CN115970057B - Petal-shaped TiO2Preparation method of nano-pore antibacterial coating - Google Patents
Petal-shaped TiO2Preparation method of nano-pore antibacterial coating Download PDFInfo
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- 238000000034 method Methods 0.000 title claims description 7
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- 239000003792 electrolyte Substances 0.000 claims description 28
- 239000002253 acid Substances 0.000 claims description 25
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- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 18
- 239000007943 implant Substances 0.000 description 13
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 12
- 230000007797 corrosion Effects 0.000 description 12
- 238000005260 corrosion Methods 0.000 description 12
- 238000012360 testing method Methods 0.000 description 10
- 229910001069 Ti alloy Inorganic materials 0.000 description 9
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 9
- 235000015165 citric acid Nutrition 0.000 description 9
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 8
- 239000013641 positive control Substances 0.000 description 8
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- 239000010936 titanium Substances 0.000 description 6
- QNVQPXNRAJFKQV-UHFFFAOYSA-N 1-fluoroethane-1,2-diol Chemical compound OCC(O)F QNVQPXNRAJFKQV-UHFFFAOYSA-N 0.000 description 5
- 241000588724 Escherichia coli Species 0.000 description 5
- 241000191967 Staphylococcus aureus Species 0.000 description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 5
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
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- 238000001878 scanning electron micrograph Methods 0.000 description 5
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- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 4
- DPZKMHVEGIUXGE-UHFFFAOYSA-N [NH4+].[F-].OCCO Chemical compound [NH4+].[F-].OCCO DPZKMHVEGIUXGE-UHFFFAOYSA-N 0.000 description 4
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- 230000015572 biosynthetic process Effects 0.000 description 4
- 210000000963 osteoblast Anatomy 0.000 description 4
- 239000011574 phosphorus Substances 0.000 description 4
- 229910052719 titanium Inorganic materials 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 206010067268 Post procedural infection Diseases 0.000 description 3
- 239000012620 biological material Substances 0.000 description 3
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- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
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- 230000007547 defect Effects 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
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- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 1
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical group O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
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- 230000008621 organismal health Effects 0.000 description 1
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- 235000019260 propionic acid Nutrition 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
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- 239000011780 sodium chloride Substances 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
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Classifications
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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
Landscapes
- Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
- Materials For Medical Uses (AREA)
Abstract
The invention discloses a preparation method of a petal-shaped TiO 2 nano-pore antibacterial coating, which comprises the following steps: removing oil from the TC4 metal product, blasting sand, ultrasonically cleaning, pickling, washing the pickled metal product with purified water for 2min, washing for 10s, spraying for 10s, and washing with absolute ethyl alcohol for 10s; oxidizing for 80-150 min at 20-30V; 24-38V oxidation is more than or equal to 40min; oxidizing for 30min at 34-52V; oxidation is carried out for more than or equal to 40 minutes at 56-78V; the total oxidation time is 200-300min; washing with purified water, washing, spraying, and washing with absolute ethyl alcohol; heat treatment, namely, raising the temperature from room temperature to 200 ℃ and raising the temperature at a rate of 3.0 ℃/min; preserving heat for 10min; heating to 200deg.C to 400deg.C at a heating rate of 4.0deg.C/min; preserving heat at 400 ℃ for 20min; heating to 600 ℃ at 400 ℃ and the heating rate is 5.0 ℃/min, and preserving heat for 1h; cooling to below 100 ℃ and discharging.
Description
Technical Field
The invention relates to the technical field of metal biological materials, in particular to a preparation method of petal-shaped TiO 2 nano-structure.
Background
Titanium and titanium alloy are the most widely used implant metal biomaterials at present, and have the advantages of low density, high specific strength, low elastic modulus and good biocompatibility, but the hardness is low, the friction resistance is poor, the corrosion resistance is poor, the wear resistance influences the service life of an implant device, harmful metal particles or micro-scraps can be generated, inflammatory, corrosion and toxic reactions of surrounding tissues are caused, and metal ions or harmful ions are released from titanium and titanium alloy dental implants due to corrosion, so that the health of organisms is influenced.
