CN115970057A - Petal-shaped TiO 2 Preparation method of nano-pore antibacterial coating - Google Patents
Petal-shaped TiO 2 Preparation method of nano-pore antibacterial coating Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 14
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/30—Against vector-borne diseases, e.g. mosquito-borne, fly-borne, tick-borne or waterborne diseases whose impact is exacerbated by climate change
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- Materials For Medical Uses (AREA)
Abstract
The invention discloses a petal-shaped TiO 2 The preparation method of the nano-pore antibacterial coating comprises the following steps: removing oil from a TC4 metal product, sand blasting, ultrasonic cleaning, acid washing, washing the metal product with purified water for 2min, washing for 10s, spraying for 10s, and washing for 10s with absolute ethyl alcohol; oxidizing for 80-150 min at 20-30V; the oxidation is carried out for more than or equal to 40min at the voltage of 24-38V; oxidizing for 30min at 34-52V; 56-78V oxidation is more than or equal to 40min; the total oxidation time is 200-300min; washing, flushing and spraying purified water, and flushing with absolute ethyl alcohol; heat treatment, heating from room temperature to 200 deg.C at a heating rate of 3.0 deg.C/min; preserving the heat for 10min; heating the mixture to the temperature of 200 ℃ to 400 ℃,the heating rate is 4.0 ℃/min; keeping the temperature at 400 ℃ for 20min; raising the temperature to 600 ℃ at the temperature of 400 ℃, keeping the temperature for 1h at the temperature raising rate of 5.0 ℃/min; cooling to below 100 ℃ and discharging.
Description
Technical Field
The invention relates to the technical field of metal biomaterials, in particular to petal-shaped TiO 2 A method for preparing a nanostructure.
Background
Titanium and titanium alloys are the most used implant metal biomaterials at present, and have the advantages of low density, high specific strength, low elastic modulus and good biocompatibility, but have low hardness, poor abrasion resistance and corrosion resistance, and the wear resistance affects the life span of an implant device, and may generate harmful metal particles or micro-debris to cause inflammatory, corrosive and toxic reactions of surrounding tissues, and metal ions or harmful ions are released from titanium and titanium alloy dental implants due to corrosion to affect the health of organisms.
In recent years, the continuous breakthrough of material science, the development of various internal implantation instruments in the orthopedic field is rapid, the clinical application scale of the muscle-skeleton system repair and percutaneous implantation instruments at home and abroad is increasingly huge, the growth is rapid, and the use ratio of the internal fixation instruments and the prostheses is increased year by year. The use of these devices for implanting inside the organism does allow the patient to obtain a better therapeutic effect, but also brings some risks. The most problematic of these is post-operative infection of the endoprosthesis. Postoperative infection remains one of the most common and serious complications, and adhesion, proliferation and bacterial biofilm formation of bacteria at the level of the implant is the major cause of such complications. Titanium and titanium alloy do not have the bacteriostatic function, so that the titanium and titanium alloy has very important practical significance for modifying the surface of the titanium and endowing the titanium and titanium alloy with the function of inhibiting bacteria from adhering to the surface of the titanium and titanium alloy.
Therefore, the technical problem to be solved is to provide a metal biomaterial with friction resistance, corrosion resistance and bacteriostatic function.
Disclosure of Invention
In view of this, the invention provides petal-shaped TiO 2 The preparation method of the nano-pore antibacterial coating is beneficial to the adhesion and proliferation of osteoblasts, the surface of the osteoblasts can induce the deposition of mineralized substances, the mineralized area is increased, and the formed modified layer has the function of inhibiting bacteria from adhering to the surface of the osteoblasts and has the advantages of high hardness, corrosion resistance, friction resistance and the like.
