CN115558323B - Antibacterial poly-titanium-nitrogen-alkane coating composition and preparation method thereof - Google Patents
Antibacterial poly-titanium-nitrogen-alkane coating composition and preparation method thereof Download PDFInfo
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- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 36
- 239000008199 coating composition Substances 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title abstract description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 96
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims abstract description 36
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims abstract description 36
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims abstract description 36
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims abstract description 36
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 35
- 239000010936 titanium Substances 0.000 claims abstract description 35
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 35
- 239000002048 multi walled nanotube Substances 0.000 claims abstract description 30
- 229920001709 polysilazane Polymers 0.000 claims abstract description 16
- 239000002994 raw material Substances 0.000 claims abstract description 15
- 239000000243 solution Substances 0.000 claims description 43
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 26
- 239000000203 mixture Substances 0.000 claims description 21
- 101710134784 Agnoprotein Proteins 0.000 claims description 16
- 230000000845 anti-microbial effect Effects 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 11
- 239000002253 acid Substances 0.000 claims description 10
- 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
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 8
- 229920002554 vinyl polymer Polymers 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 239000004599 antimicrobial Substances 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 239000006185 dispersion Substances 0.000 claims description 3
- 238000003760 magnetic stirring Methods 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 238000000576 coating method Methods 0.000 abstract description 40
- 239000011248 coating agent Substances 0.000 abstract description 37
- 230000007797 corrosion Effects 0.000 abstract description 13
- 238000005260 corrosion Methods 0.000 abstract description 13
- 239000000725 suspension Substances 0.000 description 20
- 229910000831 Steel Inorganic materials 0.000 description 13
- 239000010959 steel Substances 0.000 description 13
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 10
- 238000003618 dip coating Methods 0.000 description 10
- 239000010410 layer Substances 0.000 description 9
- 238000004321 preservation Methods 0.000 description 9
- 239000002086 nanomaterial Substances 0.000 description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 5
- 229910017604 nitric acid Inorganic materials 0.000 description 5
- 241000894006 Bacteria Species 0.000 description 4
- 239000002243 precursor Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 239000002609 medium Substances 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000012086 standard solution Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 239000002390 adhesive tape Substances 0.000 description 2
- 239000002041 carbon nanotube Substances 0.000 description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 239000011247 coating layer Substances 0.000 description 2
- LOKCTEFSRHRXRJ-UHFFFAOYSA-I dipotassium trisodium dihydrogen phosphate hydrogen phosphate dichloride Chemical compound P(=O)(O)(O)[O-].[K+].P(=O)(O)([O-])[O-].[Na+].[Na+].[Cl-].[K+].[Cl-].[Na+] LOKCTEFSRHRXRJ-UHFFFAOYSA-I 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 230000004060 metabolic process Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 244000005700 microbiome Species 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 239000002953 phosphate buffered saline Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000013535 sea water Substances 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- -1 silver ions Chemical class 0.000 description 2
- 239000002344 surface layer Substances 0.000 description 2
- 241000195493 Cryptophyta Species 0.000 description 1
- 241000588724 Escherichia coli Species 0.000 description 1
- 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
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 230000001580 bacterial effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 238000010349 cathodic reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
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- 238000001035 drying Methods 0.000 description 1
- 239000001963 growth medium Substances 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 229920000592 inorganic polymer Polymers 0.000 description 1
- 238000009364 mariculture Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
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- 238000002844 melting Methods 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 235000020638 mussel Nutrition 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 238000002390 rotary evaporation Methods 0.000 description 1
- 238000007788 roughening Methods 0.000 description 1
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- 230000008023 solidification Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000003075 superhydrophobic effect Effects 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
- 238000003260 vortexing Methods 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Classifications
-
- 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
