaction temperature and the reaction time of 160 ℃ and 4 hours respectively, carrying out ultrasonic cleaning on a sample taken out after water cooling in deionized water, and airing at normal temperature;

as can be seen from FIG. 3, the titanium dioxide film with the exposed flaky {001} crystal face appears on the substrate, the surface appearance of the film is uniform, the film completely covers the surface of the substrate, and a layer of dense hydroxyapatite is formed on the surface of the titanium dioxide film after soaking for 24 hours by 1.5 times of SBF. FIG. 3 (a) is a micrograph at 500 nm; FIG. 3 (b) is a micrograph of a titanium sheet after soaking in a constant temperature incubator at 36.5 ℃ with 1.5 times of SBF for 24 hours.

Example 5

The method for preparing the anatase titanium dioxide film with the exposed {001} crystal face in situ provided by the embodiment comprises the following steps:

1) annealing pretreatment of the titanium sheet: shearing to 25' 10 mm²The titanium substrate is alternately cleaned by acetone and ethanol,washing for 5min each time, circulating for 3 times, and washing with deionized water for 3 times. Then, annealing the titanium sheet in a muffle furnace at 450 ℃ for 1.5h, cleaning in the same way after taking out, and airing at normal temperature for later use;

2) preparing 200mL of reaction precursor liquid, taking fluotitanic acid as a titanium source and a fluorine source, wherein the concentration of the fluotitanic acid is 0.885mM, the concentration of hydrochloric acid is 13mM, and the concentration of isopropanol is 33 mM;

3) simultaneously putting the precursor solution and the titanium sheet into a stainless steel high-pressure reaction kettle, carrying out hydrothermal reaction in an electrothermal blowing dry box at the reaction temperature and the reaction time of 160 ℃ and 5 hours respectively, carrying out ultrasonic cleaning on a sample taken out after water cooling in deionized water, and airing at normal temperature;

the titanium dioxide film exposed to the {001} crystal face of the sheet appears on the substrate. The surface appearance of the film is uniform, the film completely covers the surface of the substrate, and a layer of compact hydroxyapatite is formed on the surface of the titanium dioxide film after the film is soaked for 24 hours by 1.5 times of SBF.

Example 6

The method for preparing the anatase titanium dioxide film with the exposed {001} crystal face in situ provided by the embodiment comprises the following steps:

1) annealing pretreatment of the titanium sheet: shearing to 25' 10 mm²The titanium substrate is alternately cleaned by acetone and ethanol, each cleaning is carried out for 5min, the circulation is carried out for 3 times, and then the titanium substrate is cleaned by deionized water for 3 times. Then, annealing the titanium sheet in a muffle furnace at 450 ℃ for 1.5h, cleaning in the same way after taking out, and airing at normal temperature for later use;

2) preparing 200mL of reaction precursor liquid, taking fluotitanic acid as a titanium source and a fluorine source, wherein the concentration of the fluotitanic acid is 0.885mM, the concentration of hydrochloric acid is 13mM, and the concentration of isopropanol is 33 mM;

3) simultaneously putting the precursor solution and the titanium sheet into a stainless steel high-pressure reaction kettle, carrying out hydrothermal reaction in an electrothermal blowing dry box at the reaction temperature and the reaction time of 80 ℃ and 2 hours respectively, carrying out ultrasonic cleaning on a sample taken out after water cooling in deionized water, and airing at normal temperature;

the titanium dioxide film exposed to the {001} crystal face of the sheet appears on the substrate. The surface appearance of the film is uniform, the film completely covers the surface of the substrate, and a layer of compact hydroxyapatite is formed on the surface of the titanium dioxide film after the film is soaked for 24 hours by 1.5 times of SBF.

Example 7

The method for preparing the anatase titanium dioxide film with the exposed {001} crystal face in situ provided by the embodiment comprises the following steps:

1) annealing pretreatment of the titanium sheet: shearing to 25' 10 mm²The titanium substrate is alternately cleaned by acetone and ethanol, each cleaning is carried out for 5min, the circulation is carried out for 3 times, and then the titanium substrate is cleaned by deionized water for 3 times. Then, annealing the titanium sheet in a muffle furnace at 450 ℃ for 1.5h, cleaning in the same way after taking out, and airing at normal temperature for later use;

2) preparing 200mL of reaction precursor liquid, taking fluotitanic acid as a titanium source and a fluorine source, wherein the concentration of the fluotitanic acid is 0.885mM, the concentration of hydrochloric acid is 13mM, and the concentration of isopropanol is 33 mM;

3) simultaneously putting the precursor solution and the titanium sheet into a stainless steel high-pressure reaction kettle, carrying out hydrothermal reaction in an electrothermal blowing dry box at the reaction temperature and the reaction time of 100 ℃ and 2 hours respectively, carrying out ultrasonic cleaning on a sample taken out after water cooling in deionized water, and airing at normal temperature;

as can be seen from fig. 4, a flaky titanium dioxide film exposed on the {001} crystal face appears on the substrate, the surface appearance of the film is uniform, the film completely covers the surface of the substrate, and a layer of dense hydroxyapatite is formed on the surface of the titanium dioxide film after soaking for 24 hours by 1.5 times of SBF, and fig. 4 (a) is a microscopic appearance image with a scale of 500 nm; FIG. 4 (b) is a micrograph of a titanium sheet after soaking in a constant temperature incubator at 36.5 ℃ with 1.5 times of SBF for 24 hours.

