CN115558323A - Antibacterial polytitanium azane coating composition and preparation method thereof - Google Patents
Antibacterial polytitanium azane coating composition and preparation method thereof Download PDFInfo
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- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims abstract description 38
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- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 9
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 9
- 229920002554 vinyl polymer Polymers 0.000 claims description 9
- 230000000845 anti-microbial effect Effects 0.000 claims description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
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- 238000000576 coating method Methods 0.000 abstract description 55
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- 238000005260 corrosion Methods 0.000 abstract description 13
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- 241000237536 Mytilus edulis Species 0.000 description 1
- 101100244625 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) pph-1 gene Proteins 0.000 description 1
- 229910007991 Si-N Inorganic materials 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 229910006294 Si—N Inorganic materials 0.000 description 1
- COGOJRKCCAQAPE-UHFFFAOYSA-N [N].[Si].[Ti] Chemical compound [N].[Si].[Ti] COGOJRKCCAQAPE-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/14—Paints containing biocides, e.g. fungicides, insecticides or pesticides
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- C—CHEMISTRY; METALLURGY
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- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
- C09D183/16—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers in which all the silicon atoms are connected by linkages other than oxygen atoms
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- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/16—Antifouling paints; Underwater paints
- C09D5/1606—Antifouling paints; Underwater paints characterised by the anti-fouling agent
- C09D5/1612—Non-macromolecular compounds
- C09D5/1618—Non-macromolecular compounds inorganic
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- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/16—Antifouling paints; Underwater paints
- C09D5/1656—Antifouling paints; Underwater paints characterised by the film-forming substance
- C09D5/1662—Synthetic film-forming substance
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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Abstract
The invention relates to a coating, in particular to an antibacterial polytitanium azane coating composition and a preparation method thereof. The invention provides an antibacterial titanium polynitrogen coating composition and a preparation method thereof, aiming at solving the problem of biofouling in the existing marine corrosion. The raw materials of the coating composition comprise 10% ethanol solution of Polytitasilazane (PTSZ), ag-MWCNTs, sodium Dodecyl Sulfate (SDS) and polyvinylpyrrolidone (PVP). Compared with the prior art, the coating formed by the antibacterial polytitanium azane coating composition provided by the invention has excellent antibacterial performance and super-hydrophilic performance, and can solve the problems of micro-biofouling and macro-biofouling of biofouling in marine corrosion.
Description
Technical Field
The invention relates to a coating, in particular to an antibacterial poly titanium nitrogen alkane coating composition and a preparation method thereof.
Background
Polysilazanes are inorganic polymers with Si-N bond repeating units as main chains, have many advantages as marine anti-biofouling precursor coatings, and firstly, the coating obtained after curing mainly contains inorganic SiO 2 The coating has lower surface energy and excellent hydrophobic property, and can greatly reduce the attachment of marine organisms such as bacteria, algae, mussels and the like; secondly, the curing process of polysilazane is very simple. However, the application of the method in the field of marine antifouling still has some problems to be solved urgently, and because marine organisms have various species and complex fouling process, the biofouling has particularly serious influence on the corrosion of metal materials. Biofouling in marine corrosion can be divided into two broad categories, namely micro biofouling and macro biofouling, wherein the effect of micro biofouling is mainly that microbial metabolic processes affect the corrosion rate of metal surfaces, such as acid metabolism produces substances capable of initiating a cathode reaction. Macroscopic biofouling refers to attachment of macroscopic organisms, which can increase navigation resistance of ships, cause huge losses due to blockage of seawater pipelines, mariculture and the like, and can also accelerate the local corrosion speed of materials.
Disclosure of Invention
The invention provides an antibacterial titanium polynitrogen coating composition and a preparation method thereof, aiming at solving the problem of biofouling in the existing marine corrosion.