-
- 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
- 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
-
- 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
- C09D5/16—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
-
- 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
- C09D5/16—Antifouling paints; Underwater paints
- C09D5/1656—Antifouling paints; Underwater paints characterised by the film-forming substance
- C09D5/1662—Synthetic film-forming substance
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/08—Metals
- C08K2003/0806—Silver
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
-
- 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
Abstract
The invention relates to a coating, in particular to an antibacterial poly-titanium-nitrogen-alkane coating composition and a preparation method thereof. In order to solve the biofouling problem in the existing marine corrosion, the invention provides an antibacterial poly-titanium-nitrogen-alkane coating composition and a preparation method thereof. The raw materials of the coating composition comprise 10% of a titanium Polysilazane (PTSZ) ethanol solution, ag-MWCNTs, sodium Dodecyl Sulfate (SDS) and polyvinylpyrrolidone (PVP). Compared with the prior art, the coating formed by the antibacterial poly-titanium-nitrogen-alkane coating composition has excellent antibacterial property and super-hydrophilic property, 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
Polysilazane is an inorganic polymer with Si-N bond repeating units as a main chain, and has many advantages as a precursor coating for marine biofouling resistance, and firstly, the coating obtained after curing mainly contains inorganic SiO 2 The coating has lower surface energy, and excellent hydrophobic property can greatly reduce the adhesion of marine organisms such as bacteria, algae, mussels and the like; second, the polysilazane curing process is very simple. However, there are still some urgent needs to be solved in the field of marine antifoulingIs complicated by the large number of marine organisms and the complex fouling process, wherein the impact of biofouling on corrosion of metallic materials is particularly severe. Biofouling in marine corrosion can be divided into two major categories, microscopic biofouling and macroscopic biofouling, where the effect of microscopic biofouling is primarily that the microbial metabolic process affects the rate of corrosion of the metal surface, such as acid metabolism producing a substance capable of initiating a cathodic reaction. Macroscopic biofouling refers to attachment of macroscopic organisms, which can increase navigation resistance of ships, blockage of seawater pipelines, great loss caused by mariculture and the like, and can also accelerate the local corrosion speed of materials.
Disclosure of Invention
In order to solve the biofouling problem in the existing marine corrosion, the invention provides an antibacterial poly-titanium-nitrogen-alkane coating composition and a preparation method thereof.
The invention overcomes the defects in the prior art, provides an antibacterial poly-titanium-nitrogen-alkane coating composition and a preparation method thereof, and adopts a mode of blending nano silver after modifying a carbon nano tube with poly-titanium-silicon-nitrogen alkane and then utilizing water vapor to cure at high temperature to prepare an antibacterial and super-hydrophilic coating with high hardness, wherein Ag nano particles are deposited on the surface of a multi-wall carbon nano tube (MWCNTs) through reduction of silver ions by ethanol, so that the antibacterial and super-hydrophilic coating has the advantages of environmental protection and no pollution.
In order to solve the technical problems, the invention is realized by the following technical scheme:
the invention provides an antibacterial poly-titanium-nitrogen-alkane coating composition, wherein the raw materials of the coating composition comprise 10% of poly-titanium-silicon-nitrogen-alkane (PTSZ) ethanol solution and Ag-MWCNTs.
The invention provides an antibacterial poly-titanium-nitrogen-alkane coating composition, wherein the raw materials of the coating composition comprise 10% of poly-titanium-silicon-nitrogen-alkane (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% of a titanium Polysilazane (PTSZ) ethanol solution, 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% of a titanium Polysilazane (PTSZ) ethanol solution, 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 silazane ethanol solution comprise titanium (IV) isopropoxide, vinyl Polysilazane (PVSZ) and ethanol.
Further, the raw materials of the 10% poly-titanium 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 Ag-MWCNTs raw material comprises multi-wall carbon nanotubes (MWCNTs), and AgNO 3 A solution.
Further, the Ag-MWCNTs raw material comprises 10 g of multi-wall carbon nanotubes (MWCNTs) and 50ml of 17g of AgNO 3 A solution. 17g is AgNO 3 Is a mass of (3).
Further, the Ag-MWCNTs raw material comprises multi-wall carbon nanotubes (MWCNTs), agNO 3 Solution, acid, and ethanol.
Further, the AgNO 3 The solution is AgNO 3 Standard solution.
Further, the acid is nitric acid (H 3 NO 3 ) And sulfuric acid (H) 2 SO 4 ). Said nitric acid (H) 3 NO 3 ) And sulfuric acid (H) 2 SO 4 ) The volume ratio of (3): 1.
the coating formed by the antibacterial poly-titanium-nitrogen-alkane coating composition has excellent antibacterial performance and super-hydrophilic performance, and is also called an antibacterial limit super-hydrophilic poly-titanium-nitrogen-alkane coating composition.