Example 8

The method for preparing the anatase titanium dioxide film with the exposed {001} crystal face in situ provided by the embodiment comprises the following steps:

1) annealing pretreatment of the titanium sheet: shearing to 25' 10 mm²The titanium substrate is alternately cleaned by acetone and ethanol for 5min each time, circulated for 3 times, cleaned by deionized water for 3 times, then annealed at 450 ℃ for 1.5h in a muffle furnace, cleaned in the same way after being taken out, and dried at normal temperature for later use;

2) preparing 200mL of reaction precursor liquid, taking fluotitanic acid as a titanium source and a fluorine source, wherein the concentration of the fluotitanic acid is 0.885mM, the concentration of hydrochloric acid is 13mM, and the concentration of isopropanol is 33 mM;

3) simultaneously putting the precursor solution and the titanium sheet into a stainless steel high-pressure reaction kettle, carrying out hydrothermal reaction in an electrothermal blowing dry box at the reaction temperature and the reaction time of 120 ℃ and 2 hours respectively, carrying out ultrasonic cleaning on a sample taken out after water cooling in deionized water, and airing at normal temperature;

as can be seen from FIG. 5, the titanium dioxide film with the exposed flaky {001} crystal face appears on the substrate, the surface appearance of the film is uniform, the film completely covers the surface of the substrate, and a layer of dense hydroxyapatite is formed on the surface of the titanium dioxide film after soaking for 24 hours by 1.5 times of SBF. FIG. 5 (a) is a micrograph at 500 nm; FIG. 5 (b) is a micrograph of a titanium sheet after soaking in a constant temperature incubator at 36.5 ℃ with 1.5 times of SBF for 24 hours.

Example 9

The method for preparing the anatase titanium dioxide film with the exposed {001} crystal face in situ provided by the embodiment comprises the following steps:

1) annealing pretreatment of the titanium sheet: shearing to 25' 10 mm²The titanium substrate is alternately cleaned by acetone and ethanol for 5min each time, circulated for 3 times, cleaned by deionized water for 3 times, then annealed at 450 ℃ for 1.5h in a muffle furnace, cleaned in the same way after being taken out, and dried at normal temperature for later use;

2) preparing 200mL of reaction precursor liquid, taking fluotitanic acid as a titanium source and a fluorine source, wherein the concentration of the fluotitanic acid is 0.885mM, the concentration of hydrochloric acid is 13mM, and the concentration of isopropanol is 33 mM;

3) simultaneously putting the precursor solution and the titanium sheet into a stainless steel high-pressure reaction kettle, carrying out hydrothermal reaction in an electrothermal blowing dry box at the reaction temperature of 140 ℃ for 2 hours, carrying out ultrasonic cleaning on a sample taken out after water cooling in deionized water, and airing at normal temperature; as can be seen from FIG. 6, a titanium oxide film with exposed {001} crystal plane appears on the substrate in a sheet form. The film has uniform surface appearance and completely covers the surface of the substrate. And a layer of compact hydroxyapatite is formed on the surface of the titanium dioxide film after the titanium dioxide film is soaked for 24 hours by 1.5 times of SBF. FIG. 6 (a) is a micrograph at 500 nm; FIG. 6 (b) is a micrograph of a titanium sheet after soaking in a constant temperature incubator at 36.5 ℃ with 1.5 times of SBF for 24 hours.

Example 10

The method for preparing the anatase titanium dioxide film with the exposed {001} crystal face in situ provided by the embodiment comprises the following steps:

1) annealing pretreatment of the titanium sheet: shearing to 25' 10 mm²The titanium substrate is alternately cleaned by acetone and ethanol for 5min each time, circulated for 3 times, cleaned by deionized water for 3 times, then annealed at 450 ℃ for 1.5h in a muffle furnace, cleaned in the same way after being taken out, and dried at normal temperature for later use;

2) preparing 200mL of reaction precursor liquid, taking fluotitanic acid as a titanium source and a fluorine source, wherein the concentration of the fluotitanic acid is 0.885mM, the concentration of hydrochloric acid is 13mM, and the concentration of isopropanol is 33 mM;

3) simultaneously putting the precursor solution and the titanium sheet into a stainless steel high-pressure reaction kettle, carrying out hydrothermal reaction in an electrothermal blowing dry box at the reaction temperature of 180 ℃ for 2 hours, carrying out ultrasonic cleaning on a sample taken out after water cooling in deionized water, and airing at normal temperature;

as can be seen from FIG. 7, the titanium dioxide film with the exposed flaky {001} crystal face appears on the substrate, the surface appearance of the film is uniform, the film completely covers the surface of the substrate, and a layer of dense hydroxyapatite is formed on the surface of the titanium dioxide film after soaking for 24 hours by 1.5 times of SBF. FIG. 7 (a) is a micrograph at 500 nm; FIG. 7 (b) is a micrograph of a titanium sheet after soaking in a constant temperature incubator at 36.5 ℃ with 1.5 times SBF for 24 hours.