The invention overcomes the defects in the prior art, and provides an antibacterial polytitanium azide coating composition and a preparation method thereof, wherein a coating with high hardness and adhesive force and antibacterial and super-hydrophilic properties is prepared by blending modified carbon nano-tubes with polytitanium azide with nano-silver and then curing the mixture at high temperature by water vapor, wherein Ag nano-particles are deposited on the surfaces of multi-walled carbon nano-tubes (MWCNTs) by reducing silver ions with ethanol, so that the coating is environment-friendly and pollution-free.
In order to solve the technical problems, the invention is realized by the following technical scheme:
the invention provides an antibacterial polytitanium azane coating composition, which comprises 10% of polytitanium silazane (PTSZ) ethanol solution and Ag-MWCNTs.
The invention provides an antibacterial polytitanium azane coating composition, which comprises 10% of polytitanium silazane (PTSZ) ethanol solution, ag-MWCNTs, sodium Dodecyl Sulfate (SDS) and polyvinylpyrrolidone (PVP).
Further, the raw materials of the coating composition comprise 100 parts of 10% ethanol solution of Polytitasilazane (PTSZ), 1-4 parts of Ag-MWCNTs, 0.5-2 parts of Sodium Dodecyl Sulfate (SDS) and 0.25-1 part of polyvinylpyrrolidone (PVP); the parts are parts by mass.
Further, the raw materials of the coating composition comprise 100 parts of 10% ethanol solution of Polytitasilazane (PTSZ), 2 parts of Ag-MWCNTs, 1 part of Sodium Dodecyl Sulfate (SDS) and 0.5 part of polyvinylpyrrolidone (PVP); the parts are parts by mass.
Further, the raw materials of the 10% poly titanium silicon nitrogen alkyl alcohol solution include titanium (IV) isopropoxide, vinyl Polysilazane (PVSZ), and ethanol.
Further, the raw materials of the 10% polytitanium silazane ethanol solution comprise 3 parts of titanium (IV) isopropoxide, 4 parts of vinyl Polysilazane (PVSZ) and 63 parts of ethanol; the parts are parts by mass.
Further, the raw materials of the Ag-MWCNTs comprise multi-walled carbon nanotubes (MWCNTs) and AgNO 3 And (3) solution.
Furthermore, the raw material of the Ag-MWCNTs comprises 10 grams of multi-walled carbon nanotubes (MWCNTs) and 50ml of 17 grams of AgNO 3 And (3) solution. 17g is AgNO 3 The quality of (c).
Further, the raw material of the Ag-MWCNTs comprises multi-walled carbon nanotubes (MWCNTs), agNO 3 Solution, acid, and ethanol.
Further, the AgNO 3 The solution being AgNO 3 And (4) standard solution.
Further, theThe acid of (A) is nitric acid (H) 3 NO 3 ) And sulfuric acid (H) 2 SO 4 ). The nitric acid (H) 3 NO 3 ) And sulfuric acid (H) 2 SO 4 ) Is 3:1.
a coating formed by the antibacterial poly titanium nitrogen alkane coating composition has excellent antibacterial performance and super-hydrophilic performance, and is also called as an antibacterial limit super-hydrophilic poly titanium nitrogen alkane coating composition.
In another aspect, the present invention provides a method for preparing an antibacterial polytitazane coating composition, the method comprising the steps of:
(1) Uniformly mixing a certain amount of titanium (IV) isopropoxide and vinyl Polysilazane (PVSZ), transferring the mixture into a round-bottom flask, heating the mixture in a water bath, replacing air in the flask with nitrogen, and performing oil bath at high temperature to obtain the polytitanium silazane (PTSZ); adding a certain amount of ethanol into the polytitanium silazane (PTSZ), and uniformly mixing to prepare a 10% polytitanium silazane ethanol solution;
(2) Subjecting multi-walled carbon nanotubes (MWCNTs) to ultrasonic treatment in acid, washing with deionized water, ultrasonically dispersing centrifugally dried MWCNTs, and slowly dropwise adding AgNO 3 The solution, after magnetic stirring, was filtered and the residual AgNO was taken up with ethanol 3 Obtaining multi-wall carbon nano-tubes (Ag-MWCNTs) attached with Ag particles;
(3) And (3) adding the 10% poly titanium silicon nitrogen alkyl ethanol solution obtained in the step (1) into the Ag-MWCNTs obtained in the step (2), adding Sodium Dodecyl Sulfate (SDS) and polyvinylpyrrolidone (PVP), and dispersing and mixing through ultrasonic oscillation to obtain the antibacterial poly titanium nitrogen alkyl coating composition.
