CN111647880B - Method for growing titanium dioxide nanoparticles on surface of titanium or titanium alloy substrate - Google Patents
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Abstract
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 with uniform and compact distribution and controllable size 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.
Description
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 of titanium dioxide nano-film prepared by hydrothermal reaction of sodium chloride solution for 5 hours in example 3 according to 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 Al 2 O 3 、SiC、SiO 2 And ZrO 2 Any 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, the obtained substrate with the titanium dioxide nano particles growing on the surface is cleaned and dried, so that the titanium dioxide nano particles are uniformly and densely distributed on the surface of the substrate to form a compact film 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 nano particles with the optimal photocatalytic performance are preferably selected through the regulation and control of the size of the nano particles.
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.
Example 1
Adopting hydrogen peroxide and hydrochloric acid for treatment, preparing titanium dioxide nano gel layer on the surface of pure titanium
Pure titanium with the size of 25 multiplied by 3mm is taken as a matrix, SiC sand paper with the size of 400 meshes, 800 meshes, 1200 meshes and 2000 meshes is adopted to polish the matrix, and then the matrix is ultrasonically cleaned in absolute ethyl alcohol and deionized water for 20min respectively to remove oil stains.
Configuration 30% H 2 O 2 And 30ml (15 ml each) of a mixed solution of 0.1M HCl, putting the titanium substrate into the mixed solution, transferring the titanium substrate into an oven at 80 ℃, keeping the temperature for 40min, taking out the titanium substrate, and washing the titanium substrate with deionized water. And then putting the cleaned sample into an oven at 150 ℃, and preserving the heat for 1 h. As shown in fig. 1, pure titanium is etched by hydrogen peroxide and hydrochloric acid to form a porous spongy surface structure with a depth of about 200 nm.
Example 2
Preparing titanium dioxide nano film by treating pure titanium surface with sodium chloride solution hydrothermal for 1 hour
The steps of preparing the titanium dioxide nano gel layer on the surface of pure titanium in the embodiment are shown in the embodiment 1, the appearance is shown in fig. 1, and the specific preparation steps are as follows:
pure titanium with the size of 25 multiplied by 3mm is taken as a matrix, SiC sand paper with the size of 400 meshes, 800 meshes, 1200 meshes and 2000 meshes is adopted to polish the matrix, and then the matrix is ultrasonically cleaned in absolute ethyl alcohol and deionized water for 20min respectively to remove oil stains.
Configuration 30% H 2 O 2 And 30ml (15 ml each) of a mixed solution of 0.1M HCl, putting the titanium substrate into the mixed solution, transferring the titanium substrate into an oven at 80 ℃, keeping the temperature for 40min, taking out the titanium substrate, and washing the titanium substrate with deionized water. And then putting the cleaned sample into an oven at 150 ℃ and preserving the temperature for 1 h.
Preparing 5% sodium chloride solution, adding the sodium chloride solution into a hydrothermal kettle with a polytetrafluoroethylene lining, filling the hydrothermal kettle with the sodium chloride solution at a filling rate of 50%, and putting a sample into the hydrothermal kettle to perform hydrothermal treatment at 200 ℃ for 1 hour. And after the hydrothermal reaction is finished, taking out the sample, washing the sample with deionized water, and drying the sample. As shown in FIG. 2, after hydrothermal treatment, the original network-like coarse structure begins to dissolve, and particles of 100 to 200nm are formed.
Example 3
Preparing titanium dioxide nano-film by treating pure titanium surface with sodium chloride solution hydrothermal for 5 hours
The steps of preparing the titanium dioxide nano gel layer on the surface of pure titanium in the embodiment are shown in the embodiment 1, the appearance is shown in fig. 1, and the specific preparation steps are as follows:
pure titanium with the size of 25 multiplied by 3mm is taken as a matrix, SiC sand paper with the size of 400 meshes, 800 meshes, 1200 meshes and 2000 meshes is adopted to polish the matrix, and then the matrix is ultrasonically cleaned in absolute ethyl alcohol and deionized water for 20min respectively to remove oil stains.