In recent years, the continuous breakthrough of material science and the rapid development of various endoprosthesis devices in the orthopaedics field, the clinical application scale of the repair of the muscular-skeletal system and the percutaneous implantation devices at home and abroad are increasingly huge, the growth is rapid, and the use proportion of the endoprosthesis devices and the prostheses is increased year by year. The use of these implantable devices does allow the patient to achieve better therapeutic results, but also presents some potential hazards. The most difficult of these is postoperative infection of the implanted endoprosthesis. Post-operative infection remains one of the most common and serious complications, with bacterial adhesion, proliferation and bacterial biofilm formation on the implanted surfaces being the primary causes of such complications. Titanium and titanium alloy have no antibacterial function, so that the surface modification of titanium and titanium alloy has very important practical significance for endowing the titanium and titanium alloy with the function of inhibiting bacteria from adhering to the surface.
Therefore, how to provide a friction-resistant, corrosion-resistant and bacteriostatic metal biomaterial is a technical problem to be solved by those skilled in the art.
Disclosure of Invention
In view of the above, the invention provides a preparation method of petal-shaped TiO 2 nanometer pore antibacterial coating, which is favorable for the adhesion and proliferation of osteoblasts and the deposition of mineralized substances induced on the surface of the osteoblasts, so that the mineralized area is increased, and the formed modified layer has the function of inhibiting bacteria from adhering on the surface of the modified layer and has the advantages of high hardness, corrosion resistance, friction resistance and the like.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
The preparation method of the petal-shaped TiO 2 nano-pore antibacterial coating comprises the following steps:
1) Pretreatment: removing oil, sand blasting and ultrasonic cleaning of the machined TC4 metal product to obtain a pretreated metal product;
2) Acid washing: carrying out acid washing treatment on the pretreated TC4 metal product;
3) Washing, flushing and spraying: washing the TC4 metal product after pickling 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 24-38V oxidizing for more than or equal to 40min; oxidizing for 30min at 34-52V; oxidation is carried out for more than or equal to 40 minutes at 56-78V; the total oxidation time is 200-300min; the total time of four steps of anodic oxidation can be preferably 240-270min, the anodic oxidation time of the first step can be preferably 120min, the anodic oxidation time of the second step can be preferably 60min, the anodic oxidation time of the third step can be preferably 30min, and the anodic oxidation time of the fourth step can be preferably the same as that of the second step;
5) Washing: washing the product with purified water, washing, spraying, and finally washing with absolute ethyl alcohol;
6) And (3) heat treatment: raising the temperature from room temperature to 200 ℃ with the temperature raising rate of 3.0 ℃/min; preserving heat for 10min; raising the temperature from 200 ℃ to 400 ℃ at a heating rate of 4.0 ℃/min; preserving heat at 400 ℃ for 20min; heating from 400 ℃ to 600 ℃, wherein the heating rate is 5.0 ℃/min, and preserving heat for 1h; cooling to below 100 ℃ and discharging.
As a preferable technical scheme of the technical scheme, the acid washing is as follows: adding 50g of citric acid and 4HF2 g of NH to 1L of water to prepare pickling solution; the pickling treatment time was 3min at 30 ℃.
As a preferable technical scheme of the technical scheme, the electrolyte is a mixture containing organic acid and inorganic acid;
As a preferable technical scheme, the inorganic acid is sulfuric acid; the organic acid is oxalic acid.
As a preferable technical scheme, the oxalic acid content is 25-37 g/L, preferably 26-35 g/L, and more preferably 28-30 g/L calculated by 1L electrolyte. The sulfuric acid content is 25 to 30g/L, preferably 25 to 38g/L, and more preferably 25 to 27g/L, calculated on 1L of the electrolyte.