Further, the method comprises the following steps:
(1) Certain amounts of titanium (IV) isopropoxide and vinyl Polysilazane (PVSZ) are mixed uniformly and transferred to a round bottom flask, heated in a water bath, the air in the flask is replaced by nitrogen and subjected to oil bath at high temperature. The color of the mixed solution slowly changes from milky white to yellow, then to blackish green and finally to reddish brown. Finally, adding a certain amount of ethanol solution into the obtained polytitanium silazane (PTSZ) and uniformly mixing to prepare a 10% polytitanium silazane ethanol solution.
(2) Subjecting multi-wall carbon nanotubes (MWCNTs) to ultrasonic treatment in excessive acid, washing with deionized water, ultrasonically dispersing centrifugally dried MWCNTs, and slowly dropwise adding AgNO 3 The solution, after magnetic stirring, was filtered and the residual AgNO was taken up with ethanol 3 And obtaining the multi-wall carbon nano-tube (Ag-MWCNTs) attached with Ag particles.
(3) And (3) adding the 10% polytitazenitridoethanol solution obtained in the step (1) into the Ag-MWCNTs obtained in the step (2), adding Sodium Dodecyl Sulfate (SDS) and polyvinylpyrrolidone (PVP), and dispersing and mixing by ultrasonic oscillation to obtain a stable antibacterial polytitazenitridoethane coating composition (also called antibacterial limit super-hydrophilic suspension).
Coating a layer of antibacterial polytitanium azane coating composition on the surface of a DH36 steel sample by a dip coating method, heating the coating composition to 800 ℃ in a tubular furnace, curing the coating by water vapor, and taking out the coating after the coating is kept warm for 2 hours. The antimicrobial titanyl azide coating composition forms a coating.
Further, the mass ratio of the titanium (IV) isopropoxide to the vinyl Polysilazane (PVSZ) in the step (1) is 3:4.
further, the water bath heating in the step (1) refers to water bath at 80 ℃ for 30min.
Further, the high temperature oil bath in the step (1) means that the oil bath is carried out at 160 ℃ for 8 hours.
Further, the ethanol added in the step (1) is 9 times of the mass of the Polytitasilazane (PTSZ), and a PTSZ ethanol solution with the mass fraction of 10% is prepared.
Further, the acid in the step (2) is nitric acid (H) 3 NO 3 ) And sulfuric acid (H) 2 SO 4 )。
Further, the acid in the step (2) is nitric acid (H) 3 NO 3 ) And sulfuric acid (H) 2 SO 4 ) Added nitric acid (H) 3 NO 3 ) And sulfuric acid (H) 2 SO 4 ) Is 3:1.
further, the washing of step (2) with deionized water is carried out until the pH is 7.0.
Further, agNO described in step (2) 3 The solution was 50ml of 17g AgNO 3 And (4) standard solution.
Further, the mass ratio of the Ag-MWCNTs, the Sodium Dodecyl Sulfate (SDS) and the polyvinylpyrrolidone (PVP) in the step (3) is 4:2:1.
aiming at the micro biofouling of biofouling in marine corrosion, a coating formed by the coating composition provided by the invention can resist bacteria, inhibit the growth of microorganisms, and play roles in protecting metal and preventing corrosion in the aspect of microorganisms; aiming at the macroscopic biofouling of biofouling in marine corrosion, the super-hydrophilic action of the coating ensures that the surface water spreadability of the coating is good, and some macroscopic marine organisms are not easy to be stained on the coating and are easy to be taken away by seawater, thereby playing the effect of preventing corrosion.