Configuration 30% H 2 O 2 And 30ml (15 ml each) of a mixed solution of 0.1M HCl, putting the titanium substrate into the mixed solution, transferring the titanium substrate into an oven at 80 ℃, keeping the temperature for 40min, taking out the titanium substrate, and washing the titanium substrate with deionized water. And then putting the cleaned sample into an oven at 150 ℃ and preserving the temperature for 1 h.
Preparing 5% sodium chloride solution, adding the sodium chloride solution into a hydrothermal kettle with a polytetrafluoroethylene lining, filling the hydrothermal kettle with the sodium chloride solution at a filling rate of 50%, and putting a sample into the hydrothermal kettle to perform hydrothermal reaction at 200 ℃ for 5 hours. And after the hydrothermal reaction is finished, taking out the sample, washing the sample with deionized water, and drying the sample. As shown in FIG. 3, after hydrothermal treatment, the original network-like coarse structure is completely dissolved, forming small particles of about 50nm and long particles of 100-200 nm.
Example 4
Preparing titanium dioxide nano-film by treating pure titanium surface with sodium chloride solution hydrothermal for 10 hours
The steps of preparing the titanium dioxide nano gel layer on the surface of pure titanium in the embodiment are shown in the embodiment 1, the appearance is shown in fig. 1, and the specific preparation steps are as follows:
pure titanium with the size of 25 multiplied by 3mm is taken as a matrix, SiC sand paper with the size of 400 meshes, 800 meshes, 1200 meshes and 2000 meshes is adopted to polish the matrix, and then the matrix is ultrasonically cleaned in absolute ethyl alcohol and deionized water for 20min respectively to remove oil stains.
Configuration 30% H 2 O 2 And 30ml (15 ml each) of a mixed solution of 0.1M HCl, putting the titanium substrate into the mixed solution, transferring the titanium substrate into an oven at 80 ℃, keeping the temperature for 40min, taking out the titanium substrate, and washing the titanium substrate with deionized water. And then putting the cleaned sample into an oven at 150 ℃, and preserving the heat for 1 h.
Preparing 5% sodium chloride solution, adding the sodium chloride solution into a hydrothermal kettle with a polytetrafluoroethylene lining, filling the hydrothermal kettle with the sodium chloride solution at a filling rate of 50%, and then heating the hydrothermal kettle at 200 ℃ for 10 hours. And after the hydrothermal reaction is finished, taking out the sample, washing the sample with deionized water, and drying the sample. As shown in FIG. 4, after hydrothermal treatment, the original network-like coarse structure is completely dissolved, and regular diamond-shaped particles of about 30-50 nm are formed.
Example 5
Preparing titanium dioxide nano film by treating pure titanium surface with sodium fluoride solution hydrothermal for 5 hours
The specific preparation steps for preparing titanium dioxide nanoparticles on the surface of pure titanium in the embodiment are as follows:
pure titanium with the size of 25 multiplied by 3mm is taken as a matrix, SiC sand paper with the size of 400 meshes, 800 meshes, 1200 meshes and 2000 meshes is adopted to polish the matrix, and then the matrix is ultrasonically cleaned in absolute ethyl alcohol and deionized water for 20min respectively to remove oil stains.
Preparing 0.14M sodium fluoride solution, adding the solution into a hydrothermal kettle with a polytetrafluoroethylene lining, filling the hydrothermal kettle with the solution with the filling rate of 50 percent, and putting a sample into the hydrothermal kettle to perform hydrothermal reaction for 5 hours at 200 ℃. And after the hydrothermal reaction is finished, taking out the sample, washing the sample with deionized water, and drying the sample. As shown in FIG. 5, after hydrothermal treatment, a layer of diamond grains with different sizes is formed on the surface of the titanium substrate, the small size of the diamond grains is 30-50 nm, and large grains with the size of 100-400 nm are distributed above the small diamond grains.