Example 11

The method for preparing the anatase titanium dioxide film with the exposed {001} crystal face in situ provided by the embodiment comprises the following steps:

1) annealing pretreatment of the titanium sheet: shearing to 25' 10 mm²The titanium substrate is alternately cleaned by acetone and ethanol, each cleaning is carried out for 5min, the circulation is carried out for 3 times, and then the titanium substrate is cleaned by deionized water for 3 times. Thereafter, the titanium sheet was mounted on a muffleAnnealing at 450 ℃ for 1.5h in a furnace, cleaning in the same way after taking out, and airing at normal temperature for later use;

2) preparing 200mL of reaction precursor liquid, taking fluotitanic acid as a titanium source and a fluorine source, wherein the concentration of the fluotitanic acid is 1.6mM, the concentration of hydrochloric acid is 36mM, and the concentration of isopropanol is 33 mM;

3) simultaneously putting the precursor solution and the titanium sheet into a stainless steel high-pressure reaction kettle, carrying out hydrothermal reaction in an electrothermal blowing dry box at the reaction temperature and the reaction time of 200 ℃ and 2 hours respectively, carrying out ultrasonic cleaning on a sample taken out after water cooling in deionized water, and airing at normal temperature;

the titanium dioxide film exposed to the {001} crystal face of the sheet appears on the substrate. The surface appearance of the film is uniform, the film completely covers the surface of the substrate, and a layer of compact hydroxyapatite is formed on the surface of the titanium dioxide film after the film is soaked for 24 hours by 1.5 times of SBF.

Example 12

The method for preparing the anatase titanium dioxide film with the exposed {001} crystal face in situ provided by the embodiment comprises the following steps:

1) annealing pretreatment of the titanium sheet: shearing to 25' 10 mm²The titanium substrate is alternately cleaned by acetone and ethanol, each cleaning is carried out for 5min, the circulation is carried out for 3 times, and then the titanium substrate is cleaned by deionized water for 3 times. Then, annealing the titanium sheet in a muffle furnace at 450 ℃ for 1.5h, cleaning in the same way after taking out, and airing at normal temperature for later use;

2) preparing 100mL of reaction precursor liquid, taking fluotitanic acid as a titanium source and a fluorine source, wherein the concentration of the fluotitanic acid is 0.885mM, the concentration of hydrochloric acid is 26mM, and the concentration of isopropanol is 22 mM;

3) simultaneously putting the precursor solution and the titanium sheet into a stainless steel high-pressure reaction kettle, carrying out hydrothermal reaction in an electrothermal blowing dry box at the reaction temperature and the reaction time of 160 ℃ and 2 hours respectively, carrying out ultrasonic cleaning on a sample taken out after water cooling in deionized water, and airing at normal temperature;

as can be seen from fig. 8, a titanium dioxide film with a flaky {001} crystal face exposed appears on the substrate, the surface appearance of the film is uniform, the film completely covers the surface of the substrate, and a layer of dense hydroxyapatite is formed on the surface of the titanium dioxide film after soaking for 24 hours by 1.5 times of SBF, and fig. 8 (a) is a microscopic appearance image with a scale of 500 nm; FIG. 8 (b) is a micrograph of a titanium sheet after soaking in a constant temperature incubator at 36.5 ℃ with 1.5 times SBF for 24 hours.

Example 13

The method for preparing the anatase titanium dioxide film with the exposed {001} crystal face in situ provided by the embodiment comprises the following steps:

1) annealing pretreatment of the titanium sheet: shearing to 25' 10 mm²The titanium substrate is alternately cleaned by acetone and ethanol for 5min each time, circulated for 3 times, cleaned by deionized water for 3 times, then annealed at 450 ℃ for 1.5h in a muffle furnace, cleaned in the same way after being taken out, and dried at normal temperature for standby,

2) preparing 100mL of reaction precursor solution by using fluotitanic acid as a titanium source and a fluorine source, wherein the concentration of the fluotitanic acid is 0.885mM, the concentration of hydrochloric acid is 26mM, the concentration of isopropanol is 66mM,

3) putting the precursor solution and the titanium sheet into a stainless steel high-pressure reaction kettle at the same time, carrying out hydrothermal reaction in an electrothermal blowing dry box at the reaction temperature and the reaction time of 160 ℃ and 2 hours respectively, carrying out ultrasonic cleaning on a sample taken out after water cooling in deionized water, airing at normal temperature,

as can be seen from fig. 9, a titanium dioxide film with a flaky {001} crystal face exposed appears on the substrate, the surface appearance of the film is uniform, the film completely covers the surface of the substrate, and a layer of dense hydroxyapatite is formed on the surface of the titanium dioxide film after soaking for 24 hours by 1.5 times of SBF, and fig. 9 (a) is a microscopic appearance image with a scale of 500 nm; FIG. 9 (b) is a micrograph of a titanium sheet after soaking in a constant temperature incubator at 36.5 ℃ with 1.5 times SBF for 24 hours.