The principle of the invention for forming petal-shaped structures is as follows: under a certain voltage and temperature, once a voltage is applied to the titanium alloy, an oxide film, namely a barrier layer, is formed on the surface of the titanium alloy, the film layer is dissolved again after film formation under the applied voltage to form film formation-dissolution-film formation dynamic balance, the film layer is dissolved into electrochemical dissolution under direct current, the film formation-dissolution-film formation dynamic balance causes ordered rugged surface of the film layer, the rugged surface of the film layer causes uneven current distribution, the concave resistance is small but the current is large, the convex opposite direction, the concave with high current generates electrochemical dissolution of the oxide film under the action of an electric field, the concave deepens into holes, the original holes continue to be downwards formed into film-dissolution-film formation dynamic balance under the voltage continuously increased, then the ordered porous oxide film is formed, the original oxide film can be broken down only by increasing the voltage, and the current at the broken part rapidly rises to accelerate the growth of the titanium dioxide nanotube.
In order to solve the problems of hardness, corrosiveness and postoperative infection of the coating, the invention aims at overcoming the defects existing in the prior art, and the ordered nano-pore structure can be obtained by adopting green environment-friendly fluorine-free substances for anodic oxidation, so that the obtained nano-pore coating has the functions of improving corrosion resistance and hardness and inhibiting bacteria from adhering on the surface of the coating; the method overcomes the defects that ordered nanopores are obtained only by carrying out anodic oxidation treatment on a mixture which is mild and contains ethylene glycol fluoride, the existing anodic oxidation process of the mixture of ethylene glycol fluoride adopts toxic fluoride and viscous liquid, the reaction of diffusion and permeation of the viscous solution of the mixture of ethylene glycol fluoride into a film layer is difficult, the conductivity is poor, the process time is long, the coating is easy to fall off or cannot form a nano-structure coating due to poor control of the fluoride amount, the ethylene glycol has strong hygroscopicity and needs to be prepared at present, the mixture of ethylene glycol fluoride cannot be recycled as a disposable working solution, and the coating has poor hardness, corrosion resistance and wear resistance due to the anodic oxidation of the mixture of ethylene glycol fluoride.
The petal-shaped TiO2 nano-pore nano-structure obtained by treatment of the invention has large specific surface area, each petal consists of a plurality of regular and tiny nano-pores, the diameter of each petal is 0.15-1.2um, the pore diameter of each pore is 7-20nm on average, the pore depth is 20-300nm, the larger the nano-pore is, the stronger the capability of inhibiting bacteria from adhering to the surface of the nano-pore is, the poorer the hardness and the wear resistance of the nano-pore are, and the special physical surface structure with 7-20nm of pore diameter can reduce the adsorbable contact area of bacteria and has hydrophilicity, so that the effect (physical effect) of inhibiting bacteria from adhering to the surface of the nano-pore is achieved. The TiO2 nano coating with petal-shaped structure is beneficial to the adhesion and proliferation of osteoblasts and the deposition of mineralized substances induced on the surface of the osteoblasts, so that the mineralized area is increased, and the formed modified layer has the function of inhibiting the adhesion of bacteria on the surface of the modified layer 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 that are required to be used in the embodiments or the description of the prior art will be briefly described below, and it is obvious that the drawings in the following description are only embodiments of the present invention, and that other drawings can be obtained according to the provided drawings without inventive effort for a person skilled in the art.