In order to achieve the purpose, the invention adopts the following technical scheme:
petal-shaped TiO 2 The preparation method of the nano-pore antibacterial coating comprises the following steps:
1) Pretreatment: removing oil from the machined TC4 metal product, sandblasting and ultrasonically cleaning to obtain a pretreated metal product;
2) Acid washing: carrying out acid washing treatment on the pretreated TC4 metal product;
3) Washing, rinsing and spraying: washing the washed TC4 metal product with purified water for 2min, washing for 10s, spraying for 10s, and washing with absolute ethyl alcohol for 10s;
4) Anodic oxidation: electrolyzing and oxidizing the cleaned product in electrolyte for 80-150 min at 20-30V; then oxidizing for more than or equal to 40min at the voltage of 24-38V; oxidizing for 30min at 34-52V; 56-78V oxidation is more than or equal to 40min; the total oxidation time is 200-300min; the total time of the four steps of anodic oxidation is preferably 240-270min, the time of anodic oxidation in the first step is preferably 120min, the time of anodic oxidation in the second step is preferably 60min, the time of anodic oxidation in the third step is preferably 30min, and the time of anodic oxidation in the fourth step is preferably the same as that in the second step;
5) Washing: washing, washing and spraying the product by purified water, and finally washing by absolute ethyl alcohol;
6) And (3) heat treatment: heating from room temperature to 200 deg.C at a rate of 3.0 deg.C/min; preserving the heat for 10min; heating from 200 deg.C to 400 deg.C at a heating rate of 4.0 deg.C/min; keeping the temperature at 400 ℃ for 20min; heating from 400 ℃ to 600 ℃, wherein the heating rate is 5.0 ℃/min, and keeping the temperature for 1h; cooling to below 100 ℃ and discharging.
As a preferable technical scheme of the above technical scheme, the acid washing is: adding citric acid into 1L water50g、NH 4 HF 2 10g, preparing pickling solution; the acid washing treatment time is 3min, and the temperature is 30 ℃.
As a preferable embodiment of the above technical means, the electrolyte is a mixture containing an organic acid and an inorganic acid;
as a preferable technical solution of the above technical solution, the inorganic acid is sulfuric acid; the organic acid is oxalic acid.
As a preferable embodiment of the above-mentioned embodiment, the oxalic acid content is 25 to 37g/L, preferably 26 to 35g/L, and more preferably 28 to 30g/L, based on 1L of the electrolyte solution. The sulfuric acid content is 25 to 30g/L, preferably 25 to 38g/L, and more preferably 25 to 27g/L, based on 1L of the electrolyte.
The principle of forming the petal-shaped structure is as follows: the titanium alloy is in a strong acid solution under a certain voltage and temperature, once a voltage is applied, an oxide film, namely a barrier layer, is formed on the surface of the titanium alloy, the film layer is dissolved after the film is formed under the applied voltage, film forming-dissolution-film forming dynamic balance is formed, the film layer is dissolved through electrochemical dissolution under direct current, the film forming-dissolution-film forming dynamic balance causes ordered unevenness of the film layer, the unevenness of the film layer causes uneven current distribution, the resistance of a concave part is small, but the current is large, the protrusion is opposite, the concave part with high current generates electrochemical dissolution of the oxide film under the action of an electric field, the concave part is deepened into a cavity, the original cavity continues to form the film forming-dissolution-film forming dynamic balance under the continuously increased voltage, and then the ordered porous oxide film is formed, the original oxide film layer can be punctured only by increasing the voltage, the current at the punctured part can quickly increase, and the growth of the titanium dioxide nanotube can be accelerated.
In order to solve the problems of coating hardness, corrosivity and postoperative infection, the invention aims to overcome the defects in the prior art, and the ordered nanopore structure can be obtained by carrying out anodic oxidation on the green environment-friendly fluorine-free substance, so that the obtained nanopore coating has the functions of improving corrosion resistance and hardness and inhibiting bacteria from adhering to the surface of the nanopore; the method overcomes the defects that ordered nano-pores are obtained only by carrying out anodic oxidation treatment on a mixed solution containing ethylene glycol fluoride mildly, the existing anodic oxidation process of the mixed solution containing ethylene glycol fluoride has the defects that toxic fluoride and viscous liquid are adopted, the mixed solution containing ethylene glycol fluoride has the defects that the viscous solution is difficult to diffuse and permeate into a film layer to react, the conductivity is poor, the process time is too long, the coating is difficult to fall off or cannot form a nano-structure coating due to poor fluoride control, the ethylene glycol has strong hygroscopicity and needs to be prepared at present, the mixed solution containing ethylene glycol fluoride cannot be recycled as a disposable working solution, and the hardness, the corrosion resistance and the wear resistance of the coating obtained by adopting the anodic oxidation of the mixed solution containing ethylene glycol fluoride are poor.
