CN112981495B - Preparation of BaTiO on titanium surface3/TiO2Method for piezoelectric antibacterial coating - Google Patents

Preparation of BaTiO on titanium surface3/TiO2Method for piezoelectric antibacterial coating Download PDF

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CN112981495B
CN112981495B CN202110181052.3A CN202110181052A CN112981495B CN 112981495 B CN112981495 B CN 112981495B CN 202110181052 A CN202110181052 A CN 202110181052A CN 112981495 B CN112981495 B CN 112981495B
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titanium
batio
tio
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CN112981495A (en
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刘磊
王若云
周潼
刘洁
杨剑飞
胡文斌
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Shanghai Jiaotong University
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02—Anodisation
    • C25D11/26—Anodisation of refractory metals or alloys based thereon
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02—Anodisation
    • C25D11/024—Anodisation under pulsed or modulated current or potential
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02—Anodisation
    • C25D11/026—Anodisation with spark discharge
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D15/00—Electrolytic or electrophoretic production of coatings containing embedded materials, e.g. particles, whiskers, wires

Abstract

The invention provides a method for preparing BaTiO on the surface of titanium3/TiO2A method of piezoelectric antimicrobial coating comprising: A. pretreating a titanium substrateC, trimming; B. immersing the pretreated titanium substrate into electrolyte, and carrying out micro-arc oxidation treatment to obtain BaTiO3/TiO2A piezoelectric antimicrobial coating; in the step B, the electrolyte comprises the following components in concentration: 0.007 to 0.028mol/L sodium silicate nonahydrate, 0.008 to 0.033mol/L sodium hexametaphosphate and 0.002 to 0.035mol/L barium titanate powder. The invention prepares BaTiO in situ on the surface of the titanium substrate by utilizing the micro-arc oxidation technology3Doped TiO 22Modifying titanium coating to obtain BaTiO with piezoelectric response3/TiO2The composite ceramic coating has antibacterial property and corrosion and wear resistance, and can be used as a surface antibacterial protective layer for underwater long-term service facilities and the like.

Description

Preparation of BaTiO on titanium surface3/TiO2Method for piezoelectric antibacterial coating
Technical Field
The invention relates to the technical field of metal surface coatings, in particular to a method for preparing BaTiO on a titanium surface3/TiO2A method for piezoelectric antibacterial coating.
Background
Because titanium and its alloy have the excellent characteristics of low density, non-magnetism, high specific strength, good biocompatibility, non-toxicity, corrosion resistance and the like, titanium and its alloy are widely used as materials of aeronautical industry, marine vessels, medical surgical instruments and the like, and particularly as marine service facilities, the titanium and its alloy can be used for treating chloride ions (Cl) in service environments-) The corrosion resistance is better. Although metallic titanium is widely used in various fields due to its excellent combination of properties, there are still some problems in practical use as the application range thereof is widened. Firstly, titanium-based metals have poor wear resistance, which affects the safety and durability of their use. Secondly, the titanium metal itself does not have antibacterial activity and is liable to cause bacterial adhesion orSurface biofouling, for example, a titanium alloy naval vessel structural member inevitably faces the problem that microorganisms in a water body attach to the surface of the titanium alloy naval vessel structural member and form biofouling when the titanium alloy naval vessel structural member is in service underwater for a long time, and the biofouling can cause a series of serious problems such as acceleration of corrosion of titanium metal of marine equipment, for example, marine organisms attached to the surface of the naval vessel can increase the weight of a ship body and increase navigation resistance, so that the speed is reduced, the fuel consumption is increased, carbon dioxide emission is increased, and the greenhouse effect is aggravated.