FIG. 1 is a drawing showing an SEM image of the surface of the petal-shaped TiO 2 nano-coating obtained in example 1;
FIG. 2 is a drawing showing an SEM image of the surface of the petal-shaped TiO 2 nano-coating obtained in example 2;
FIG. 3 is a drawing showing an SEM image of the surface of the petal-shaped TiO 2 nano-coating obtained in example 4;
FIG. 4 is a graph showing EDS analysis of the petal-shaped TiO 2 nano-coating surface obtained in example 1;
FIG. 5 is a graph showing the EDS analysis of the surface of the petal-shaped TiO 2 nm-coated implant obtained in example 1 after in vitro simulated body fluid SBF soaking;
FIG. 6 is a graph showing the distribution of the number of viable bacteria of the petal-shaped TiO 2 nano-implant inoculated with Staphylococcus aureus obtained in example 1 after 24 hours of culture; the left side is a staphylococcus aureus control group, and the right side is a staphylococcus aureus to-be-tested group;
FIG. 7 is a graph showing the distribution of the number of viable bacteria of the petal-shaped TiO 2 nano-implant inoculated with E.coli obtained in example 1 after 24 hours of culture; the left side is an escherichia coli control group, and the right side is an escherichia coli to-be-detected group;
FIG. 8 is a graph of open circuit potential versus time; FIG. 8-1 is a graph of open circuit potential versus time for a petal-shaped TiO 2 nm coating obtained in example 1; FIG. 8-2 is a graph of open circuit potential versus time for a coating obtained by anodic oxidation in a prior art ethylene glycol ammonium fluoride mixture;
FIG. 9 is a graph showing the antimicrobial properties of a coating prepared using electrode solution A against Staphylococcus aureus; the left side is a control, the colony number 386, the right side is a group to be tested, and the colony number 141;
FIG. 10 is a graph showing the antibacterial properties of a coating prepared using electrode solution A against E.coli; the left side is a control, the colony number is 231, the right side is a group to be tested, and the colony number is 78;
FIG. 11 is a graph showing EDS analysis of the surface of a coated implant obtained using electrolyte A after in vitro simulated body fluid SBF soaking; after the implant is soaked in vitro simulated body fluid SBF, the coating has only 0.2 percent of phosphorus element and no calcium element. The phosphorus element may be derived from phosphoric acid in the electrolyte, indicating that the coating does not induce Ca-P coating growth;
FIG. 12 is a graph showing the antimicrobial properties of a coating prepared using electrode solution B against Staphylococcus aureus; control, colony count 628 on the left, test set, colony count 435 on the right;
FIG. 13 is a graph showing the antibacterial properties of a coating prepared using electrode solution B against E.coli; the left side is a control, the colony number is 400, the right side is a group to be tested, and the colony number is 281;
FIG. 14 is a graph showing the EDS analysis of the surface of a coated implant obtained using electrolyte B after in vitro simulated body fluid SBF soaking; after the implant is soaked in vitro simulated body fluid SBF, the coating has only 0.16% phosphorus element and no calcium element. The phosphorus element may be derived from phosphoric acid in the electrolyte, indicating that the coating does not induce Ca-P coating growth;
FIG. 15 is a graph showing open circuit potential versus time for a coating obtained with electrolyte A;
FIG. 16 is a graph showing open circuit potential versus time for a coating obtained with electrolyte B.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
A preparation method of a petal-shaped TiO 2 nanometer structure comprises the following steps:
1) Deoiling: carrying out oil removal treatment on the machined TC4 metal product;
2) Sand blasting: sand blasting is carried out on the TC4 metal product after machining so as to achieve uniform surface;
3) Cleaning: ultrasonic cleaning is carried out for 15 minutes;
4) Acid washing: carrying out acid washing treatment, namely 50g of citric acid, 4HF2 g of NH, and the balance of water by 1L of acid washing liquid, wherein the time of the acid washing treatment is 3min, and the temperature is 30 ℃;
5) Washing the TC4 metal product after pickling with purified water for 2min, washing for 10s, spraying for 10s, and washing with absolute ethyl alcohol for 10s;
6) The TC4 metal product is anodized, and calculated by 1L electrolyte, oxalic acid is 30g/L, sulfuric acid is 25g/L, the anodic oxidation voltage of the first step is 26V, the anodic oxidation time is 120 minutes, the anodic oxidation voltage of the second step is 6V higher than the voltage of the first step, and the anodic oxidation time of the second step is half of the first step; 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 24V higher than that of the third step, and the anodic oxidation time of the fourth step is the same as that of the second step;
7) Washing the product with purified water, washing, spraying, and finally washing with absolute ethyl alcohol;
8) Heat treatment, namely slowly increasing the temperature, wherein the heat treatment condition is that the temperature is increased from room temperature to 200 ℃ in the first step, the temperature increasing rate is 3.0 ℃ per minute, the temperature is kept for 10 minutes in the second step at 200 ℃, the temperature is increased to 400 ℃ in the third step, and the temperature increasing rate is 4.0 ℃ per minute; the fourth step of heat preservation at 400 ℃ for 20 minutes, the fifth step of heat preservation at 400 ℃ to 600 ℃ at the temperature rising rate of 5.0 ℃ per minute, the sixth step of heat preservation at 600 ℃ for 1 hour, and the seventh step of furnace cooling to below 100 ℃ along with furnace discharging. The SEM diagram of the obtained petal-shaped TiO 2 nanometer coating surface is shown in figure 1, and the surface EDS analysis spectrum is shown in figure 4.