The petal-shaped TiO2 nano-pore nano-structure obtained by the treatment of the invention has large specific surface area, each petal consists of a plurality of regular fine nano-pores, the diameter of each petal is 0.15-1.2um, the average pore diameter of the fine pores is 7-20nm, the depth of the pores is 20-300nm, the larger the nano-pores are, the stronger the adhesion capability of inhibiting bacteria on the surface of the petal-shaped TiO2 nano-structure is, the larger the pore diameter of the nano-pores is, the poorer the hardness and the wear resistance of the nano-pores are, and the special physical surface structure with the pore diameter of 7-20nm can reduce the adsorbable contact area of the bacteria and has hydrophilicity, thereby achieving the effect (physical effect) of inhibiting the bacteria from adhering on the surface of the petal. The TiO2 nano coating with the petal-shaped structure is beneficial to the adhesion and proliferation of osteoblasts, the surface of the osteoblasts can induce the deposition of mineralized substances, the mineralized area is increased, and the formed modified layer has the function of inhibiting bacteria from adhering to the surface of the osteoblasts and has the advantages of high hardness, corrosion resistance, friction resistance and the like.
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 embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the provided drawings without creative efforts.
FIG. 1 accompanying drawing is the petaloid TiO obtained in example 1 2 SEM images of the nanocoating surface;
FIG. 2 is the petal-shaped TiO obtained in example 2 2 SEM images of the nanocoating surface;
FIG. 3 is the petaloid TiO of example 4 2 SEM images of the nanocoating surface;
FIG. 4 accompanying drawing is the petaloid TiO obtained in example 1 2 EDS analysis spectrogram of the surface of the nano coating;
FIG. 5 accompanying drawing is the petaloid TiO obtained in example 1 2 Surface EDS analysis spectrogram of the nano-coating implant after in-vitro simulation of body fluid SBF soaking;
FIG. 6 is a drawing showing petal-shaped TiO obtained in example 1 2 The number distribution of viable bacteria after the nano implant is inoculated with staphylococcus aureus and cultured for 24 hours; the left side is a staphylococcus aureus control group, and the right side is a staphylococcus aureus group to be detected;
FIG. 7 is a drawing showing petal-shaped TiO obtained in example 1 2 The number distribution of viable bacteria is carried out after the nano implant is inoculated with escherichia coli and cultured for 24 hours; the left side is an escherichia coli control group, and the right side is an escherichia coli group to be detected;
FIG. 8 is a graph of open circuit potential versus time; FIG. 8-1 shows petal-shaped TiO obtained in example 1 2 A nano coating open circuit potential-time curve graph; FIG. 8-2 is a graph of open circuit potential versus time for a coating formed by anodization in a prior art ethylene glycol ammonium fluoride mixture;
FIG. 9 is a graph showing the antibacterial performance of the coating prepared using electrode solution A against Staphylococcus aureus; the control is arranged on the left side, the colony number is 386, the group to be detected is arranged on the right side, and the colony number is 141;
FIG. 10 is a graph showing the antibacterial performance of the coating prepared using electrode solution A against E.coli; the control on the left side, the colony count 231, the test group on the right side, the colony count 78;
FIG. 11 is the EDS spectrum of the surface of the coated implant soaked in SBF in vitro simulated body fluid using electrolyte A; after the implant is soaked in simulated body fluid SBF in vitro, the coating only contains 0.2 percent of phosphorus element and no calcium element. The phosphorus element possibly comes from phosphoric acid in the electrolyte, which indicates that the coating does not induce the growth of the Ca-P coating;
FIG. 12 is a graph showing the antimicrobial performance of a coating prepared using electrode solution B against Staphylococcus aureus; the control on the left side, colony number 628, the test group on the right side, colony number 435;
FIG. 13 is a graph showing the antibacterial performance of the coating prepared using electrode solution B against E.coli; the control on the left side, the colony count 400, the test group on the right side, the colony count 281;
FIG. 14 is a graph showing the surface EDS analysis of coated implants obtained using electrolyte B after in vitro simulated body fluid SBF soaking; after the implant is soaked in simulated body fluid SBF in vitro, the coating only contains 0.16 percent of phosphorus element and no calcium element. Phosphorus possibly comes from phosphoric acid in the electrolyte, and the coating does not induce the growth of the Ca-P coating;
FIG. 15 is a graph of open circuit potential versus time for the resulting coating of electrolyte A;
FIG. 16 is a graph showing the open circuit potential versus time of the resulting coating for electrolyte B.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without making any creative effort based on the embodiments in the present invention, belong to the protection scope of the present invention.