In order to solve the problem of adhesion of microorganisms or formation of bacterial biofilm on the surface of titanium, researchers have devised various methods for preparing antibacterial titanium coatings, wherein preparing titanium coatings loaded with chemical drugs can kill bacteria by releasing the drugs, and preparing biomimetic superhydrophobic titanium surfaces can inhibit adhesion of bacteria on the surfaces thereof by virtue of their hydrophobic properties are currently the mainstream methods. (1) Because the micro-arc oxidation technology can grow compact oxide ceramic coating which is well combined with the matrix in situ on the surface of the titanium matrix, and the ceramic coating has excellent corrosion resistance and abrasion resistance. Therefore, inorganic antibacterial agents such as Ag, Cu and Zn with broad-spectrum bactericidal activity are often doped into the micro-arc oxidation coating to improve the antibacterial performance of the micro-arc oxidation titanium coating (see Chinese patent with application number 201510796626.2, disclosing that "pure titanium surface Ag/Sr co-doped TiO coating2Preparation method of porous film "; see "International Journal of reflective Metals and Hard Materials" Journal No. "54: 417-2O/ZnO nanoparticles on Ti6Al 4V'), but still face the problem that the release of the antibacterial heavy metal ions is uncontrollable and the excessive use is caused, the heavy metal ions as the antifouling coating of the ship body can be accumulated in marine organisms and influence the human health through a food chain, the released heavy metal ions can generate adverse effects on the ecological environment, and the like. Therefore, the micro-arc oxidation coating doped with the antibacterial heavy metal elements can seriously harm the ecological environment and influence the survival of aquatic organisms. (2) Since some organisms (lotus leaf, dolphin, shark, etc.) in nature are placed in water, but can resist the adhesion of other substances, the design has low surface energyThe bionic microstructure is used as a super-hydrophobic film layer to prevent the attachment of microorganisms. The bionic microstructure surface is an environment-friendly antifouling film layer, however, the film layer has poor wear resistance and weak combination with a substrate, which greatly influences the durability of the anti-microbial fouling, and the industrialization actually needs a period of time.
Patent CN103290454A discloses a method for preparing BaTiO by improving micro-arc oxidation technology3And SrTiO3The method for preparing the BaTiO film with good surface appearance on the titanium surface by adopting the micro-arc oxidation technology3Or SrTiO3The film has a surface roughness value of 0.89 μm at least, excellent dielectric property, simple process and high film forming speed. However, the micro-arc oxidation electrolyte is single, so that the growth of the film layer is not facilitated, the prepared micro-arc oxidation layer is extremely thin and can be used for a dielectric film, and if the micro-arc oxidation layer is used as an ocean anticorrosion and antifouling coating, the micro-arc oxidation layer is extremely non-wear-resistant and cannot meet service conditions; secondly, the film prepared by the method is easy to generate BaCO3The phase is extremely easy to corrode under a slightly acidic condition, so that the integrity of the film is damaged, the corrosion of titanium metal is accelerated, and the like.
In view of the current research situation and problems, the invention aims to provide a preparation method of an antibacterial and antifouling coating based on piezoelectric response on a titanium surface, namely, a microarc oxidation technology is adopted to use spontaneously polarized BaTiO3The micro-nano particles modify the titanium surface (under the excitation of sea waves, ultrasound or other external forces, the polarization phenomenon of the modified titanium surface is more obvious), so that the titanium matrix has excellent antibacterial, corrosion-resistant and wear-resistant properties, and the problems that the traditional antibacterial micro-arc titanium oxide coating releases and sterilizes heavy metal ions to harm the ecological environment and influence the biological health are avoided. It accords with the design strategy of green, economic and long-acting antibacterial and antifouling coating.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a method for preparing BaTiO on the surface of titanium3/TiO2The method of piezoelectric antibacterial coating is based on the principle of utilizing ferroelectric BaTiO3Micro-arc oxidation coating capable of spontaneous polarization or polarization under external force actionThe surface generates electric potential difference, and relates to a new piezoelectric response antibacterial coating design strategy. Namely, micro-arc oxidation is adopted to carry out surface modification treatment on the pretreated titanium, so as to endow the TiO with corrosion resistance and wear resistance2The micro-arc oxidation coating has antibacterial performance. The prepared coating has wide application prospect for underwater long-term service facilities.