Example 2
A preparation method of a petal-shaped TiO 2 nanometer structure comprises the following steps:
1) Deoiling: carrying out oil removal treatment on the machined TC4 metal product;
2) Sand blasting: sand blasting is carried out on the TC4 metal product after machining so as to achieve uniform surface;
3) Cleaning: ultrasonic cleaning is carried out for 15 minutes;
4) Acid washing: carrying out acid washing treatment, namely 50g of citric acid, 4HF2 g of NH, and the balance of water by 1L of acid washing liquid, wherein the time of the acid washing treatment is 3min, and the temperature is 30 ℃;
5) Washing the TC4 metal product after acid washing with purified water for 2min, washing for 10s, spraying for 10s, and washing with absolute ethyl alcohol for 10s
6) The TC4 metal product is anodized, and calculated by 1L electrolyte, oxalic acid is 28g/L, sulfuric acid is 26g/L, the anodic oxidation voltage of the first step is 27V, the anodic oxidation time is 110 minutes, the anodic oxidation voltage of the second step is 6V higher than the voltage of the first step, the anodic oxidation time is 60 minutes, the anodic oxidation voltage of the third step is 12V higher than the second step, the anodic oxidation time is half of the second step, the anodic oxidation voltage of the fourth step is 24V higher than the voltage of the third step, and the anodic oxidation time of the fourth step is the same as the anodic oxidation time of the second step;
7) Washing the product with purified water, washing, spraying, and finally washing with absolute ethyl alcohol;
8) Heat treatment in the same manner as in step 8) of example 1; an SEM image of the obtained petal-shaped TiO 2 nano-coating surface is shown in fig. 2.
Example 3
A preparation method of a petal-shaped TiO 2 nanometer structure comprises the following steps:
1) Deoiling: deoiling the machined TC4 metal product
2) Sand blasting: sand blasting is carried out on the TC4 metal product after machining so as to achieve uniform surface;
3) Cleaning: ultrasonic cleaning is carried out for 15 minutes;
4) Acid washing: carrying out acid washing treatment, namely 50g of citric acid, 4HF2 g of NH, and the balance of water by 1L of acid washing liquid, wherein the time of the acid washing treatment is 3min, and the temperature is 30 ℃;
5) Washing the TC4 metal product after pickling with purified water for 2min, washing for 10s, spraying for 10s, and washing with absolute ethyl alcohol for 10s;
6) Anodizing TC4 metal products, namely 30g/L oxalic acid and 27g/L sulfuric acid in 1L 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 24V higher than that of the third step, and the anodic oxidation time of the fourth step is the same as that of the second step;
7) Washing the product with purified water, washing, spraying, and finally washing with absolute ethyl alcohol;
8) Heat treatment in the same manner as in step 8) of example 1.
Example 4
A preparation method of a petal-shaped TiO 2 nanometer structure comprises the following steps:
1) Deoiling: carrying out oil removal treatment on the machined TC4 metal product;
2) Sand blasting: sand blasting is carried out on the machined aluminum alloy product to achieve uniform surface;
3) Cleaning: ultrasonic cleaning is carried out for 15 minutes;
4) Acid washing: carrying out acid washing treatment, namely 50g of citric acid, 4HF2 g of NH, and the balance of water by 1L of acid washing liquid, wherein the time of the acid washing treatment is 3min, and the temperature is 30 ℃;
5) Washing the TC4 metal product after acid washing with purified water for 2min, washing for 10s, spraying for 10s, and washing with absolute ethyl alcohol for 10s
6) Anodizing TC4 metal products, namely 30g/L oxalic acid and 27g/L sulfuric acid in 1L 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 the anodic oxidation 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 24V higher than that of the third step, and the anodic oxidation time of the fourth step is the same as that of the second step;
7) Washing the product with purified water, washing, spraying, and finally washing with absolute ethyl alcohol;
8) Heat treatment in the same manner as in step 8) of example 1; an SEM image of the obtained petal-shaped TiO 2 nano-coating surface is shown in fig. 3.