Example 14

The method for preparing the anatase titanium dioxide film with the exposed {001} crystal face in situ provided by the embodiment comprises the following steps:

1) annealing pretreatment of the titanium sheet: shearing to 25' 10 mm²The titanium substrate is alternately cleaned by acetone and ethanol for 5min each time, circulated for 3 times, cleaned by deionized water for 3 times, and then annealed at 450 ℃ in a muffle furnaceCleaning in the same way after being taken out for 1.5h, and airing at normal temperature for later use;

2) preparing 250mL of reaction precursor liquid, taking fluotitanic acid as a titanium source and a fluorine source, wherein the concentration of the fluotitanic acid is 0.885mM, the concentration of hydrochloric acid is 6.5mM, and the concentration of isopropanol is 33 mM;

3) simultaneously putting the precursor solution and the titanium sheet into a stainless steel high-pressure reaction kettle, carrying out hydrothermal reaction in an electrothermal blowing dry box at the reaction temperature and the reaction time of 160 ℃ and 2 hours respectively, carrying out ultrasonic cleaning on a sample taken out after water cooling in deionized water, and airing at normal temperature;

as can be seen from fig. 10, a titanium dioxide film with a flaky {001} crystal face exposed appears on the substrate, the surface appearance of the film is uniform, the film completely covers the surface of the substrate, and a layer of dense hydroxyapatite is formed on the surface of the titanium dioxide film after soaking for 24 hours by 1.5 times of SBF, and fig. 10 (a) is a microscopic appearance image with a scale of 500 nm; FIG. 10 (b) is a micrograph of a titanium sheet after soaking in a constant temperature incubator at 36.5 ℃ with 1.5 times SBF for 24 hours.

Example 15

The method for preparing the anatase titanium dioxide film with the exposed {001} crystal face in situ provided by the embodiment comprises the following steps:

1) annealing pretreatment of the titanium sheet: shearing to 25' 10 mm²The titanium substrate is alternately cleaned by acetone and ethanol for 5min each time, circulated for 3 times, cleaned by deionized water for 3 times, then annealed at 450 ℃ for 1.5h in a muffle furnace, cleaned in the same way after being taken out, and dried at normal temperature for later use;

2) preparing 250mL of reaction precursor liquid, taking fluotitanic acid as a titanium source and a fluorine source, wherein the concentration of the fluotitanic acid is 0.885mM, the concentration of hydrochloric acid is 26mM, and the concentration of isopropanol is 33 mM;

3) simultaneously putting the precursor solution and the titanium sheet into a stainless steel high-pressure reaction kettle, carrying out hydrothermal reaction in an electrothermal blowing dry box at the reaction temperature and the reaction time of 160 ℃ and 2 hours respectively, carrying out ultrasonic cleaning on a sample taken out after water cooling in deionized water, and airing at normal temperature;

as can be seen from fig. 11, a titanium dioxide film with exposed sheet {001} crystal face appears on the substrate, the surface appearance of the film is uniform, the film completely covers the surface of the substrate, and a layer of dense hydroxyapatite is formed on the surface of the titanium dioxide film after soaking for 24 hours by 1.5 times of SBF, and fig. 11 (a) is a microscopic appearance image with a scale of 500 nm; FIG. 11 (b) is a micrograph of a titanium sheet after soaking in a constant temperature incubator at 36.5 ℃ with 1.5 times SBF for 24 hours.

Example 16

The method for preparing the anatase titanium dioxide film with the exposed {001} crystal face in situ provided by the embodiment comprises the following steps:

1) annealing pretreatment of the titanium sheet: shearing to 25' 10 mm²The titanium substrate is alternately cleaned by acetone and ethanol for 5min each time, circulated for 3 times, cleaned by deionized water for 3 times, then annealed at 450 ℃ for 1.5h in a muffle furnace, cleaned in the same way after being taken out, and dried at normal temperature for later use;

(2) preparing 250mL of reaction precursor liquid, taking fluotitanic acid as a titanium source and a fluorine source, wherein the concentration of the fluotitanic acid is 0.885mM, the concentration of hydrochloric acid is 56mM, and the concentration of isopropanol is 33 mM;

(3) simultaneously putting the precursor solution and the titanium sheet into a stainless steel high-pressure reaction kettle, carrying out hydrothermal reaction in an electrothermal blowing dry box at the reaction temperature and the reaction time of 160 ℃ and 2 hours respectively, carrying out ultrasonic cleaning on a sample taken out after water cooling in deionized water, and airing at normal temperature;

as can be seen from fig. 12, a titanium dioxide film with a flaky {001} crystal face exposed appears on the substrate, the surface appearance of the film is uniform, the film completely covers the surface of the substrate, and a layer of dense hydroxyapatite is formed on the surface of the titanium dioxide film after soaking for 24 hours by 1.5 times of SBF, and fig. 12 (a) is a microscopic appearance image with a scale of 500 nm; FIG. 12 (b) is a micrograph of a titanium sheet after soaking in a constant temperature incubator at 36.5 ℃ with 1.5 times SBF for 24 hours.