Compared with the prior art, the invention has the beneficial effects that:
from the perspective of environmental protection, ag nanoparticles are successfully deposited on the surfaces of multi-walled carbon nanotubes (MWCNTs) by reducing silver ions through ethanol. And then the Ag-MWCNTs are uniformly dispersed in an alcohol solution of the polytitasilazane, so that Ag nanoparticles can be uniformly distributed, agglomeration is reduced, the MWCNTs become a basic framework of a micro-nano structure during solidification, a surface layer with the micro-nano structure is woven, and the antibacterial suspension precursor is obtained. By controlling the curing temperature, the poly-titanium-silicon-nitrogen-alkane is cured along the surface of the poly-titanium-silicon-alkane, so that the effects of antibiosis and extreme super-hydrophilicity are achieved. Values for the contact angle of the coating surface less than 3 ° may be referred to as superhydrophilic; because the contact angle of the surface of the coating can reach 0 degrees, the coating is called extreme super-hydrophilicity.
Compared with the prior art, the coating formed by the antibacterial polytitanium azane coating composition provided by the invention has excellent antibacterial performance and super-hydrophilic performance, and can solve the problems of micro-biofouling and macro-biofouling of biofouling in marine corrosion.
Drawings
FIG. 1 is an equivalent simulation diagram of Ag-MWCNTs.
Detailed Description
The following description of the preferred embodiments of the present invention is provided for the purpose of illustration and description and is not intended to be limiting.
In examples 1-4: preparing an ethanol solution of PTSZ with a mass fraction of 10%: titanium (IV) isopropoxide and vinyl Polysilazane (PVSZ) were mixed in the ratio of 3. The color of the mixed solution slowly changes from milky white to yellow, then to dark green, and finally to reddish brown. Finally, the obtained Polytitazenitridosilane (PTSZ) was stored in a nitrogen atmosphere under a sealed condition. Adding 9 times of ethanol solution into the polytitanium silazane (PTSZ), and uniformly mixing to prepare the 10% polytitanium silazane ethanol solution.
Preparing Ag-MWCNTs: 10 g of MWCNTs were dissolved in an excess of acid (H) 2 SO 4 :HNO 3 Is 1); then the MWCNTs-COOH after centrifugal drying is dispersed in 250ml ethanol in an ultrasonic mode, and 50ml of 17g of AgNO is slowly dripped 3 Standard solution, after magnetic stirring for one hour, it was filtered and the residual AgNO was taken up with ethanol 3 And obtaining the Ag-MWCNTs.
The coating formed by the antibacterial polytitanium azane coating composition provided by the embodiment of the invention, the coating formed by the comparative example and the steel plate provided by the comparative example 2 are subjected to main performance detection by adopting the following method.
Pencil hardness (H): the test was carried out according to GB/T6739-86 using a pencil hardness tester of the PPH-1 type. And (3) after the coating is cured, placing the sample plate in a horizontal position, pushing a pencil with gradually increased hardness to determine the surface position of the coating, and taking the pencil hardness when no scratch appears on the surface as the hardness value of the coating pencil.
Adhesion test (B): the surface of the coating film was cut into 10X 10 grids spaced 2mm apart by a scriber according to GB/T9286-1998 test for adhesion by scriber method, and an adhesive tape was applied to the grids, followed by tearing at a proper and uniform speed. And (3) performing adhesion tests at three different positions of the coating, wherein the number of the falling grids is 0, less than 5%, 5% -15%, 15% -35%, 35% -65% and more than 65%, and the adhesion grades are respectively 5B-0B.
Contact angle CA (°): the wetting angle of the water drop on the sample is tested by a contact angle tester and a water drop method. The smaller the contact angle tested, the better the hydrophilic properties, and those having a contact angle of less than 3 ° are currently referred to as superhydrophilic.