In another aspect, the present invention provides a method of preparing an antimicrobial poly-titanium-nitrogen-alkane coating composition, the method comprising the steps of:
(1) Mixing a certain amount of titanium (IV) isopropoxide and vinyl Polysilazane (PVSZ) uniformly, transferring the mixture into a round-bottomed flask, heating in a water bath, replacing air in the flask with nitrogen, and carrying out oil bath at a high temperature to obtain the Polysilazane (PTSZ); adding a certain amount of ethanol into the poly-titanium silazane (PTSZ) and uniformly mixing to prepare 10% poly-titanium silazane ethanol solution;
(2) Ultrasonically treating multi-wall carbon nanotubes (MWCNTs) in acid, washing with deionized water, ultrasonically dispersing the centrifugally dried MWCNTs, and slowly dripping AgNO 3 After magnetic stirring, the solution was filtered and the remaining AgNO was extracted with ethanol 3 Obtaining multi-wall carbon nanotubes (Ag-MWCNTs) attached with Ag particles;
(3) Adding the Ag-MWCNTs obtained in the step (2) into the 10% poly-titanium silazane ethanol solution obtained in the step (1), adding Sodium Dodecyl Sulfate (SDS) and polyvinylpyrrolidone (PVP), and performing ultrasonic vibration dispersion mixing to obtain the antibacterial poly-titanium silazane coating composition.
Further, the method comprises the steps of:
(1) A certain amount of titanium (IV) isopropoxide and vinyl Polysilazane (PVSZ) are taken, uniformly mixed and transferred into a round bottom flask, after heating in a water bath, air in the flask is replaced by nitrogen, and the flask is subjected to oil bath at high temperature. The color of the mixed solution is changed from milky white to yellow, then changed to dark green, and finally changed to reddish brown. Finally, adding a certain amount of ethanol solution into the obtained poly-titanium silazane (PTSZ) and uniformly mixing to prepare 10% poly-titanium silazane ethanol solution.
(2) Ultrasonically treating multi-wall carbon nanotubes (MWCNTs) in excessive acid, washing with deionized water, ultrasonically dispersing the centrifugally dried MWCNTs, and slowly dripping AgNO 3 After magnetic stirring, the solution was filtered and the remaining AgNO was extracted with ethanol 3 To obtain multi-wall carbon nanotubes (Ag-MWCNTs) with Ag particles attached.
(3) Adding the Ag-MWCNTs obtained in the step (2) into the 10% poly-titanium silazane ethanol solution obtained in the step (1), adding Sodium Dodecyl Sulfate (SDS) and polyvinylpyrrolidone (PVP), and performing ultrasonic vibration dispersion mixing to obtain a stable antibacterial poly-titanium silazane coating composition (also called an antibacterial limit super-hydrophilic suspension).
An antibacterial poly-titanium-nitrogen-alkane coating composition is coated on the surface of a DH36 steel sample by a dip coating method, the mixture is heated to 800 ℃ in a tube furnace, water vapor is solidified, and the mixture is taken out after heat preservation for 2 hours. The antimicrobial poly (titanium-nitrogen) coating composition forms a coating.
Further, the mass ratio of the titanium (IV) isopropoxide to the vinyl Polysilazane (PVSZ) added in the step (1) is 3:4.
further, the water bath heating in the step (1) means water bath at 80 ℃ for 30min.
Further, the high-temperature oil bath in the step (1) means an oil bath at 160 ℃ for 8 hours.
Further, the mass of the ethanol added in the step (1) is 9 times of that of the poly-titanium silazane (PTSZ), and an ethanol solution with the mass fraction of 10% of PTSZ 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 ) Nitric acid (H) 3 NO 3 ) And sulfuric acid (H) 2 SO 4 ) The volume ratio of (3): 1.
further, the step (2) is performed by washing with deionized water until the pH is 7.0.
Further, agNO described in the step (2) 3 Solution of 50ml of 17g AgNO 3 Standard solution.
Further, the mass ratio of Ag-MWCNTs, sodium Dodecyl Sulfate (SDS) and polyvinylpyrrolidone (PVP) in the step (3) is 4:2:1.
aiming at microscopic biofouling of biofouling in marine corrosion, the coating formed by the coating composition provided by the invention can resist bacteria, inhibit the growth of microorganisms, and play roles in protecting metals and preventing corrosion in terms of microorganisms; aiming at macroscopic biofouling of biofouling in marine corrosion, the coating has good water spreadability on the surface of the coating due to the super-hydrophilic effect, and some macroscopic marine organisms are not easy to be stained on the coating and are easy to be taken away by seawater, so that the effect of preventing corrosion is achieved.