Example 1
Petal-shaped TiO 2 The preparation method of the nano structure comprises the following steps:
1) Oil removal: carrying out oil removal treatment on the machined TC4 metal product;
2) Sand blasting: blasting sand to the machined TC4 metal product to achieve uniform surface;
3) Cleaning: carrying out ultrasonic cleaning for 15 minutes;
4) Acid washing: an acid washing treatment was performed, based on 1L of a pickling solution, with 50g of citric acid 4 HF 2 10g of water, and the balance of water, wherein the pickling treatment time is 3min and the temperature is 30 ℃;
5) Washing the washed TC4 metal product with purified water for 2min, washing for 10s, spraying for 10s, and washing with absolute ethyl alcohol for 10s;
6) Anodizing a TC4 metal product, wherein the anodizing voltage of the first step is 26V, the anodizing time is 120 minutes, the anodizing voltage of the second step is 6V higher than the voltage of the first step, and the anodizing time of the second step is half of the time of the first step, and the oxalic acid is 30g/L and the sulfuric acid is 25g/L in terms of 1L of electrolyte; the anodic oxidation voltage ratio of the third step is 12V higher than that of the second step, and the anodic oxidation time is half of that of the second step; the anodic oxidation voltage of the fourth step is higher than that of the third step by 24V, and the anodic oxidation time of the fourth step is the same as that of the second step;
7) Washing, washing and spraying the product by purified water, and finally washing by absolute ethyl alcohol;
8) Heat treatment, namely slowly increasing the temperature, wherein the heat treatment conditions comprise that the temperature is increased from room temperature to 200 ℃ in the first step, the temperature increase rate is 3.0 ℃ per minute, the temperature is maintained for 10 minutes at 200 ℃ in the second step, the temperature is increased to 400 ℃ in the third step, and the temperature increase rate is 4.0 ℃ per minute; fourthly, keeping the temperature at 400 ℃ for 20 minutes, increasing the temperature at 400 ℃ to 600 ℃ in the fifth step, keeping the temperature at 600 ℃ for 1 hour in the sixth step, and discharging the steel after the steel is cooled to below 100 ℃ along with the furnace in the seventh step. The obtained petal-shaped TiO 2 The SEM image of the surface of the nano coating is shown in figure 1, and the EDS analysis spectrum of the surface is shown in figure 4.