Mean peak to valley deviation of coating profile Rz (μm): the sum of the average value of 5 maximum profile peak heights and the average value of 5 maximum profile valley depths in the range of the test sampling length is represented and directly tested by a roughness meter. The larger Rz in a certain range is, the rougher the surface is, and the more prominent the micro-nano structure of the surface is. The micro-nano structure refers to a microstructure on the surface of the coating after curing, and is highlighted due to the skeleton supporting effect of the carbon nano tubes. The larger the Rz is, the more obvious the micro-nano structure is.
Number of colonies (number) in the medium after 24 hours: coating the antibacterial polytitanium azane coating composition (also called antibacterial super-hydrophobic suspension) in a culture medium, then keeping the temperature at 400 ℃ for 2h in a curing process, sequentially treating the sample by using ethanol and an ultraviolet lamp, sterilizing the surface of the sample, and then putting the treated sample in a saturated escherichia coli solution (10) 8 CFU/mL). After a period of soaking, the surface bacteria solution was gently washed away with Phosphate Buffered Saline (PBS), and the bacteria attached to the sample surface were vortexed down. 100. Mu.L of the bacterial liquid was applied to the medium, and the number of colonies on the medium was counted after 24 hours. The smaller the number of colonies, the more excellent the antibacterial property.
Example 1:
the present example provides an antimicrobial titanium polyazane coating composition, and a coating formed therefrom.
To 100 parts of a 10% ethanol solution of Polytitazanlazane (PTSZ), 2 parts of Ag-MWCNTs, 1 part of Sodium Dodecyl Sulfate (SDS) and 0.5 part of polyvinylpyrrolidone (PVP) were added, and dispersed by ultrasonic oscillation to obtain a stable antibacterial polytitazan coating composition (also referred to as an antibacterial limit superhydrophilic suspension, or a limit superhydrophilic suspension).
Coating a layer of extreme super-hydrophilic suspension on the surface of a DH36 steel sample by a dip coating method, heating the suspension to 800 ℃ in a tubular furnace, curing the suspension by water vapor, and taking out the suspension after the heat preservation is carried out for 2 hours. A coating with a thickness of about 5 μm was produced.
Example 2:
preparing a 10% ethanol solution of Polytitasilazane (PTSZ), adding 1 part of Ag-MWCNTs, 0.5 part of Sodium Dodecyl Sulfate (SDS) and 0.25 part of polyvinylpyrrolidone (PVP) into the ethanol solution, and dispersing by ultrasonic oscillation to obtain a stable antibacterial limit super-hydrophilic suspension.
Coating a layer of extreme super-hydrophilic suspension on the surface of a DH36 steel sample by a dip coating method, heating the suspension to 800 ℃ in a tubular furnace, curing the suspension by water vapor, and taking out the suspension after the heat preservation is carried out for 2 hours. A coating with a thickness of about 5 μm was produced.
Example 3:
preparing a 10% ethanol solution of Polytitasilazane (PTSZ), adding 3 parts of Ag-MWCNTs, 1.5 parts of Sodium Dodecyl Sulfate (SDS) and 0.75 part of polyvinylpyrrolidone (PVP) into the ethanol solution, and dispersing by ultrasonic oscillation to obtain a stable antibacterial limit super-hydrophilic suspension.
Coating a layer of extreme super-hydrophilic suspension on the surface of a DH36 steel sample by a dip coating method, heating the suspension to 800 ℃ in a tubular furnace, curing the suspension by water vapor, and taking out the suspension after the heat preservation is carried out for 2 hours. A coating with a thickness of about 5 μm was produced.
Example 4:
preparing a 10% ethanol solution of Polytitasilazane (PTSZ), adding 4 parts of Ag-MWCNTs, 2 parts of Sodium Dodecyl Sulfate (SDS) and 1 part of polyvinylpyrrolidone (PVP) into the ethanol solution, and dispersing by ultrasonic oscillation to obtain a stable antibacterial limit super-hydrophilic suspension.
Coating a layer of extreme super-hydrophilic suspension on the surface of a DH36 steel sample by a dip coating method, heating to 800 ℃ in a tubular furnace, curing by water vapor, preserving heat for 2 hours, and taking out. A paint film having a thickness of about 5 μm was produced.