Compared with the prior art, the invention has the beneficial effects that:
from the environmental protection point of view, the Ag nano particles are successfully deposited on the surface of the multi-wall carbon nano tube (MWCNTs) through ethanol reduction of silver ions. And then uniformly dispersing the Ag-MWCNTs in the alcoholic solution of the poly-titanium silazane, so that the Ag nano particles can be uniformly distributed, the agglomeration is reduced, the MWCNTs become a basic skeleton of the micro-nano structure during solidification, and a surface layer with the micro-nano structure is woven to obtain the antimicrobial suspension precursor. By controlling the curing temperature, the poly-titanium silazane is cured along the surface thereof, thereby playing the roles of antibiosis and extreme super-hydrophilicity. A value of the coating surface contact angle less than 3 ° may be referred to as superhydrophilic; the surface contact angle of the coating can reach 0 DEG, so the coating is called ultimate super-hydrophilicity.
Compared with the prior art, the coating formed by the antibacterial poly-titanium-nitrogen-alkane coating composition has excellent antibacterial property and super-hydrophilic property, 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 preferred embodiments of the present invention are described below, which are only for illustrating and explaining the present invention, and are not limited thereto.
In examples 1-4: preparing an ethanol solution of PTSZ with the mass fraction of 10 percent: titanium (IV) isopropoxide and vinyl Polysilazane (PVSZ) were mixed in a ratio of 3:4, transferred to a round bottom flask after mixing well, water-bath at 80℃for 30min, and with rotary evaporation to remove some small organic low melting point molecular groups, then air in the flask was replaced with nitrogen, and oil-bath was carried out at 160℃for 8h. The color of the mixed solution is changed from milky white to yellow slowly, then changed to dark green, and finally changed to reddish brown. Finally, the obtained poly-titanium silazane (PTSZ) was stored in a sealed condition in a nitrogen atmosphere. Adding 9 times of ethanol solution into the poly-titanium silazane (PTSZ) and uniformly mixing to prepare 10% poly-titanium silazane ethanol solution.
Preparation of Ag-MWCNTs: 10 g of MWCNTs are reacted with excess acid (H 2 SO 4 :HNO 3 Is treated by ultrasonic for one hour in the volume ratio of 1:3) so as to generate a large amount of-COOH and-OH active groups on the surface of the MWCNTs, and then the MWCNTs are washed by deionized water until the pH=7.0; then the MWCNTs-COOH after centrifugal drying is dispersed in 250ml ethanol by ultrasonic, and 50ml 17gAgNO is slowly added dropwise 3 Standard solution, after magnetically stirring for one hour, was filtered and residual AgNO was extracted with ethanol 3 Obtaining Ag-MWCNTs.
The coating layer formed by the antibacterial poly-titanium-nitrogen-alkane coating composition provided by the embodiment of the invention, the coating layer formed by the comparative example and the steel plate provided by the comparative example 2 are tested for main properties by the following methods.
Pencil hardness (H): the test was carried out according to GB/T6739-86 standard using a PPH-1 pencil hardness tester. After the coating is solidified, the template is placed at a horizontal position, and a pencil with gradually increased hardness is pushed to measure the position of the surface layer of the coating, and the pencil hardness when no scratch appears on the surface is taken as the pencil hardness value of the coating.
Adhesion test (B): according to GB/T9286-1998 Standard for adhesive force test of paint and varnish, the surface of a film was cut into 10X 10 grids spaced 2mm apart by a dicer by using a dicer method, and an adhesive tape was applied to the grids, followed by tearing the adhesive tape at a proper and uniform speed. And (3) carrying out 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 5B-0B respectively.
Contact angle CA (°): the wetting angle of a water drop on a sample was measured by a contact angle tester using a water drop method. The smaller the contact angle tested, the better the hydrophilic properties, presently referred to as superhydrophilic with contact angles less than 3 °.
Average peak-to-valley deviation Rz (μm) of the coating profile: the sum of the average value of 5 maximum profile peak heights and the average value of 5 maximum profile valley depths in the test sampling length range is directly tested by a roughening instrument. The larger Rz is in a certain range, the rougher the surface is, and the more remarkable the micro-nano structure of the surface is. The micro-nano structure refers to a microstructure of the cured surface of the coating, and the micro-nano structure is prominent after the coating is cured due to the skeleton supporting function of the carbon nano tube. The larger Rz indicates that the micro-nanostructure is about apparent.