Example 2
Petal-shaped TiO 2 The preparation method of the nano structure comprises the following steps:
1) Oil removal: carrying out oil removal treatment on the machined TC4 metal product;
2) Sand blasting: blasting sand to the machined TC4 metal product to achieve uniform surface;
3) Cleaning: carrying out ultrasonic cleaning for 15 minutes;
4) Acid washing: an acid washing treatment was performed, based on 1L of a pickling solution, with 50g of citric acid 4 HF 2 10g of water, and the balance of water, wherein the pickling treatment time is 3min and the temperature is 30 ℃;
5) Washing the washed TC4 metal product with purified water for 2min, washing for 10s, spraying for 10s, and washing with anhydrous ethanol for 10s
6) Anodizing the TC4 metal product, wherein the anodizing voltage of the first step is 27V, the anodizing time is 110 minutes, the anodizing voltage of the second step is 6V higher than that of the first step, the anodizing time is 60 minutes, the anodizing voltage of the third step is 12V higher than that of the second step, the anodizing time is half of that of the second step, the anodizing voltage of the fourth step is 24V higher than that of the third step, and the anodizing time of the fourth step is the same as that of the second step;
7) The product is washed by purified water, washed and sprayed, and finally washed by absolute ethyl alcohol;
8) Heat treatment in a furnace in the same manner as in step 8) of example 1; the obtained petal-shaped TiO 2 The SEM image of the nanocoating surface is shown in fig. 2.
Example 3
Petal-shaped TiO 2 The preparation method of the nano structure comprises the following steps:
1) Oil removal: deoiling treatment is carried out on the TC4 metal product after machining
2) Sand blasting: blasting sand to the machined TC4 metal product to achieve uniform surface;
3) Cleaning: carrying out ultrasonic cleaning for 15 minutes;
4) Acid washing: an acid washing treatment was carried out by using 50g of citric acid and NH as 1L of a pickling solution 4 HF 2 10g of water, and the balance of water, wherein the pickling treatment time is 3min and the temperature is 30 ℃;
5) Washing the washed TC4 metal product with purified water for 2min, washing for 10s, spraying for 10s, and washing with absolute ethyl alcohol for 10s;
6) Anodizing a TC4 metal product, wherein the anodic oxidation is 30g/L of oxalic acid and 27g/L of sulfuric acid in 1L of electrolyte; the anodic oxidation voltage of the first step is 28V, the anodic oxidation time is 100 minutes, the anodic oxidation voltage of the second step is 6V higher than the voltage of the first step, and the anodic oxidation time is 60 minutes; the anodic oxidation voltage of the third step is 12V higher than that of the second step, and the anodic oxidation time is half of that of the second step; the anodic oxidation voltage of the fourth step is higher than that of the third step by 24V, and the anodic oxidation time of the fourth step is the same as that of the second step;
7) Washing, washing and spraying the product by purified water, and finally washing by absolute ethyl alcohol;
8) The heat treatment furnace was processed in the same manner as in step 8) of example 1.
Example 4
Petal-shaped TiO 2 The preparation method of the nano structure comprises the following steps:
1) Oil removal: carrying out oil removal treatment on the machined TC4 metal product;
2) Sand blasting: performing sand blasting treatment on the machined aluminum alloy product to achieve uniform surface;
3) Cleaning: carrying out ultrasonic cleaning for 15 minutes;
4) Acid washing: an acid washing treatment was performed, based on 1L of a pickling solution, with 50g of citric acid 4 HF 2 10g of water, and the balance of water, wherein the pickling treatment time is 3min and the temperature is 30 ℃;
5) Washing the pickled TC4 metal product with purified water for 2min, washing for 10s, spraying for 10s, and washing with anhydrous ethanol for 10s
6) Anodizing a TC4 metal product, wherein the anodic oxidation is 30g/L of oxalic acid and 27g/L of sulfuric acid in 1L of electrolyte; the anodic oxidation voltage of the first step is 30V, the anodic oxidation time is 90 minutes, the anodic oxidation voltage of the second step is 6V higher than that of the first step, and the anodic oxidation time is 60 minutes; the anodic oxidation voltage of the third step is 12V higher than that of the second step, and the anodic oxidation time is half of that of the second step; the anodic oxidation voltage of the fourth step is higher than that of the third step by 24V, and the anodic oxidation time of the fourth step is the same as that of the second step;
7) Washing, washing and spraying the product by purified water, and finally washing by absolute ethyl alcohol;
8) Heat treatment in a furnace in the same manner as in step 8) of example 1; the obtained petal-shaped TiO 2 The SEM image of the nanocoating surface is shown in fig. 3.
