阅读说明：本技术 一种于钛或钛合金基底表面生长二氧化钛纳米颗粒的方法 (Method for growing titanium dioxide nanoparticles on surface of titanium or titanium alloy substrate ) 是由 赵文杰 顾青山 王艳君 吴文婷 *** 薛群基 于 2019-03-04 设计创作，主要内容包括：本发明公开了一种于钛或钛合金基底表面生长二氧化钛纳米颗粒的方法,包括：以水热溶液对钛或钛合金基底表面进行水热处理,从而在所述基底表面生长形成二氧化钛纳米颗粒,所述水热溶液采用含氯离子和/或氟离子的盐溶液。本发明可以在钛或钛合金基底表面获得分布均匀致密且大小可控的纳米颗粒。且工艺简便、处理温度较低、成本低廉、清洁环保、实用性强、操作性强,可用于调控钛表面不同尺度的纳米颗粒,且可用于钛及钛合金基底表面的改性,为钛表面处理提供了一个新的方法。(The invention discloses a method for growing titanium dioxide nanoparticles on the surface of a titanium or titanium alloy substrate, which comprises the following steps: carrying out hydrothermal treatment on the surface of a titanium or titanium alloy substrate by using a hydrothermal solution, so as to grow and form titanium dioxide nanoparticles on the surface of the substrate, wherein the hydrothermal solution adopts a salt solution containing chloride ions and/or fluoride ions. The invention can obtain nano particles which are uniformly and compactly distributed and have controllable sizes on the surface of the titanium or titanium alloy substrate. The method has the advantages of simple process, low treatment temperature, low cost, cleanness, environmental protection, strong practicability and strong operability, can be used for regulating and controlling the nano particles with different scales on the surface of the titanium, can be used for modifying the surface of the titanium and titanium alloy substrate, and provides a new method for treating the surface of the titanium.)

1. A method of growing titanium dioxide nanoparticles on a surface of a titanium or titanium alloy substrate, comprising: carrying out hydrothermal treatment on the surface of a titanium or titanium alloy substrate by using a hydrothermal solution, so as to grow and form titanium dioxide nanoparticles on the surface of the substrate, wherein the hydrothermal solution adopts a salt solution containing chloride ions and/or fluoride ions.

2. The method of claim 1, further comprising etching the surface of the substrate with a solution of hydrogen peroxide and an acid to form a layer of titania nanogel on the surface of the substrate, followed by the hydrothermal treatment of the titania nanogel layer; preferably, the acid comprises hydrochloric acid and/or nitric acid.

3. The method of growing titanium dioxide nanoparticles on a surface of a titanium or titanium alloy substrate of claim 2, further comprising: etching the surface of the substrate by adopting a mixed solution of 27-30% of hydrogen peroxide and 0.1M hydrochloric acid, wherein the etching temperature is 60-150 ℃, and the etching time is 30-90 min, so that a titanium dioxide nano gel layer is formed on the surface of the substrate; and/or the thickness of the titanium dioxide gel layer is 200-500 nm.

4. A method of growing titanium dioxide nanoparticles on a surface of a titanium or titanium alloy substrate as claimed in any one of claims 1 to 3 further comprising: polishing and/or sandblasting and/or cleaning the substrate surface, followed by said hydrothermal treatment of the substrate surface;

the polishing treatment comprises the following steps: polishing the surface of the substrate by using 150-2000-mesh sand paper;

the sand blasting treatment comprises the following steps: hard particles are adopted as sand blasting particles, the sand blasting time is 10-60 s, and the sand blasting particles comprise Al₂O₃、SiC、SiO₂And ZrO₂Any one or a combination of two or more of them;

the cleaning treatment comprises the following steps: and ultrasonically washing the surface of the substrate for 10-20 minutes by using absolute ethyl alcohol and deionized water.

5. The method of growing titanium dioxide nanoparticles on the surface of a titanium or titanium alloy substrate according to claim 1 or 2, wherein said hydrothermal treatment comprises: and in a hydrothermal kettle, contacting the surface of the substrate with a hydrothermal solution to carry out hydrothermal reaction, wherein the reaction temperature is 100-300 ℃, the reaction time is 0.5-24 h, and the pressure is 0-20 Mpa.