After 24h the number of colonies on the medium (number): the antibacterial poly-titanium-nitrogen-alkane coating composition (also called antibacterial super-hydrophobic suspension) is coated in a culture medium, then the curing process is carried out at 400 ℃ for 2 hours, ethanol and an ultraviolet lamp are sequentially used for treatment, the surface of a sample is sterilized, and then the treated sample is treated in a saturated escherichia coli solution (10) 8 CFU/mL). After soaking for a period of time, the surface bacteria liquid is gently washed off with Phosphate Buffered Saline (PBS), and then the attached bacteria on the surface of the sample are removed by vortexing. mu.L of the bacterial liquid was taken out on the medium, and the colony count on the medium was counted after 24 hours. The smaller the number of colonies, the more excellent the antibacterial performance.
Example 1:
the present example provides an antimicrobial poly-titanium-nitrogen-alkane coating composition, and coatings formed therefrom.
To 100 parts of a 10% strength solution of a poly (titanium silazane) (PTSZ) ethanol solution were added 2 parts of Ag-MWCNTs, 1 part of Sodium Dodecyl Sulfate (SDS) and 0.5 part of polyvinylpyrrolidone (PVP), and dispersed by ultrasonic vibration to obtain a stable antibacterial poly (titanium silazane) coating composition (also referred to as an antibacterial extreme super-hydrophilic suspension, or extreme super-hydrophilic suspension).
A layer of extreme super-hydrophilic suspension is coated on the surface of a DH36 steel sample by a dip coating method, the mixture is heated to 800 ℃ in a tube furnace, water vapor is solidified, and the mixture is taken out after heat preservation for 2 hours. A coating having a thickness of about 5 μm was produced.
Example 2:
preparation of a 10% strength solution of a poly (titanium silazane) (PTSZ) ethanol solution 100 parts were added 1 part of Ag-MWCNTs, 0.5 part of Sodium Dodecyl Sulfate (SDS) and 0.25 part of polyvinylpyrrolidone (PVP), and dispersed by ultrasonic vibration to obtain a stable antimicrobial extreme super-hydrophilic suspension.
A layer of extreme super-hydrophilic suspension is coated on the surface of a DH36 steel sample by a dip coating method, the mixture is heated to 800 ℃ in a tube furnace, water vapor is solidified, and the mixture is taken out after heat preservation for 2 hours. A coating having a thickness of about 5 μm was produced.
Example 3:
preparation of a 10% strength solution of a poly (titanium silazane) (PTSZ) ethanol solution 100 parts were added 3 parts of Ag-MWCNTs, 1.5 parts of Sodium Dodecyl Sulfate (SDS) and 0.75 parts of polyvinylpyrrolidone (PVP) and dispersed by ultrasonic vibration to obtain a stable antimicrobial extreme super-hydrophilic suspension.
A layer of extreme super-hydrophilic suspension is coated on the surface of a DH36 steel sample by a dip coating method, the mixture is heated to 800 ℃ in a tube furnace, water vapor is solidified, and the mixture is taken out after heat preservation for 2 hours. A coating having a thickness of about 5 μm was produced.
Example 4:
preparation of a 10% strength solution of a poly (titanium silazane) (PTSZ) ethanol solution 100 parts were added 4 parts of Ag-MWCNTs, 2 parts of Sodium Dodecyl Sulfate (SDS) and 1 part of polyvinylpyrrolidone (PVP) and dispersed by ultrasonic vibration to obtain a stable antimicrobial extreme super-hydrophilic suspension.
A layer of extreme super-hydrophilic suspension is coated on the surface of a DH36 steel sample by a dip coating method, the mixture is heated to 800 ℃ in a tube furnace, water vapor is solidified, and the mixture is taken out after heat preservation for 2 hours. A paint film having a thickness of about 5 μm was produced.
Comparative example 1
An ethanol solution of a titanium Polysilazane (PTSZ) with a mass fraction of 10% was prepared as a precursor of the corrosion resistant coating. After being uniformly mixed, a layer of precursor solution is coated on the surface of the DH36 steel sample by a dip coating method, and the mixture is air-dried for 15min. Finally, the sample is hung in an oven, a basin of water is placed in the oven, and the water vapor is cured for 2 hours at the temperature of 150 ℃. A coating having a thickness of about 5 μm was produced.
Comparative example 2
DH36 steel samples were surface cleaned and used as a control.
Comparative example 3
Preparation of a 10% strength solution of a poly (titanium silazane) (PTSZ) ethanol solution 100 parts were added 2 parts of Ag-MWCNTs, 0.2 part of Sodium Dodecyl Sulfate (SDS) and 0.1 part of polyvinylpyrrolidone (PVP), and dispersed by ultrasonic vibration to obtain a stable antimicrobial extreme super-hydrophilic suspension.