The purpose of the invention is realized by the following technical scheme:
the invention provides a method for preparing BaTiO on the surface of titanium3/TiO2A method of piezoelectric antimicrobial coating comprising the steps of:
A. pretreating a titanium substrate;
B. immersing the pretreated titanium substrate into electrolyte for micro-arc oxidation treatment to obtain BaTiO3/TiO2A piezoelectric antimicrobial coating;
in the step B, the electrolyte comprises the following components in concentration: 0.007 to 0.028mol/L sodium silicate nonahydrate, 0.008 to 0.033mol/L sodium hexametaphosphate and 0.002 to 0.035mol/L barium titanate powder (the concentration of barium titanate is too low: the prepared BaTiO3/TiO2BaTiO on the surface of coating3The particles are distributed less, and the expected antibacterial effect cannot be achieved; too high a concentration: the conductivity of the micro-arc oxidation electrolyte is reduced, the growth of the film layer is slowed, and the expected coating thickness cannot be achieved).
Preferably, in step a, the titanium substrate is titanium or a titanium alloy.
Preferably, in step a, the titanium matrix is TA1, whose chemical composition in wt.% includes: fe: 0.03 to 0.05%, C: 0.08%, N: 0.03%, H: 0.014 to 0.018%, O: 0.015-0.018%, and the balance of Ti.
Preferably, in step a, the pretreatment step comprises: sequentially polishing the titanium substrate by using 180#, 360#, 800# and 1200# SiC waterproof abrasive paper, then sequentially ultrasonically cleaning the polished sample in acetone, ethanol and pure water for 10min, and drying by cold air.
Preferably, in step B, the electrolyte comprises the following components in concentration: 0.014mol/L sodium silicate nonahydrate (Na)2SiO3·9H2O), 0.017mol/L sodium hexametaphosphate ((NaPO)3)6) 0.026mol/L barium titanate (BaTiO)3) And (3) powder.
Preferably, the barium titanate powder has a particle size of less than 3 μm and a purity of not less than 99.5%.
Preferably, in the step B, the electrolyte is prepared by pure water and is uniformly stirred, and BaTiO in the electrolyte3The powder is in suspension.
Preferably, the operation of immersing the titanium substrate into the electrolyte is as follows: the titanium matrix is hung on the bracket through the aluminum lead, and is completely immersed into the electrolyte, and meanwhile, the titanium matrix is prevented from touching the bottom and the periphery of the stainless steel electrolytic cell.
Preferably, in the step B, the operation mode of the pulse dc power supply used for the micro-arc oxidation treatment is selected from any one of a constant voltage mode and a constant current mode.
Preferably, in step B, the parameters of the constant voltage mode adopted for the micro-arc oxidation treatment are as follows: the voltage is 450-750V, the frequency is 500-1000 Hz, the pulse duty ratio is 10-40%, and the processing time is 5-20 min;
or a positive and negative pulse constant voltage mode is adopted, and the parameters are as follows: the positive pulse voltage is 500-700V, the negative pulse voltage is 50-80V, the frequency is 500-900 Hz, the positive pulse duty ratio is 20-40%, the negative pulse duty ratio is 10-20%, the number ratio of positive pulses to negative pulses is 4: 1-8: 1, and the processing time is 5-20 min;
the parameters of the micro-arc oxidation treatment adopting a constant current mode are as follows: the current is 0.2-0.6A, the frequency is 700-900 Hz, the pulse duty ratio is 20-40%, and the processing time is 5-15 min.