The hardness of the coatings obtained in examples 1 to 4 were measured, respectively, as shown in Table 1;
TABLE 1
Example 1-example 4 the oxalic acid in step 6) may be replaced with citric acid, acetic acid, tartaric acid, malic acid or propionic acid; sulfuric acid may be replaced with phosphoric acid or nitric acid.
Example 1 the resulting coating in vitro simulates SBF soaking in body fluid to induce Ca-P coating growth
The coating implant obtained in example 1 simulates body fluid SBF soaking in vitro to induce the growth of a Ca-P coating, the soaking is carried out for 16 days, the SBF solution is replaced for 1 time every two days, the coating is taken out after the soaking is carried out for 16 days, purified water is used for washing and washing, finally absolute ethyl alcohol is used for washing and drying, the coating is subjected to EDS component analysis, the coating can be seen from a spectrogram, the coating contains Ti, C and O elements, ca, P and other elements, the spectrogram is shown in figure 5, ca/P =2.65/1.7=1.55, and the fact that the petal-shaped structure has a lot of fine TiO is shown in figure 5, and the Ca/P =2.65/1.7=1.55 2 The specific surface area of the nano-pore coating is large enough, and the porous structure can induce the growth of the Ca-P coating.
Example 1 the resulting coated implants were tested for bacterial anti-adhesion
Respectively adding a certain amount of test bacteria to the petal-shaped TiO 2 Eluting the nano coating to-be-detected group and the positive control group sample, and eluting the eluted petal-shaped TiO 2 And detecting the residual test bacteria number on the sample sheets of the nano coating to be detected and the positive control group, wherein the difference of the average residual viable bacteria number of the test bacteria on the sample sheets of the positive control group and the test group is the bacteria anti-adhesion rate of the test group. See fig. 6 and 7.
The method comprises the following steps: 6 samples of the group to be tested and 6 samples of the positive control group, and 3 samples of each test bacterium are respectively detected.
Respectively eluting the sample wafer (3) of the sample group to be detected and the sample wafer (3) of the positive control group, which are added with a certain amount of test bacteria, detecting residual test bacteria on the sample wafer of the sample group to be detected and the sample wafer of the positive control group after elution, and culturing for 24 hours after inoculation, wherein the bacterial anti-adhesion rate of the sample group to be detected is not less than (the average viable count on the sample wafer of the positive control group-the average viable count on the sample wafer to be detected)/the average viable count on the sample wafer of the positive control group is 100 percent.
See table 2;
table 2 example 1, 2 anti-adhesion rate of bacteria with petaloid TiO2 nano-coating
Open circuit potential testing of the coated implants obtained in example 1
The open circuit potential is the potential measured when the metal reaches a stable corrosion state in the absence of an applied current. Open circuit potential-time curves were measured through the working electrode reference electrode and the three-electrode system for the counter electrode, see fig. 8; no current flows in the circuit, the voltage of the battery is equivalent to the voltage of the open circuit state, the operation is carried out in 0.9% sodium chloride saline, the open circuit potential of the obtained coating,
the open circuit potential of the coating obtained in example 1 was in a relatively stable state during 3 hours of immersion, and the open circuit potential of fig. 8-1 was stable at 180mv, indicating that the corrosion resistance can be effectively improved by applying the coating, and the open circuit potential of the coating obtained from the prior art ethylene glycol ammonium fluoride mixture fluctuates from-92.5 mv to (-118 mv) in the upper and lower directions, as shown in fig. 8-2, which is inferior to the present technique, indicating that the coating obtained from the present technique has better corrosion resistance than the coating obtained from the ethylene glycol ammonium fluoride mixture.
The coated implant obtained in example 1 was subjected to a scratch resistance test
The method comprises the following steps: the sample to be tested with the petal-type coating is placed on a flat experiment table, under the action of constant normal force of 5N, a diamond pressure head is used for stably cutting the coating at a constant speed along a straight line according to the surface shape of a product, the scratch depth is 1.04 mu m, and the scratch resistance of the coating is close to that of a micro-arc (black and gray) anodic oxidation film layer.