Example 17

The method for preparing the anatase titanium dioxide film with the exposed {001} crystal face in situ provided by the embodiment comprises the following steps:

1) annealing pretreatment of the titanium sheet: shearing to 25' 10 mm²The titanium substrate is alternately cleaned by acetone and ethanol for 5min each time, circulated for 3 times, cleaned by deionized water for 3 times, then annealed at 450 ℃ for 1.5h in a muffle furnace, cleaned in the same way after being taken out, and dried at normal temperature for later use;

2) 250mL of reaction precursor solution is prepared, fluotitanic acid is used as a titanium source and a fluorine source, the concentration of the fluotitanic acid is 0.22125mM, the concentration of hydrochloric acid is 13mM, and the concentration of isopropanol is 33mM

3) Simultaneously putting the precursor solution and the titanium sheet into a stainless steel high-pressure reaction kettle, carrying out hydrothermal reaction in an electrothermal blowing dry box at the reaction temperature and the reaction time of 160 ℃ and 2 hours respectively, carrying out ultrasonic cleaning on a sample taken out after water cooling in deionized water, and airing at normal temperature;

as can be seen from fig. 13, a titanium dioxide film with exposed granular {001} crystal face appears on the substrate, the surface appearance of the film is uniform, the film completely covers the surface of the substrate, and a layer of dense hydroxyapatite is formed on the surface of the titanium dioxide film after soaking for 24 hours by 1.5 times of SBF, and fig. 13 (a) is a microscopic appearance image with a scale of 500 nm; FIG. 13 (b) is a micrograph of a titanium sheet after soaking in a constant temperature incubator at 36.5 ℃ with 1.5 times SBF for 24 hours.

Example 18

The method for preparing the anatase titanium dioxide film with the exposed {001} crystal face in situ provided by the embodiment comprises the following steps:

1) annealing pretreatment of the titanium sheet: shearing to 25' 10 mm²The titanium substrate is alternately cleaned by acetone and ethanol for 5min each time, circulated for 3 times, cleaned by deionized water for 3 times, then annealed at 450 ℃ for 1.5h in a muffle furnace, cleaned in the same way after being taken out, and dried at normal temperature for later use;

2) preparing 250mL of reaction precursor liquid, taking fluotitanic acid as a titanium source and a fluorine source, wherein the concentration of the fluotitanic acid is 0.4425mM, the concentration of hydrochloric acid is 13mM, and the concentration of isopropanol is 33 mM;

3) simultaneously putting the precursor solution and the titanium sheet into a stainless steel high-pressure reaction kettle, carrying out hydrothermal reaction in an electrothermal blowing dry box at the reaction temperature and the reaction time of 160 ℃ and 2 hours respectively, carrying out ultrasonic cleaning on a sample taken out after water cooling in deionized water, and airing at normal temperature;

as can be seen from fig. 14, a titanium dioxide film with exposed grain {001} crystal face appears on the substrate, the surface appearance of the film is uniform, the film completely covers the surface of the substrate, and a layer of dense hydroxyapatite is formed on the surface of the titanium dioxide film after soaking for 24 hours by 1.5 times of SBF, and fig. 14 (a) is a microscopic appearance image with a scale of 500 nm; FIG. 14 (b) is a micrograph of a titanium sheet after soaking in a constant temperature incubator at 36.5 ℃ with 1.5 times SBF for 24 hours.

Example 19

The method for preparing the anatase titanium dioxide film with the exposed {001} crystal face in situ provided by the embodiment comprises the following steps:

1) annealing pretreatment of the titanium sheet: shearing to 25' 10 mm²The titanium substrate is alternately cleaned by acetone and ethanol for 5min each time, circulated for 3 times, cleaned by deionized water for 3 times, then annealed at 450 ℃ for 1.5h in a muffle furnace, cleaned in the same way after being taken out, and dried at normal temperature for later use;

2) preparing 250mL of reaction precursor liquid, taking fluotitanic acid as a titanium source and a fluorine source, wherein the concentration of the fluotitanic acid is 0.885mM, the concentration of nitric acid is 13mM, and the concentration of isopropanol is 33 mM;

3) simultaneously putting the precursor solution and the titanium sheet into a stainless steel high-pressure reaction kettle, carrying out hydrothermal reaction in an electrothermal blowing dry box at the reaction temperature and the reaction time of 160 ℃ and 2 hours respectively, carrying out ultrasonic cleaning on a sample taken out after water cooling in deionized water, and airing at normal temperature;

the titanium dioxide film exposed by the flaky {001} crystal face appears on the substrate, the surface appearance of the film is uniform, the film completely covers the surface of the substrate, and a layer of compact hydroxyapatite is formed on the surface of the titanium dioxide film after the titanium dioxide film is soaked for 24 hours by 1.5 times of SBF.