More preferably, in step B, the parameters of the constant voltage mode adopted for the micro-arc oxidation treatment are as follows: the voltage is 500V, the frequency is 600Hz, the pulse duty ratio is 20 percent, and the processing time is 10 min;
the parameters of the positive and negative pulse constant voltage mode are as follows: the positive pulse voltage is 500V, the negative pulse voltage is 60V, the frequency is 600Hz, the positive pulse duty ratio is 20%, the negative pulse duty ratio is 10%, the ratio of the number of positive pulses to the number of negative pulses is 4:1, and the processing time is 10 min.
The parameters of the micro-arc oxidation treatment adopting a constant current mode are as follows: the current is 0.25A, the frequency is 800Hz, the pulse duty ratio is 30 percent, and the processing time is 10 min.
Preferably, the temperature of the electrolyte is kept below 30 ℃ during the micro-arc oxidation treatment.
Preferably, the micro-arc oxidation treatment is performed in a stainless steel electrolytic cell, and the pretreated titanium substrate and the stainless steel electrolytic cell are respectively connected with the anode and the cathode of a micro-arc oxidation power supply (i.e., a pulse direct current power supply).
Preferably, after the treatment of the step B, BaTiO is generated3/TiO2And ultrasonically cleaning and drying the titanium substrate of the piezoelectric antibacterial coating.
The invention also provides BaTiO prepared by the method3/TiO2And (3) piezoelectric antibacterial coating.
Compared with the prior art, the invention has the following beneficial effects:
(1) BaTiO is prepared on the surface of a titanium substrate in situ by utilizing a micro-arc oxidation technology3Doped TiO 22Modifying titanium coating to obtain BaTiO with piezoelectric response3/TiO2The composite ceramic coating realizes that a multi-component composite coating with piezoelectric effect can be constructed by micro-arc oxidation technology.
(2) BaTiO is regulated and controlled by optimizing the components of the micro-arc oxidation electrolyte3The loading capacity of the micro-nano particles in the composite coating realizes TiO2BaTiO in the coating3The controllable preparation of the particle load provides theoretical and technical basis for the design and preparation of the composite ceramic coating with piezoelectric property.
(3) By adopting the method of the invention, the problem of corrosion resistance and wear resistance of the TiO prepared by micro-arc oxidation is solved2The surface of the ceramic coating with the porous structure is easy to adhere to biological macromolecules, bacteria and other microorganisms, and the obtained anti-corrosion wear-resistant BaTiO with antibacterial performance3/TiO2And (4) composite coating. Can be used for surface antibacterial protective layers of underwater long-term service facilities (such as naval vessels, water pipelines, submarine cables and the like).
(4) The method provides the concept of dynamic surface antibacterial and antifouling, and opens up a new antibacterial and marine antifouling path based on piezoelectric response.
(5) The method is a new antibacterial coating design strategy, has simple preparation process, high production efficiency and low cost, can solve the defects of short effective period and the like of the existing antibacterial and antifouling coatings (the traditional antibacterial metal ion (Ag, Cu, Zn and the like) doped micro-arc oxidation coating is easy to release the antibacterial metal ion and does not have the antibacterial effect in the later period), and the BaTiO in the antibacterial coating of the invention3Extremely stable and not easy to release, and thus has long-lasting antibacterial properties).
Drawings
Other features, objects and advantages of the invention will become more apparent upon reading of the detailed description of non-limiting embodiments with reference to the following drawings:
FIG. 1 is a schematic view of a micro-arc oxidation apparatus used in the present invention; 1-micro arc oxidation pulse direct current power supply, 2-titanium substrate (anode), 3-stainless steel electrolytic cell (cathode), 4-stirrer and 5-circulating cooling water tank device;
FIG. 2 is BaTiO prepared in example 13/TiO2Coating surface SEM microscopic morphology picture;
FIG. 3 shows BaTiO in example 13/TiO2BaTiO on the surface of coating3Surface potential differences resulting from spontaneous particle polarization;
FIG. 4 shows untreated titanium samples (Ti) and BaTiO3/TiO2The contrast picture of the bacterial reproduction colony on the coating surface, and the white dots in the picture represent the bacterial colony.