6. The method of growing titanium dioxide nanoparticles on a surface of a titanium or titanium alloy substrate of claim 5, wherein: the concentration of the hydrothermal solution is 0.1-10 mol/L; and/or the lining of the hydrothermal kettle is a polytetrafluoroethylene lining; and/or in the hydrothermal treatment, the volume filling rate of the hydrothermal solution in the lining of the hydrothermal kettle is 50-70%.

7. The method of growing titanium dioxide nanoparticles on a surface of a titanium or titanium alloy substrate according to claim 1 or 2, further comprising: after the hydrothermal treatment is finished, carrying out heat treatment on the obtained substrate with the titanium dioxide nano particles growing on the surface at the temperature of 80-1000 ℃ to form nano titanium dioxide particles with different crystal forms.

8. The method of growing titanium dioxide nanoparticles on a surface of a titanium or titanium alloy substrate of claim 1, wherein: the particle size of the titanium dioxide nano particles is 20-600 nm; the crystal form of the titanium dioxide nano particles is anatase type and/or rutile type.

9. The method of growing titanium dioxide nanoparticles on a surface of a titanium or titanium alloy substrate of claim 1, further comprising: and after the hydrothermal treatment is finished, cleaning and drying the obtained substrate with the titanium dioxide nano particles growing on the surface.

10. The method of growing titanium dioxide nanoparticles on a surface of a titanium or titanium alloy substrate of claim 1, wherein: the titanium dioxide nanoparticles are uniformly and densely distributed on the surface of the substrate to form a dense film-like structure.

Technical Field

The invention relates to the technical field of nano materials, in particular to a titanium or titanium alloy substrate with titanium dioxide nano particles growing on the surface and a method for growing the titanium dioxide nano particles on the surface of the titanium or titanium alloy substrate.

Background

According to the hydrothermal method, a specific solution is adopted as a reaction medium in a specific container, and a high-temperature and high-pressure reaction environment is created through heating, so that some insoluble or slightly soluble substances are promoted to be dissolved and recrystallized. The surface microstructure constructed by a hydrothermal method is complex and fine, has various shapes and is generally in a nanoscale, and the surface nanoparticles with controllable scale can be obtained by regulating and controlling experimental parameters such as reaction temperature, time, pressure, reaction medium and the like.

The titanium dioxide nano-particles are a high-efficiency, nontoxic and stable photocatalytic material, and have important and wide application in the field of photocatalysis. At present, people prepare titanium dioxide nano powder by a multi-purpose sol-gel method, but the titanium dioxide nano powder has the defects of small size, easy agglomeration, difficult sedimentation, difficult recovery and the like, so that the repeated recovery and utilization of the catalyst in practical application are not facilitated.

Disclosure of Invention

The main object of the present invention is to provide a method for growing titanium dioxide nanoparticles on the surface of a titanium or titanium alloy substrate, thereby overcoming the disadvantages of the prior art.

In order to achieve the purpose, the invention adopts the following technical scheme:

a method of growing titanium dioxide nanoparticles on a surface of a titanium or titanium alloy substrate, comprising: carrying out hydrothermal treatment on the surface of a titanium or titanium alloy substrate by using a hydrothermal solution, so as to grow and form titanium dioxide nanoparticles on the surface of the substrate, wherein the hydrothermal solution adopts a salt solution containing chloride ions and/or fluoride ions.

In some embodiments, the method further comprises etching the substrate surface with a mixed solution of hydrogen peroxide and an acid to form a titania nanogel layer on the substrate surface, and then performing the hydrothermal treatment on the titania nanogel layer.

Compared with the prior art, the invention has the beneficial effects that:

(1) according to the method for growing the titanium dioxide nanoparticles on the surface of the titanium or titanium alloy substrate, provided by the embodiment of the invention, a layer of titanium dioxide gel layer can be obtained by etching a mixed solution of hydrogen peroxide and hydrochloric acid, and then the titanium or titanium alloy substrate is subjected to hydrothermal treatment, so that the nanoparticles which are uniformly and compactly distributed and have controllable sizes can be obtained on the surface of the titanium or titanium alloy substrate.