Example 20

The method for preparing the anatase titanium dioxide film with the exposed {001} crystal face in situ provided by the embodiment comprises the following steps:

1) annealing pretreatment of the titanium sheet: shearing to 25' 10 mm²The titanium substrate of (a) is provided,cleaning with acetone and ethanol alternately for 5min each time, circulating for 3 times, cleaning with deionized water for 3 times, annealing the titanium sheet in a muffle furnace at 450 deg.C for 1.5h, cleaning in the same manner, and air drying at room temperature;

2) preparing 250mL of reaction precursor liquid, taking fluotitanic acid as a titanium source and a fluorine source, wherein the concentration of the fluotitanic acid is 0.885mM, the concentration of sulfuric acid is 6.5mM, and the concentration of isopropanol is 33 mM;

3) simultaneously putting the precursor solution and the titanium sheet into a stainless steel high-pressure reaction kettle, carrying out hydrothermal reaction in an electrothermal blowing dry box at the reaction temperature and the reaction time of 160 ℃ and 2 hours respectively, carrying out ultrasonic cleaning on a sample taken out after water cooling in deionized water, and airing at normal temperature;

the titanium dioxide film exposed to the {001} crystal face of the sheet appears on the substrate. The surface appearance of the film is uniform, the film completely covers the surface of the substrate, and a layer of compact hydroxyapatite is formed on the surface of the titanium dioxide film after the film is soaked for 24 hours by 1.5 times of SBF.

Example 21

The method for preparing the anatase titanium dioxide film with the exposed {001} crystal face in situ provided by the embodiment comprises the following steps:

1) annealing pretreatment of the titanium sheet: shearing to 25' 10 mm²The titanium substrate is alternately cleaned by acetone and ethanol for 5min each time, circulated for 3 times, cleaned by deionized water for 3 times, then annealed at 450 ℃ for 1.5h in a muffle furnace, cleaned in the same way after being taken out, and dried at normal temperature for later use;

2) preparing 250mL of reaction precursor liquid, taking ammonium fluotitanate as a titanium source and a fluorine source, wherein the concentration of the ammonium fluotitanate is 0.885mM, the concentration of hydrochloric acid is 13mM, and the concentration of isopropanol is 33 mM;

3) simultaneously putting the precursor solution and the titanium sheet into a stainless steel high-pressure reaction kettle, carrying out hydrothermal reaction in an electrothermal blowing dry box at the reaction temperature and the reaction time of 160 ℃ and 2 hours respectively, carrying out ultrasonic cleaning on a sample taken out after water cooling in deionized water, and airing at normal temperature;

the titanium dioxide film exposed to the {001} crystal face of the sheet appears on the substrate. The surface appearance of the film is uniform, the film completely covers the surface of the substrate, and a layer of compact hydroxyapatite is formed on the surface of the titanium dioxide film after the film is soaked for 24 hours by 1.5 times of SBF.

Example 22

The method for preparing the anatase titanium dioxide film with the exposed {001} crystal face in situ provided by the embodiment comprises the following steps:

1) annealing pretreatment of the titanium sheet: shearing to 25' 10 mm²The titanium substrate is alternately cleaned by acetone and ethanol for 5min each time, the cleaning is carried out for 3 times in a circulating way, then deionized water is used for cleaning for 3 times, then the titanium sheet is annealed at 500 ℃ in a muffle furnace for 2h, and is cleaned in the same way after being taken out and is dried at normal temperature for standby;

2) preparing 250mL of reaction precursor liquid, taking titanium tetrafluoride as a titanium source and a fluorine source, wherein the concentration of the titanium tetrafluoride is 0.885mM, the concentration of hydrochloric acid is 13mM, and the concentration of isopropanol is 33 mM;

3) simultaneously putting the precursor solution and the titanium sheet into a stainless steel high-pressure reaction kettle, carrying out hydrothermal reaction in an electrothermal blowing dry box at the reaction temperature and the reaction time of 160 ℃ and 2 hours respectively, carrying out ultrasonic cleaning on a sample taken out after water cooling in deionized water, and airing at normal temperature;

the titanium dioxide film exposed to the {001} crystal face of the sheet appears on the substrate. The surface appearance of the film is uniform, the film completely covers the surface of the substrate, and a layer of compact hydroxyapatite is formed on the surface of the titanium dioxide film after the film is soaked for 24 hours by 1.5 times of SBF.

Example 23

The method for preparing the anatase titanium dioxide film with the exposed {001} crystal face in situ provided by the embodiment comprises the following steps:

1) annealing pretreatment of the titanium sheet: shearing to 25' 10 mm²The titanium substrate is alternately cleaned by acetone and ethanol for 5min each time, circulated for 3 times, cleaned by deionized water for 3 times, then annealed at 450 ℃ for 1.5h in a muffle furnace, cleaned in the same way after being taken out, and dried at normal temperature for later use;

2) preparing 250mL of reaction precursor liquid, taking titanium trichloride as a titanium source and sodium fluoride as a fluorine source, wherein the concentration of the titanium trichloride is 0.885mM, the concentration of the sodium fluoride is 5.31mM, the concentration of hydrochloric acid is 13mM, and the concentration of isopropanol is 33 mM;

3) simultaneously putting the precursor solution and the titanium sheet into a stainless steel high-pressure reaction kettle, carrying out hydrothermal reaction in an electrothermal blowing dry box at the reaction temperature and the reaction time of 160 ℃ and 2 hours respectively, carrying out ultrasonic cleaning on a sample taken out after water cooling in deionized water, and airing at normal temperature;

the titanium dioxide film exposed to the {001} crystal face of the sheet appears on the substrate. The surface appearance of the film is uniform, the film completely covers the surface of the substrate, and a layer of compact hydroxyapatite is formed on the surface of the titanium dioxide film after the film is soaked for 24 hours by 1.5 times of SBF.