Comparative example 1
Preparing an ethanol solution of Polytitasilazane (PTSZ) with the mass fraction of 10% as a precursor of the corrosion-resistant coating. After uniform mixing, a layer of precursor solution is coated on the surface of a DH36 steel sample by a dip coating method, and the mixture is dried in air for 15min. Finally, the sample was suspended in an oven, and a pot of water was placed in the oven, and the water was steam cured at 150 ℃ for 2h. A coating with a thickness of about 5 μm was produced.
Comparative example 2
The DH36 steel samples were surface cleaned as controls.
Comparative example 3
Preparing a 10% ethanol solution of Polytitasilazane (PTSZ), adding 2 parts of Ag-MWCNTs, 0.2 part of Sodium Dodecyl Sulfate (SDS) and 0.1 part of polyvinylpyrrolidone (PVP) into the ethanol solution, and dispersing by ultrasonic oscillation to obtain a stable antibacterial limit super-hydrophilic suspension.
Coating a layer of extreme super-hydrophilic suspension on the surface of a DH36 steel sample by a dip coating method, heating the suspension to 800 ℃ in a tubular furnace, curing the suspension by water vapor, and taking out the suspension after the heat preservation is carried out for 2 hours. A coating with a thickness of about 5 μm was produced.
Comparative example 4
Preparing a 10% ethanol solution of Polytitasilazane (PTSZ), adding 2 parts of Ag-MWCNTs, 4 parts of Sodium Dodecyl Sulfate (SDS) and 2 parts of polyvinylpyrrolidone (PVP) into the ethanol solution, and dispersing by ultrasonic oscillation to obtain a stable antibacterial limit super-hydrophilic suspension.
Coating a layer of extreme super-hydrophilic suspension on the surface of a DH36 steel sample by a dip coating method, heating to 800 ℃ in a tubular furnace, curing by water vapor, preserving heat for 2 hours, and taking out. A coating with a thickness of about 5 μm was produced.
Comparative example 5
100 parts of ethanol solution of 10% polytitanium silazane (PTSZ) is prepared, 0.5 part of Ag-MWCNTs, 0.2 part of Sodium Dodecyl Sulfate (SDS) and 0.1 part of polyvinylpyrrolidone (PVP) are added, and stable antibacterial limit super-hydrophilic suspension is obtained through ultrasonic oscillation and dispersion.
Coating a layer of extreme super-hydrophilic suspension on the surface of a DH36 steel sample by a dip coating method, heating the suspension to 800 ℃ in a tubular furnace, curing the suspension by water vapor, and taking out the suspension after the heat preservation is carried out for 2 hours. A coating with a thickness of about 5 μm was produced.
Comparative example 6
Preparing 100 parts of 10% ethanol solution of polytitanium silazane (PTSZ), adding 5 parts of Ag-MWCNTs, 4 parts of Sodium Dodecyl Sulfate (SDS) and 2 parts of polyvinylpyrrolidone (PVP), and dispersing by ultrasonic oscillation to obtain a stable antibacterial limit super-hydrophilic suspension.
Coating a layer of extreme super-hydrophilic suspension on the surface of a DH36 steel sample by a dip coating method, heating the suspension to 800 ℃ in a tubular furnace, curing the suspension by water vapor, and taking out the suspension after the heat preservation is carried out for 2 hours. A coating with a thickness of about 5 μm was produced.
Table 1 test results for coatings provided in examples 1-4
Table 2 test results of the coatings provided in comparative examples 1, 3 to 6, and the steel sheet provided in comparative example 2
The coating formed by the antibacterial polytitanium azane coating provided by the invention has high hardness, high adhesive force, extreme super-hydrophilicity and antibacterial performance. The antibacterial polytitazane coating provided by the embodiment 1 has better comprehensive performance, and is most excellent in hydrophilicity and antibacterial property.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the scope of the present invention. All equivalent changes and modifications made according to the disclosure of the present invention are included in the scope of the claims of the present invention.