Detailed Description
The present invention will be described in detail with reference to specific examples. The following examples will aid those skilled in the art in further understanding the present invention, but are not intended to limit the invention in any manner. It should be noted that variations and modifications can be made by persons skilled in the art without departing from the concept of the invention. All falling within the scope of the present invention.
The micro-arc oxidation equipment adopted in the following embodiment is shown in fig. 1, and comprises a micro-arc oxidation pulse direct current power supply 1, a titanium substrate 2, a stainless steel electrolytic cell 3, a stirrer 4 and a circulating cooling water tank device 5.
Example 1
This example provides a method for preparing BaTiO on the surface of a titanium substrate3/TiO2The method for piezoelectric antibacterial coating comprises the following steps:
(1) cutting a titanium substrate TA1 (the chemical components of which are (wt.%), Fe is 0.03-0.05%, C is 0.08%, N is 0.03%, H is 0.014-0.018%, O is 0.015-0.018%, and the balance is Ti (purity is more than or equal to 99.8 wt.%)) into square samples of 50 x 0.5mm, sequentially grinding and polishing the square samples by 180#, 360#, 800# and 1200# abrasive paper step by step, then respectively carrying out ultrasonic cleaning on the polished titanium substrate in acetone, ethanol and pure water for 10min to obtain a pre-treated titanium sample, and drying the titanium substrate by cold air for later use;
(2) immersing the pretreated titanium sample obtained in the step (1) into a solution containing 0.014mol/L of Na through a wire2SiO3·9H2O, 0.017mol/L (NaPO)3)6And 0.026mol/L of BaTiO3Adding powder (particle diameter less than 3 μm) into electrolyte (3L prepared from above chemical reagents with pure water), pouring into stainless steel electrolytic cell, starting stirrer, stirring to ensure uniform mixing of electrolyte, and making BaTiO3The powder is in a suspension state, a circulating cooling water system is started to keep the temperature of the electrolyte below 30 ℃ in the micro-arc oxidation reaction process, the pre-treated titanium sample is hung on the bracket through an aluminum wire, the titanium sample is completely immersed in the electrolyte, and the sample is prevented from touching the bottom and the periphery of the stainless steel electrolytic cell;
then respectively connecting the pre-treated titanium sample and the stainless steel electrolytic cell with the anode and the cathode of a micro-arc oxidation pulse direct current power supply through leads to obtain a well-connected micro-arc oxidation device;
(3) opening the connected micro-arc oxidation device pulse direct current power supply in the step (2), and performing micro-arc oxidation treatment for 10min under the operation parameters that the operation mode is a constant voltage mode, namely the voltage is 500V, the frequency is 600Hz, and the pulse duty ratio is 20 percent to obtain BaTiO3Doped TiO 22And (4) coating.
(4) After the micro-arc oxidation treatment is finished, BaTiO is further obtained on the surface3/TiO2The titanium sample of the coating is processed into a square sample with the thickness of 10 multiplied by 0.5mm, and is sequentially immersed into acetone, ethanol and pure water for ultrasonic cleaning, dried by cold air and put into a drying oven for characterization analysis and performance test.
Through the steps of the embodiment, BaTiO with excellent antibacterial performance can be prepared on the surface of the titanium substrate3Doped TiO 22And (4) coating. Observed by a scanning electron microscope, the micro-nano BaTiO3The particles are uniformly distributed in the BaTiO3/TiO2The surface of the coating is filled into the micro-hole holes of the micro-arc oxidation coating (figure 2).
FIG. 3 shows BaTiO prepared in this example3/TiO2BaTiO on the surface of coating3The surface potential generated by spontaneous polarization of the particles showed that BaTiO3Particles and TiO2There is a significant potential difference between them.
FIG. 4 shows pure titanium substrate TA1 and BaTiO-containing material prepared by the procedure of this example3/TiO2The result of bacterial colony propagation on the surface of the titanium sample of the coating cultured for 24 hours under the conditions of no light and static state can be obviously seen, and BaTiO is formed by surface micro-arc oxidation3/TiO2The coating can obviously inhibit the growth and proliferation of bacteria.