The hardness of the coatings prepared in examples 1-4, respectively, was measured and is shown in Table 1;
TABLE 1
The oxalic acid in example 1-example 4 step 6) may be replaced by citric acid, acetic acid, tartaric acid, malic acid or propionic acid; the sulfuric acid may be replaced with phosphoric acid or nitric acid.
The coating obtained in example 1 simulates in vitro body fluid SBF soaking induced Ca-P coating growth
The coating implant obtained in example 1 simulates body fluid SBF soaking to induce Ca-P coating growth in vitro, soaking for 16 days, changing SBF solution for 1 time every two days, taking out after soaking for 16 days, washing with purified water, washing with absolute ethyl alcohol, finally washing with absolute ethyl alcohol, drying, and carrying out EDS component analysis on the coating, wherein the coating has elements such as Ti, C and O, ca, P and the like, the spectrogram is shown in figure 5, ca/P=2.65/1.7=1.55, and the specific surface area of the petal-shaped structure TiO 2 nano-pore coating is large enough, and the porous structure induces Ca-P coating growth.
The coated implants obtained in example 1 were tested for bacterial anti-adhesion
Eluting the petal-shaped TiO 2 nanometer coating to-be-detected group and the positive control group sample added with a certain amount of test bacteria, detecting the residual test bacteria number on the sample pieces of the eluted petal-shaped TiO 2 nanometer coating to-be-detected group and the positive control group, and determining the difference between the average residual viable bacteria numbers of the test bacteria on the sample pieces of the positive control group and the sample pieces of the test group as the bacterial anti-adhesion rate of the test group. See fig. 6 and 7.
The method comprises the following steps: 6 pieces of sample wafers of the group to be tested, 6 pieces of sample wafers of the positive control group and 3 pieces of each test bacterium are detected respectively.
Eluting the sample pieces (3 pieces) of the to-be-detected sample group and the sample pieces (3 pieces) of the positive control group, respectively, detecting residual test bacteria on the eluted sample pieces of the to-be-detected sample group and the positive control group, and culturing for 24 hours after inoculation, wherein the bacterial anti-adhesion rate of the to-be-detected sample group= (the average viable bacteria number on the sample pieces of the positive control group-the average viable bacteria number on the sample pieces of the to-be-detected sample group)/the average viable bacteria number on the sample pieces of the positive control group is 100%.
See table 2;
table 2 example 1,2 petal TiO2 nanolayered coating bacterial anti-adhesion rates
Open circuit potential detection of the coated implant obtained in example 1
The open circuit potential is the potential measured when the metal reaches a steady state of corrosion in the absence of an applied current. Open circuit potential versus time plot was measured with a three electrode system of a working electrode reference electrode and a counter electrode, see fig. 8; no current flows in the circuit, the battery is quite in open circuit state, the voltage is carried out in 0.9 percent sodium chloride brine, the open circuit potential of the obtained coating is high,
The open circuit potential of the coating obtained in example 1 is in a relatively stable state in 3 hours of soaking, and the open circuit potential of the coating is stabilized at 180mv in FIG. 8-1, which shows that the corrosion resistance can be effectively improved by applying the coating, and the open circuit potential of the coating obtained by the mixture of ethylene glycol ammonium fluoride in the prior art fluctuates up and down at-92.5 mv to (-118 mv), which is shown as the stable state of FIG. 8-2, which is worse than the stable state of the coating obtained by the mixture of ethylene glycol ammonium fluoride in the prior art, thus indicating that the coating obtained by the technology has better corrosion resistance than the coating obtained by the mixture of ethylene glycol ammonium fluoride.