Example 24

The method for preparing the anatase titanium dioxide film with the exposed {001} crystal face in situ provided by the embodiment comprises the following steps:

1) annealing pretreatment of the titanium sheet: shearing to 25' 10 mm²The titanium substrate is alternately cleaned by acetone and ethanol for 5min each time, circulated for 3 times, cleaned by deionized water for 3 times, then annealed at 450 ℃ for 1.5h in a muffle furnace, cleaned in the same way after being taken out, and dried at normal temperature for later use;

2) preparing 250mL of reaction precursor liquid, taking fluotitanic acid as a titanium source and a fluorine source, wherein the concentration of the fluotitanic acid is 0.885mM, the concentration of the oxalic acid is 6.5mM, and the concentration of the isopropanol is 33 mM;

3) simultaneously putting the precursor solution and the titanium sheet into a stainless steel high-pressure reaction kettle, carrying out hydrothermal reaction in an electrothermal blowing dry box at the reaction temperature and the reaction time of 160 ℃ and 2 hours respectively, carrying out ultrasonic cleaning on a sample taken out after water cooling in deionized water, and airing at normal temperature;

the titanium dioxide film exposed to the {001} crystal face of the sheet appears on the substrate. The surface appearance of the film is uniform, the film completely covers the surface of the substrate, and a layer of compact hydroxyapatite is formed on the surface of the titanium dioxide film after the film is soaked for 24 hours by 1.5 times of SBF.

Example 25

The method for preparing the anatase titanium dioxide film with the exposed {001} crystal face in situ provided by the embodiment comprises the following steps:

1) annealing pretreatment of the titanium sheet: shearing to 25' 10 mm²The titanium substrate is alternately cleaned by acetone and ethanol for 5min each time, circulated for 3 times, cleaned by deionized water for 3 times, and then annealed at 700 ℃ for 1h in a muffle furnace, cleaned in the same way after being taken out, and dried at normal temperature for later use;

2) preparing 250mL of reaction precursor liquid, taking fluotitanic acid as a titanium source and a fluorine source, wherein the concentration of the fluotitanic acid is 0.885mM, the concentration of acetic acid is 13mM, and the concentration of isopropanol is 33 mM;

3) simultaneously putting the precursor solution and the titanium sheet into a stainless steel high-pressure reaction kettle, carrying out hydrothermal reaction in an electrothermal blowing dry box at the reaction temperature and the reaction time of 160 ℃ and 2 hours respectively, carrying out ultrasonic cleaning on a sample taken out after water cooling in deionized water, and airing at normal temperature;

the titanium dioxide film exposed to the {001} crystal face of the sheet appears on the substrate. The surface appearance of the film is uniform, the film completely covers the surface of the substrate, and a layer of compact hydroxyapatite is formed on the surface of the titanium dioxide film after the film is soaked for 24 hours by 1.5 times of SBF.

Example 26

The method for preparing the anatase titanium dioxide film with the exposed {001} crystal face in situ provided by the embodiment comprises the following steps:

1) annealing pretreatment of the titanium sheet: shearing to 25' 10 mm²The titanium substrate is alternately cleaned by acetone and ethanol for 5min each time, the cleaning is carried out for 3 times in a circulating way, then deionized water is used for cleaning for 3 times, and then the titanium sheet is annealed at 200 ℃ in a muffle furnace for 2h, cleaned in the same way after being taken out and dried at normal temperature for standby;

2) preparing 250mL of reaction precursor solution, taking titanium sulfate as a titanium source, sodium fluoride as a fluorine source, wherein the concentration of the titanium sulfate is 0.4425mM, the concentration of the sodium fluoride is 5.31mM, the concentration of sulfuric acid is 6.5mM, and the concentration of isopropanol is 33 mM;

3) simultaneously putting the precursor solution and the titanium sheet into a stainless steel high-pressure reaction kettle, carrying out hydrothermal reaction in an electrothermal blowing dry box at the reaction temperature of 180 ℃ for 2 hours, carrying out ultrasonic cleaning on a sample taken out after water cooling in deionized water, and airing at normal temperature;

the titanium dioxide film exposed by the flaky {001} crystal face appears on the substrate, the surface appearance of the film is uniform, the film completely covers the surface of the substrate, and a layer of compact hydroxyapatite is formed on the surface of the titanium dioxide film after the titanium dioxide film is soaked for 24 hours by 1.5 times of SBF.