Example 2
This example provides a method for preparing BaTiO on the surface of a titanium substrate3/TiO2The procedure of the piezoelectric antibacterial coating method is basically the same as that of the example 1, except that: in the experimental example, in order to improve the surface roughness of the micro-arc oxidation coating in the step (3), the micro-arc oxidation voltage output is positive and negative pulses, the positive pulse voltage is 500V, the negative pulse voltage is 60V, the frequency is 600Hz, the duty ratio of the positive pulse is 20%, the duty ratio of the negative pulse is 10%, and the ratio of the number of the positive and negative pulses is 4: 1.
BaTiO prepared in this example3/TiO2The surface roughness of the coating was 1.45 μm (the surface roughness of the coating obtained in example 1 was 2.19 μm), and compared with example 1, the micro-arc discharge intensity was significantly reduced and the roughness was significantly reducedThe hardness is improved, and the internal defects of the coating are reduced.
Example 3
This example provides a method for preparing BaTiO on the surface of a titanium substrate3/TiO2The procedure of the piezoelectric antibacterial coating method is basically the same as that of the example 1, except that: in this embodiment, in order to obtain a micro-arc oxidation coating with an appreciable thickness in step (3), the micro-arc oxidation treatment is performed for 10min under the operating parameters that the operating mode is a constant current mode, that is, the current is 0.25A, the frequency is 800Hz, and the pulse duty ratio is 30%.
BaTiO prepared in this example3/TiO2The thickness of the coating was 18 μm (the thickness of the coating obtained in example 1 was 12 μm), and compared to example 1, although the oxidation resistance was increased due to the increase in the thickness of the micro arc oxidation film layer, the oxidation current was constant, so that the growth of the micro arc oxidation film layer was not reduced in the late stage.
Example 4
This example provides a method for preparing BaTiO on the surface of a titanium substrate3/TiO2The procedure of the piezoelectric antibacterial coating method is basically the same as that of the example 1, except that: in this experimental example, the electrolyte in the step (2) includes the following components in concentration: 0.007mol/L sodium silicate nonahydrate (Na)2SiO3·9H2O), 0.008mol/L sodium hexametaphosphate ((NaPO)3)6) 0.002mol/L barium titanate (BaTiO)3) And (3) powder.
BaTiO prepared in this example3/TiO2Surface of the coating BaTiO3The particles are sparsely distributed, and compared with the embodiment 1, the micro-arc discharge strength is obviously weakened due to the reduction of the concentration of the electrolyte.
Example 5
This example provides a method for preparing BaTiO on the surface of a titanium substrate3/TiO2The procedure of the piezoelectric antibacterial coating is basically the same as that of example 1, except that: in this experimental example, the electrolyte in the step (2) includes the following components in concentration: 0.028mol/L sodium silicate nonahydrate (Na)2SiO3·9H2O), 0.033mol/L sodium hexametaphosphate ((Na)PO3)6) 0.035mol/L barium titanate (BaTiO)3) And (3) powder.
BaTiO prepared in this example3/TiO2Surface BaTiO of the coating3The particles are densely distributed, compared with the embodiment 1, the micro-arc discharge strength is obviously enhanced at the initial stage due to the increase of the concentration of the electrolyte, and meanwhile, due to BaTiO in the electrolyte3The suspension powder concentration is increased, so that the conductivity of the micro-arc oxidation electrolyte is reduced, and the micro-arc discharge strength is slightly weakened in the later period.
The embodiments described above are described to facilitate an understanding and use of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.