Example 5
Comparative tests were performed according to steps 1) to 8) of example 1 (except that the electrolyte composition in step 6) and the results of the coating property tests were shown in fig. 9 to 16. Wherein, electrolyte trades electrolyte A and electrolyte B respectively, and electrolyte A constitutes: 35g/L of phosphoric acid and 5ml/L of acetic acid; the electrolyte B comprises: 35g/L of phosphoric acid and 50g/L of citric acid.
From the results of fig. 9 to 16, it is known that, when 35g/L phosphoric acid, 5ml/L acetic acid, 35g/L phosphoric acid and 50g/L citric acid were used to test the coating according to all the steps (except for the composition of the electrolyte in step 6) of example 1 and the coating was tested according to various indexes, the bacterial adhesion resistance of the obtained coating was lower than 70%, the coating did not induce the growth of the Ca-P coating, the coating hardness was lower than 400HV, and the fluctuation of the open circuit potential was very unstable, which indicates that the corrosion resistance was poor, indicating that the performance of the coating obtained by using the electrolyte composed of phosphoric acid and acetic acid did not reach the performance of the coating obtained by using the electrolyte composed of sulfuric acid and oxalic acid, and that the performance of the coating obtained by using the electrolyte composed of phosphoric acid and citric acid did not reach the performance of the coating obtained by using the electrolyte composed of sulfuric acid and oxalic acid.
The embodiments in the present description are described in a progressive manner, each embodiment focuses on differences from other embodiments, and the same and similar parts among the embodiments are referred to each other.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (5)
1. Petal-shaped TiO 2 The preparation method of the nano-pore antibacterial coating is characterized by comprising the following steps:
1) Pretreatment: removing oil from the machined TC4 metal product, sandblasting and ultrasonically cleaning to obtain a pretreated metal product;
2) Acid washing: carrying out acid washing treatment on the pretreated metal product;
3) Washing, rinsing and spraying: washing the washed TC4 metal product with purified water for 2min, washing for 10s, spraying for 10s, and washing with absolute ethyl alcohol for 10s;
4) Anodic oxidation: electrolyzing and oxidizing the cleaned product in electrolyte for 80-150 min at 20-30V; then oxidizing for more than or equal to 40min at a voltage of between 24 and 38V; oxidizing for 30min at 34-52V; 56-78V oxidation is more than or equal to 40min; the total oxidation time is 200-300min;
5) Washing: washing, washing and spraying the product by purified water, and finally washing by absolute ethyl alcohol;
6) And (3) heat treatment: heating from room temperature to 200 deg.C at a heating rate of 3.0 deg.C/min; keeping the temperature at 200 ℃ for 10min; heating from 200 ℃ to 400 ℃ at a heating rate of 4.0 ℃/min; keeping the temperature at 400 ℃ for 20min; heating from 400 ℃ to 600 ℃, wherein the heating rate is 5.0 ℃/min, and keeping the temperature at 600 ℃ for 1h; cooling to below 100 ℃ and discharging.
2. The petal-shaped TiO of claim 1 2 The preparation method of the nanopore antibacterial coating is characterized in that in the step 2), the acid washing is as follows: 50g of citric acid and NH are added into 1L of water 4 HF 2 8g, preparing pickling solution; the acid washing treatment time is 3min, and the temperature is 30 ℃.
3. The petal-shaped TiO of claim 1 2 The preparation method of the nano-pore antibacterial coating is characterized in that the electrolyte is a mixture containing organic acid and inorganic acid.
4. The petal-shaped TiO of claim 3 2 The preparation method of the nano-pore antibacterial coating is characterized in that the inorganic acid is sulfuric acid; the organic acid is oxalic acid.
5. The petal-shaped TiO of claim 4 2 The preparation method of the nano-pore antibacterial coating is characterized in that the content of oxalic acid is 25 to 37g/L and the content of sulfuric acid is calculated by 1L of electrolyteThe content of (B) is 25 to 30g/L.
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