Example 6
Preparing titanium dioxide nano film by treating pure titanium surface with ammonium fluoride solution hydrothermal for 5 hours
The specific preparation steps for preparing titanium dioxide nanoparticles on the surface of pure titanium in the embodiment are as follows:
pure titanium with the size of 25 multiplied by 3mm is taken as a matrix, SiC sand paper with the size of 400 meshes, 800 meshes, 1200 meshes and 2000 meshes is adopted to polish the matrix, and then the matrix is ultrasonically cleaned in absolute ethyl alcohol and deionized water for 20min respectively to remove oil stains.
Preparing 0.14M ammonium fluoride solution, adding the solution into a hydrothermal kettle with a polytetrafluoroethylene lining, filling the hydrothermal kettle with the solution at a filling rate of 50%, and putting a sample into the hydrothermal kettle to perform hydrothermal reaction at 200 ℃ for 5 hours. And after the hydrothermal reaction is finished, taking out the sample, washing the sample with deionized water, and drying the sample. As shown in FIG. 6, after hydrothermal treatment, a layer of rhombic grains with different sizes is formed on the surface of the titanium substrate, the grains with different sizes are closely arranged, the grains with small sizes are 30-50 nm, and large grains with sizes of 100-600 nm are distributed beside the small rhombic grains.
Example 7
Titanium dioxide nano-film prepared by adopting sodium chloride solution to carry out hydrothermal treatment on TC4 titanium alloy surface for 8 hours
The specific preparation steps for preparing titanium dioxide nanoparticles on the surface of the TC4 titanium alloy in the embodiment are as follows:
the method comprises the steps of polishing a TC4 titanium alloy with the thickness of 25 multiplied by 3mm serving as a matrix by using SiC sand paper with the sizes of 400 meshes, 800 meshes, 1200 meshes and 2000 meshes, and then ultrasonically cleaning the polished titanium alloy in absolute ethyl alcohol and deionized water for 20min respectively to remove oil stains.
Preparing 5% sodium chloride solution, adding the sodium chloride solution into a high-pressure hydrothermal kettle with the volume filling rate of 50%, setting the pressure of the hydrothermal kettle to be 5MP after a sample is placed in the hydrothermal kettle, and carrying out hydrothermal treatment at 200 ℃ for 8 hours. And after the hydrothermal reaction is finished, taking out the sample, washing the sample with deionized water, and drying the sample. As shown in FIG. 7, after hydrothermal treatment, a layer of non-compact diamond grains with the size distribution of 30-200 nm is formed on the surface of the titanium alloy.
Example 8
Preparing titanium dioxide nano film on the surface of pure titanium subjected to hydrothermal 8-hour treatment and sand blasting by adopting sodium chloride solution
The specific preparation steps for preparing the titanium dioxide nanoparticles on the surface of the sand blasting pure titanium in the embodiment are as follows:
pure titanium of 25X 3mm is taken as a matrix, and Al is adopted 2 O 3 Carrying out sand blasting treatment on the particles for 10-60 s, and then respectively carrying out ultrasonic cleaning for 10min in absolute ethyl alcohol and deionized water to remove impurities and oil stains.
Preparing 5% sodium chloride solution, adding the sodium chloride solution into a high-pressure hydrothermal kettle with the volume filling rate of 70%, setting the pressure of the hydrothermal kettle to be 5MP after a sample is placed in the hydrothermal kettle, and carrying out hydrothermal treatment at 200 ℃ for 8 hours. And after the hydrothermal reaction is finished, taking out the sample, washing the sample with deionized water, and drying the sample. As shown in FIG. 8, after hydrothermal treatment, a dense and uniform particle layer with the size distribution of 50-100 nm is formed on the surface of the sandblasted titanium matrix.