Claims (8)

1. BaTiO prepared on titanium surface3/TiO2A method of piezoelectric antimicrobial coating, comprising the steps of:
A. pretreating the titanium substrate;
B. immersing the pretreated titanium substrate into electrolyte, and carrying out micro-arc oxidation treatment to obtain BaTiO3/TiO2A piezoelectric antimicrobial coating;
in the step B, the electrolyte comprises the following components in concentration: 0.007-0.028 mol/L sodium silicate nonahydrate, 0.008-0.033 mol/L sodium hexametaphosphate and 0.002-0.035 mol/L barium titanate powder;
in the step B, the operation mode of the pulse direct current power supply adopted by the micro-arc oxidation treatment is selected from any one of a constant voltage mode and a constant current mode;
in the step B, the parameters of the micro-arc oxidation treatment adopting the constant voltage mode are as follows: the voltage is 450-750V, the frequency is 500-1000 Hz, the pulse duty ratio is 10-40%, and the processing time is 5-20 min;
or a positive and negative pulse constant voltage mode is adopted, and the parameters are as follows: the positive pulse voltage is 500-700V, the negative pulse voltage is 50-80V, the frequency is 500-900 Hz, the positive pulse duty ratio is 20-40%, the negative pulse duty ratio is 10-20%, the number ratio of positive pulses to negative pulses is 4: 1-8: 1, and the processing time is 5-20 min;
the parameters of the micro-arc oxidation treatment adopting a constant current mode are as follows: the current is 0.2-0.6A, the frequency is 700-900 Hz, the pulse duty ratio is 20-40%, and the processing time is 5-15 min.
2. The titanium surface preparation BaTiO according to claim 13/TiO2The method for the piezoelectric antibacterial coating is characterized in that in the step A, the titanium substrate is titanium or titanium alloy.
3. BaTiO prepared on titanium surface according to claim 23/TiO2The method for piezoelectric antibacterial coating is characterized in that in the step A, the titanium matrix is TA1, and the chemical composition of the titanium matrix in wt.% comprises the following steps: fe: 0.03-0.05%, C: 0.08%, N: 0.03%, H: 0.014-0.018%, O: 0.015-0.018%, and the balance of Ti.
4. The titanium surface preparation BaTiO according to claim 13/TiO2The method for piezoelectric antibacterial coating is characterized in that in the step A, the pretreatment step comprises the following steps: sequentially polishing the titanium substrate by using 180#, 360#, 800# and 1200# SiC waterproof abrasive paper, then sequentially ultrasonically cleaning the polished sample in acetone, ethanol and pure water for 10min, and drying by cold air.
5. The titanium surface preparation BaTiO according to claim 13/TiO2The method for piezoelectric antibacterial coating is characterized in that in the step B, the electrolyte comprises the following components in concentration: 0.014mol/L sodium silicate nonahydrate, 0.017mol/L sodium hexametaphosphate and 0.026mol/L barium titanate powder.
6. According to claim 1 or 5The BaTiO is prepared on the surface of the titanium3/TiO2The method for preparing the piezoelectric antibacterial coating is characterized in that the particle size of the barium titanate powder is less than 6 mu m, and the purity is 99.5% or more.
7. The titanium surface preparation BaTiO according to claim 13/TiO2The method for preparing the piezoelectric antibacterial coating is characterized by further comprising the step of generating BaTiO after the step B of treatment3/TiO2And carrying out ultrasonic cleaning and blow-drying on the titanium substrate of the piezoelectric antibacterial coating.
8. BaTiO prepared according to the method of claim 13/TiO2And (3) piezoelectric antibacterial coating.
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CN101260558A (en) * 2008-04-23 2008-09-10 哈尔滨工业大学 Method for preparing corrosion-resisting wear-proof ceramic coat on TA15 titanium alloy surface
CN106757056B (en) * 2016-11-16 2019-03-15 武汉理工大学 A kind of preparation method of barium titanate/nano titania composite film material
CN108147811A (en) * 2017-12-29 2018-06-12 中国人民解放军陆军装甲兵学院 A kind of preparation method of the doped barium titanate ceramics coating of functionalization

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