(2) The method has the advantages of simple and convenient process, lower treatment temperature, low cost, cleanness, environmental protection, strong practicability and strong operability, can be used for regulating and controlling the nano particles with different scales on the surface of the titanium, can be used for modifying the surface of the titanium and the titanium alloy substrate, and provides a new method for treating the surface of the titanium.

Drawings

In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments described in the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.

FIG. 1 is a surface topography of a titania nanogel layer prepared by hydrogen peroxide and hydrochloric acid treatment in example 1 of the invention;

FIG. 2 is a surface topography diagram of a titanium dioxide nano-film prepared by hydrothermal treatment of a sodium chloride solution for 1 hour in example 2 of the present invention;

FIG. 3 is a surface topography diagram of a titanium dioxide nano-film prepared by hydrothermal reaction of a sodium chloride solution for 5 hours in example 3 of the present invention;

FIG. 4 is a surface topography of titanium dioxide nano-film prepared by sodium chloride solution hydrothermal for 10 hours in example 4 of the present invention;

FIG. 5 is a surface topography of titanium dioxide nano-film prepared by hydrothermal treatment of sodium fluoride solution for 5 hours in example 5 of the present invention;

FIG. 6 is a surface topography of titanium dioxide nano-film prepared by ammonium fluoride solution hydrothermal for 5 hours in example 6 of the present invention

FIG. 7 is a surface topography diagram of titanium dioxide nano-film prepared by sodium chloride solution hydrothermal for 8 hours in example 7 of the present invention

FIG. 8 is a surface topography diagram of a titanium dioxide nano-film prepared by hydrothermal reaction of a sodium chloride solution for 8 hours in example 8 of the present invention.

FIG. 9 is a surface topography diagram of a titanium dioxide nano-film prepared by sodium chloride solution hydrothermal for 2 hours in example 9 of the present invention.

Detailed Description

In view of the deficiencies in the prior art, the inventors of the present invention have made extensive studies and extensive practices to propose the technical solution of the present invention, and further explain the technical solution, the implementation process and the principle thereof, etc.

In one aspect of the present invention, a method for growing titanium dioxide nanoparticles on a surface of a titanium or titanium alloy substrate comprises: carrying out hydrothermal treatment on the surface of a titanium or titanium alloy substrate by using a hydrothermal solution, so as to grow and form titanium dioxide nanoparticles on the surface of the substrate, wherein the hydrothermal solution adopts a salt solution containing chloride ions and/or fluoride ions.

In some embodiments, the method further comprises etching the substrate surface with a mixed solution of hydrogen peroxide and an acid to form a titania nanogel layer on the substrate surface, and then subjecting the titania nanogel layer to the hydrothermal treatment.

Further, the acid includes hydrochloric acid and/or nitric acid.

In some preferred embodiments, the method further comprises: and etching the surface of the substrate by adopting a mixed solution of 27-30% of hydrogen peroxide and 0.1M hydrochloric acid, wherein the etching temperature is 60-150 ℃, and the etching time is 30-90 min, so that a titanium dioxide nano gel layer is formed on the surface of the substrate.

In some preferred embodiments, the thickness of the titanium dioxide gel layer is 200 to 500 nm.

In some embodiments, further comprising: polishing and/or sandblasting and/or cleaning the substrate surface, followed by said hydrothermal treatment of the substrate surface;

the polishing treatment comprises the following steps: polishing the surface of the substrate by using 150-2000-mesh sand paper;

the sand blasting treatment comprises the following steps: hard particles are adopted as sand blasting particles, the sand blasting time is 10-60 s, and the sand blasting particles comprise Al₂O₃、SiC、SiO₂And ZrO₂Any one or a combination of two or more of them;

the cleaning treatment comprises the following steps: and ultrasonically washing the surface of the substrate for 10-20 minutes by using absolute ethyl alcohol and deionized water.

In some embodiments, the hydrothermal treatment comprises: and in a hydrothermal kettle, contacting the surface of the substrate with a hydrothermal solution to carry out hydrothermal reaction, wherein the reaction temperature is 100-300 ℃, the reaction time is 0.5-24 h, and the pressure is 0-20 Mpa.