Example 9
Preparing titanium dioxide nano-film by treating pure titanium surface with sodium chloride solution hydrothermal for 2 hours
The steps of preparing the titanium dioxide nano gel layer on the surface of pure titanium in the embodiment are shown in the embodiment 1, the appearance is shown in fig. 1, and the specific preparation steps are as follows:
pure titanium with the size of 25 multiplied by 3mm is used as a matrix, SiC sand paper with the size of 150 meshes, 400 meshes, 800 meshes, 1200 meshes and 2000 meshes is adopted to polish the pure titanium, and then the pure titanium is ultrasonically cleaned in absolute ethyl alcohol and deionized water for 20min respectively to remove oil stains.
Configuration 27% H 2 O 2 And 30ml (15 ml each) of a mixed solution of 0.1M nitric acid, putting the titanium substrate into the mixed solution, transferring the titanium substrate into an oven at the temperature of 60-150 ℃, keeping the temperature for 30-90 min, taking out the titanium substrate, and washing the titanium substrate with deionized water. And then putting the cleaned sample into an oven at 150 ℃ and preserving the temperature for 1 h.
Preparing 5% sodium chloride solution, adding the sodium chloride solution into a hydrothermal kettle with a polytetrafluoroethylene lining, wherein the volume filling rate is 50%, and placing a sample into the hydrothermal kettle to perform hydrothermal treatment for 2 hours at 200 ℃. And after the hydrothermal reaction is finished, taking out the sample, washing the sample by using deionized water, putting the sample into a muffle furnace, heating the sample to 400 ℃, preserving the heat for 4 hours, and carrying out heat treatment on the obtained substrate with the titanium dioxide nano particles growing on the surface to form the nano titanium dioxide particles with different crystal forms. As shown in FIG. 9, after hydrothermal treatment and heat treatment, dense and uniform small particles with a size distribution of 20-50 nm are formed.
In addition, the inventors of the present invention have conducted corresponding experiments using other process conditions listed above instead of the corresponding process conditions in examples 1 to 9, for example, the hydrothermal reaction temperature is 100 ℃ and 300 ℃, the reaction time is 0.5h and 24h, the reaction pressure is 20Mpa, the concentration of the hydrothermal solution is 0.1mol/L and 10mol/L, and the heat treatment temperature is 80 ℃ and 1000 ℃, and the contents to be verified are similar to those of the products in examples 1 to 9. Therefore, the contents of the verification of each example are not described herein one by one, and only examples 1 to 9 are used as representatives to describe the excellent points of the present invention.
It should be noted that, in the present context, an element defined by the phrase "comprising … …" does not exclude the presence of other identical elements in steps, processes, methods or experimental facilities including the element.
It should be understood that the above preferred embodiments are only for illustrating the present invention, and other embodiments of the present invention are also possible, but those skilled in the art will be able to adopt the technical teaching of the present invention and equivalent alternatives or modifications thereof without departing from the scope of the present invention.
Claims (4)
1. A method of growing titanium dioxide nanoparticles on a surface of a titanium or titanium alloy substrate, comprising:
etching the surface of the substrate by using 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 the thickness of the titanium dioxide nano gel layer is 200-500 nm;
contacting the surface of the substrate with a hydrothermal solution in a hydrothermal kettle to perform hydrothermal reaction, wherein the reaction temperature is 100-300 ℃, the time is 0.5-24 hours, and the pressure is 0-20 Mpa, so that titanium dioxide nanoparticles are grown on the surface of the substrate, the hydrothermal solution adopts a salt solution containing chloride ions and/or fluoride ions, the concentration of the hydrothermal solution is 0.1-10 mol/L, the lining of the hydrothermal kettle is a polytetrafluoroethylene lining, and the volume filling rate of the hydrothermal solution in the lining of the hydrothermal kettle in the hydrothermal reaction is 50-70%;
after the hydrothermal reaction 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;
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.
2. The method of growing titanium dioxide nanoparticles on a surface of a titanium or titanium alloy substrate of claim 1, further comprising: polishing and/or sand blasting and/or cleaning the substrate surface, and then etching 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 Al 2 O 3 、SiC、SiO 2 And ZrO 2 Any 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.
3. 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 reaction is finished, cleaning and drying the obtained substrate with the titanium dioxide nanoparticles growing on the surface.
4. 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.
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