Claims (10)
1. An antibacterial polytitanium nitazoxane coating composition is characterized in that raw materials of the coating composition comprise a 10% polytitanium nitazoxane ethanol solution and Ag-MWCNTs.
2. The antimicrobial titanazoane coating composition according to claim 1, characterized in that the raw materials of the coating composition comprise a 10% ethanolic solution of titanosilane (PTSZ), ag-MWCNTs, sodium Dodecyl Sulfate (SDS) and polyvinylpyrrolidone (PVP).
3. The antibacterial polytitazane coating composition according to claim 2, wherein the raw materials of the coating composition comprise 100 parts of 10% ethanol solution of Polytitasilazane (PTSZ), 1-4 parts of Ag-MWCNTs, 0.5-2 parts of Sodium Dodecyl Sulfate (SDS), and 0.25-1 part of polyvinylpyrrolidone (PVP); the parts are parts by mass.
4. The antibacterial polytitazane coating composition according to claim 3, wherein the raw materials of the coating composition comprise 100 parts of 10% ethanol solution of Polytitasilazane (PTSZ), 2 parts of Ag-MWCNTs, 1 part of Sodium Dodecyl Sulfate (SDS) and 0.5 part of polyvinylpyrrolidone (PVP); the parts are parts by mass.
5. The antimicrobial titanazepane coating composition of claim 1, wherein the starting materials for the 10% titanosilicone ethanol solution include titanium (IV) isopropoxide, vinyl Polysilazane (PVSZ), and ethanol.
6. The antimicrobial titanyl nitride coating composition of claim 5, wherein the starting materials for the 10% solution of the titanyl nitride ethanol comprises 3 parts of titanium (IV) isopropoxide, 4 parts of vinyl Polysilazane (PVSZ) and 63 parts of ethanol; the parts are parts by mass.
7. The antimicrobial polytitazane coating composition of claim 1, wherein the Ag-MWCNTs feedstock comprises multi-walled carbon nanotubes (MWCNTs), and AgNO 3 And (3) solution.
8. The antimicrobial polytitanium azotane coating composition as claimed in claim 7, wherein the raw material of Ag-MWCNTs comprises multi-walled carbon nanotubes (MWCNTs), agNO 3 Solution, acid, and ethanol.
9. A method of preparing an antimicrobial polytitazane coating composition according to any one of claims 1-8, comprising the steps of:
(1) Uniformly mixing a certain amount of titanium (IV) isopropoxide and vinyl Polysilazane (PVSZ), transferring the mixture into a round bottom flask, heating the mixture in a water bath, replacing air in the flask with nitrogen, and performing oil bath at high temperature to obtain the polytitanium silazane (PTSZ); adding a certain amount of ethanol into the polytitanium silazane (PTSZ), and uniformly mixing to prepare a 10% polytitanium silazane ethanol solution;
(2) Performing ultrasonic treatment on multi-walled carbon nanotubes (MWCNTs) in acid, washing with deionized water, performing ultrasonic dispersion on the centrifugally dried MWCNTs, and slowly dropwise adding AgNO 3 The solution, after magnetic stirring, was filtered and the residual AgNO was taken up with ethanol 3 Obtaining multi-wall carbon nano-tubes (Ag-MWCNTs) attached with Ag particles;
(3) And (2) adding the 10% of poly-titanium-silicon-nitrogen-alkyl ethanol solution obtained in the step (1) into the Ag-MWCNTs obtained in the step (2), adding Sodium Dodecyl Sulfate (SDS) and polyvinylpyrrolidone (PVP), and dispersing and mixing by ultrasonic oscillation to obtain the antibacterial poly-titanium-nitrogen-alkyl coating composition.
10. The method for preparing the antibacterial polytitazane coating composition according to claim 9, wherein the water bath heating in step (1) is performed at 80 ℃ for 30min, and the high temperature oil bath is performed at 160 ℃ for 8h.
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