Example 27

The method for preparing the anatase titanium dioxide film with the exposed {001} crystal face in situ provided by the embodiment comprises the following steps:

1) annealing pretreatment of the titanium sheet: cut 25X 10 mm²The titanium substrate is alternately cleaned by acetone and ethanol for 5min each time, circulated for 3 times, cleaned by deionized water for 3 times, then annealed at 450 ℃ for 1.5h in a muffle furnace, cleaned in the same way after being taken out, and dried at normal temperature for later use;

2) preparing 250mL of reaction precursor solution, taking titanium sulfate as a titanium source, sodium fluoride as a fluorine source, wherein the concentration of the titanium sulfate is 0.4425mM, the concentration of the sodium fluoride is 1.77mM, the concentration of sulfuric acid is 6.5mM, and the concentration of isopropanol is 33 mM;

3) simultaneously putting the precursor solution and the titanium sheet into a stainless steel high-pressure reaction kettle, carrying out hydrothermal reaction in an electrothermal blowing dry box at the reaction temperature and the reaction time of 160 ℃ and 2 hours respectively, carrying out ultrasonic cleaning on a sample taken out after water cooling in deionized water, and airing at normal temperature;

the titanium dioxide film exposed by the flaky {001} crystal face appears on the substrate, the surface appearance of the film is uniform, the film completely covers the surface of the substrate, and a layer of compact hydroxyapatite is formed on the surface of the titanium dioxide film after the titanium dioxide film is soaked for 24 hours by 1.5 times of SBF.

Example 28

The method for preparing the anatase titanium dioxide film with the exposed {001} crystal face in situ provided by the embodiment comprises the following steps:

1) annealing pretreatment of the titanium sheet: shearing a 25' 10 mm2 titanium substrate, alternately cleaning with acetone and ethanol for 5min each time, circulating for 3 times, cleaning with deionized water for 3 times, then, carrying out annealing treatment on the titanium sheet in a muffle furnace at 450 ℃ for 1.5h, cleaning in the same way after taking out, and airing at normal temperature for later use;

2) preparing 250mL of reaction precursor solution, taking titanium sulfate as a titanium source, sodium fluoride as a fluorine source, wherein the concentration of the titanium sulfate is 0.4425mM, the concentration of the sodium fluoride is 8.85mM, the concentration of sulfuric acid is 6.5mM, and the concentration of isopropanol is 33 mM;

3) simultaneously putting the precursor solution and the titanium sheet into a stainless steel high-pressure reaction kettle, carrying out hydrothermal reaction in an electrothermal blowing dry box at the reaction temperature and the reaction time of 160 ℃ and 2 hours respectively, carrying out ultrasonic cleaning on a sample taken out after water cooling in deionized water, and airing at normal temperature;

the titanium dioxide film exposed by the flaky {001} crystal face appears on the substrate, the surface appearance of the film is uniform, the film completely covers the surface of the substrate, and a layer of compact hydroxyapatite is formed on the surface of the titanium dioxide film after the titanium dioxide film is soaked for 24 hours by 1.5 times of SBF.

Example 29

The method for preparing the anatase titanium dioxide film with the exposed {001} crystal face in situ provided by the embodiment comprises the following steps:

1) pretreatment of the titanium alloy sheet: 3D printing a titanium alloy substrate with the diameter of 9mm, alternately cleaning the titanium alloy substrate with acetone and ethanol for 5min each time, circulating for 3 times, cleaning with deionized water for 3 times, and airing at normal temperature for later use;

2) preparing 250mL of reaction precursor liquid, taking fluotitanic acid as a titanium source and a fluorine source, wherein the concentration of the fluotitanic acid is 0.885mM, the concentration of hydrochloric acid is 13mM, the concentration of isopropanol is 33mM, and the concentration of hydrogen peroxide is 12.98 mM;

3) simultaneously putting the precursor solution and the titanium alloy sheet into a stainless steel high-pressure reaction kettle, carrying out hydrothermal reaction in an electrothermal blowing dry box at the reaction temperature and the reaction time of 160 ℃ and 2 hours respectively, carrying out ultrasonic cleaning on a sample taken out after water cooling in deionized water, and airing at normal temperature;

as can be seen from fig. 15, a titanium dioxide film with a flaky {001} crystal face exposed appears on the substrate, the surface appearance of the film is uniform, the film completely covers the surface of the substrate, and a layer of dense hydroxyapatite is formed on the surface of the titanium dioxide film after soaking for 24 hours by 1.5 times of SBF, and fig. 15 (a) is a microscopic appearance image with a scale of 500 nm; FIG. 15 (b) is a micrograph of the titanium alloy sheet after being immersed in a constant temperature incubator at 36.5 ℃ with 1.5 times of SBF for 24 hours.

All patents and publications mentioned in the specification of the invention are indicative of the techniques disclosed in the art to which this invention pertains and are intended to be applicable. All patents and publications cited herein are hereby incorporated by reference to the same extent as if each individual publication was specifically and individually indicated to be incorporated by reference. The invention described herein may be practiced in the absence of any element or elements, limitation or limitations, which limitation or limitations is not specifically disclosed herein. For example, the terms "comprising", "consisting essentially of … …" and "consisting of … …" in each instance herein may be substituted for the remaining 2 terms of either. The terms and expressions which have been employed herein are used as terms of description and not of limitation, and there is no intention in the use of such terms and expressions of excluding any equivalents of the features shown and described, but it is recognized that various modifications and changes may be made within the scope of the invention and the claims which follow. It is to be understood that the embodiments described herein are preferred embodiments and features and that modifications and variations may be made by one skilled in the art in light of the teachings of this disclosure, and are to be considered within the purview and scope of this invention and the scope of the appended claims and their equivalents.