Scratch resistance test of the coated implant obtained in example 1
The method comprises the following steps: the sample to be tested with the petal-type coating is placed on a flat experiment table, the coating is cut stably at a constant speed along a straight line by a diamond pressure head according to the surface shape of a product under the action of constant normal force 5N, the scratch depth is 1.04um, and the scratch resistance of the coating is close to that of a micro-arc (black gray) anodic oxidation film.
Example 5
Comparative tests were conducted according to steps 1) to 8) in example 1 (except that the electrolyte composition was different in step 6), and the coating properties were tested as shown in fig. 9 to 16. The electrolyte is replaced by electrolyte A and electrolyte B respectively, and the electrolyte A consists of: 35g/L phosphoric acid and 5ml/L acetic acid; electrolyte B composition: 35g/L phosphoric acid and 50g/L citric acid.
From the results shown in FIGS. 9-16, 35g/L of phosphoric acid, 5ml/L of acetic acid and 35g/L of phosphoric acid were used, 50g/L of citric acid was tested in all steps (except for the difference in electrolyte composition in step 6) of example 1 and the coatings were tested for the corresponding indexes, the bacterial anti-adhesion rates of the obtained coatings were all lower than 70%, the coatings did not induce Ca-P coating growth, the coating hardness was all lower than 400HV, the open circuit potential was very unstable and fluctuated greatly, indicating poor corrosion resistance, indicating that the properties of the coatings obtained from the electrolyte composed of phosphoric acid and acetic acid could not reach the properties of the coatings obtained from the electrolyte composed of sulfuric acid and oxalic acid, and the properties of the coatings obtained from the electrolyte composed of phosphoric acid and citric acid could not reach the properties of the coatings obtained from the electrolyte composed of sulfuric acid and oxalic acid.
In the present specification, each embodiment is described in a progressive manner, and each embodiment is mainly described in a different point from other embodiments, and identical and similar parts between the embodiments are all enough to refer 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 (2)
1. The preparation method of the petal-shaped TiO 2 nano-pore antibacterial coating is characterized by comprising the following steps of:
1) Pretreatment: removing oil, sand blasting and ultrasonic cleaning of the machined TC4 metal product to obtain a pretreated metal product;
2) Acid washing: carrying out acid washing treatment on the pretreated metal product;
3) Washing, flushing and spraying: washing the TC4 metal product after acid washing with purified water for 2min,
Washing for 10s, spraying for 10s, and washing with absolute ethyl alcohol for 10s;
4) Anodic oxidation: carrying out electrolytic oxidation on the cleaned product in electrolyte for 80-150 min at 20-30V; then oxidizing for more than or equal to 40 minutes at 24-38V; oxidizing for 30min at 34-52V; oxidation at 56-78V is more than or equal to 40min; the total oxidation time is 200-300min; the electrolyte is a mixture containing organic acid and inorganic acid; the inorganic acid is sulfuric acid; the organic acid is oxalic acid; the oxalic acid content is 25 to 37g/L and the sulfuric acid content is 25 to 30g/L calculated by 1L of electrolyte;
5) Washing: washing the product with purified water, washing, spraying, and finally washing with absolute ethyl alcohol;
6) And (3) heat treatment: raising the temperature from room temperature to 200 ℃ with the temperature raising rate of 3.0 ℃/min; preserving heat at 200 ℃ for 10min; raising the temperature from 200 ℃ to 400 ℃ at a heating rate of 4.0 ℃/min; preserving heat at 400 ℃ for 20min; heating from 400 ℃ to 600 ℃, wherein the heating rate is 5.0 ℃/min, and preserving heat for 1h at 600 ℃; cooling to below 100 ℃ and discharging.
2. The method for preparing the antibacterial coating with petal-shaped TiO 2 nanometer holes according to claim 1, wherein in the step 2), the acid washing is as follows: adding 50g of citric acid and 4HF2 g of NH into 1L of water to prepare pickling solution; the pickling treatment time was 3min at 30 ℃.
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