In some more preferred embodiments, the concentration of the hydrothermal solution is 0.1-10 mol/L.

In some more preferred embodiments, the hydrothermal kettle liner is a polytetrafluoroethylene liner.

In some more preferred embodiments, in the hydrothermal treatment, the volume filling rate of the hydrothermal solution in the hydrothermal kettle lining is 50-70%.

In some embodiments, further comprising: and after the hydrothermal treatment is finished, carrying out heat treatment on the obtained substrate with the titanium dioxide nanoparticles growing on the surface at the temperature of 80-1000 ℃.

In some embodiments, the titanium or titanium alloy substrate is subjected to a hydrothermal treatment, thereby forming titanium dioxide nanoparticles with different sizes on the surface of the titanium or titanium alloy substrate, wherein the particle size of the titanium dioxide nanoparticles is 20-600 nm.

In some embodiments, the titanium dioxide nanoparticles are anatase and/or rutile.

In some embodiments, further comprising: after the hydrothermal treatment is finished, cleaning and drying the obtained substrate with the titanium dioxide nanoparticles growing on the surface, so that the titanium dioxide nanoparticles are uniformly and densely distributed on the surface of the substrate to form a compact film-shaped structure.

In some embodiments, the titanium dioxide nanoparticles are uniformly densely distributed on the substrate surface to form a dense film-like structure.

In some embodiments, a method of growing titanium dioxide nanoparticles on a surface of a titanium or titanium alloy substrate comprises:

(1) providing a pure titanium or titanium alloy substrate; performing pretreatment, then putting pure titanium or titanium alloy into mixed solution of 20ml of 27-30% hydrogen peroxide and 0.1M diluted hydrochloric acid, and etching at the temperature of 60-150 ℃ for 30-90 min to obtain a titanium dioxide gel layer, wherein the thickness of the nano gel layer is 200-500 nm;

(2) carrying out heat treatment on the titanium dioxide gel layer in the step (1), then soaking the titanium dioxide gel layer into a salt solution containing chloride ions and/or fluoride ions with the concentration of 0.1-10 mol/L, and treating by adopting a hydrothermal method, wherein the filling rate of the salt solution in the lining of the hydrothermal kettle is 50-70%; the hydrothermal temperature is 100-300 ℃, the hydrothermal time is 0.5-24 h, and the hydrothermal pressure is 0-20 Mpa; obtaining titanium dioxide crystal grains after hydrothermal treatment, wherein the grain size is 20-600 nm;

(3) and (3) cleaning and drying the sample obtained by the hydrothermal treatment in the step (2), then carrying out the thermal treatment at 80-1000 ℃, and cooling to obtain the titanium dioxide nano-particles growing on the surface of the titanium or titanium alloy substrate.

According to the invention, titanium dioxide nanoparticles are grown in situ on the surface of the titanium or titanium alloy substrate by a hydrothermal method, and the problems of small and easy-to-agglomerate titanium dioxide nanopowder, difficult sedimentation, difficult recovery and the like can be effectively solved by preparing the in-situ supported titanium dioxide film, so that the repeated recovery and utilization of the catalyst in practical application are facilitated.

The method utilizes the mixed solution of hydrogen peroxide and hydrochloric acid to preliminarily etch the surface of the titanium or titanium alloy substrate, so that a titanium dioxide nano gel layer is formed on the surface of the titanium or titanium alloy substrate, and the compact titanium dioxide nano particles can be obtained through subsequent hydrothermal treatment. And then treating the titanium or titanium alloy substrate by a hydrothermal method, wherein the hydrothermal solution is a salt solution containing chloride ions and/or fluoride ions, and the surface nano-particles with different shapes and sizes can be obtained by regulating and controlling experimental parameters such as hydrothermal reaction temperature, time, pressure, reaction medium and the like. The size of the nano particles is regulated to be beneficial to optimizing the nano particles with the optimal photocatalytic performance.

The technical solutions of the present invention will be described in further detail with reference to several preferred embodiments, and it should be apparent that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention. The test methods in the following examples, which are not specified under specific conditions, are generally carried out under conventional conditions.