A layer of extreme super-hydrophilic suspension is coated on the surface of a DH36 steel sample by a dip coating method, the mixture is heated to 800 ℃ in a tube furnace, water vapor is solidified, and the mixture is taken out after heat preservation for 2 hours. A coating having a thickness of about 5 μm was produced.
Comparative example 4
Preparation of a 10% strength solution of a poly (titanium silazane) (PTSZ) ethanol solution 100 parts were added 2 parts of Ag-MWCNTs, 4 parts of Sodium Dodecyl Sulfate (SDS) and 2 parts of polyvinylpyrrolidone (PVP) and dispersed by ultrasonic vibration to obtain a stable antimicrobial extreme super-hydrophilic suspension.
A layer of extreme super-hydrophilic suspension is coated on the surface of a DH36 steel sample by a dip coating method, the mixture is heated to 800 ℃ in a tube furnace, water vapor is solidified, and the mixture is taken out after heat preservation for 2 hours. A coating having a thickness of about 5 μm was produced.
Comparative example 5
Preparation of a 10% strength solution of a poly (titanium silazane) (PTSZ) ethanol solution 100 parts were added 0.5 parts of Ag-MWCNTs, 0.2 parts of Sodium Dodecyl Sulfate (SDS) and 0.1 parts of polyvinylpyrrolidone (PVP) and dispersed by ultrasonic vibration to obtain a stable ultra-hydrophilic suspension with an antibacterial limit.
A layer of extreme super-hydrophilic suspension is coated on the surface of a DH36 steel sample by a dip coating method, the mixture is heated to 800 ℃ in a tube furnace, water vapor is solidified, and the mixture is taken out after heat preservation for 2 hours. A coating having a thickness of about 5 μm was produced.
Comparative example 6
Preparation of a 10% strength solution of a poly (titanium silazane) (PTSZ) ethanol solution 100 parts were added 5 parts of Ag-MWCNTs, 4 parts of Sodium Dodecyl Sulfate (SDS) and 2 parts of polyvinylpyrrolidone (PVP) and dispersed by ultrasonic vibration to obtain a stable antimicrobial extreme super-hydrophilic suspension.
A layer of extreme super-hydrophilic suspension is coated on the surface of a DH36 steel sample by a dip coating method, the mixture is heated to 800 ℃ in a tube furnace, water vapor is solidified, and the mixture is taken out after heat preservation for 2 hours. A coating having 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 sheets provided in comparative example 2
The coating formed by the antibacterial poly-titanium-nitrogen-alkane coating provided by the invention has high hardness, high adhesive force, extreme super-hydrophilicity and antibacterial property. Among them, the antibacterial poly-titanium-nitrogen-alkane coating provided in example 1 has better comprehensive properties, hydrophilicity and most excellent antibacterial property.
The foregoing description is only of the preferred embodiments of the present invention, and is not intended to limit the scope of the present invention. All equivalent changes and modifications made in accordance with the present invention are intended to be covered by the scope of the appended claims.
Claims (5)
1. An antibacterial poly-titanium-nitrogen-alkane coating composition is characterized in that the raw materials of the coating composition consist of the following components: 100 parts of 10% poly-titanium silazane (PTSZ) ethanol solution, 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 mass parts; the raw materials of the 10% poly-titanium silazane ethanol solution comprise titanium (IV) isopropoxide, vinyl Polysilazane (PVSZ) and ethanol; the Ag-MWCNTs raw material comprises multi-wall carbon nanotubes (MWCNTs), agNO 3 Solution, acid, and ethanol.
2. The antimicrobial poly-titanium-nitrogen-alkane coating composition according to claim 1, wherein the raw materials of the coating composition comprise 100 parts of a 10% poly-titanium-silicon-nitrogen-alkane (PTSZ) ethanol solution, 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.
3. The antibacterial poly-titanium-nitrogen-alkane coating composition according to claim 1, wherein the raw materials of the 10% poly-titanium-silicon-nitrogen-alkane ethanol solution comprise 3 parts of titanium (IV) isopropoxide, 4 parts of vinyl-poly-silicon-nitrogen-alkane (PVSZ) and 63 parts of ethanol; the parts are parts by mass.
4. A method of preparing an antimicrobial poly-titanium-nitrogen-alkane coating composition according to any one of claims 1-3, characterized in that the method comprises the steps of:
(1) Mixing a certain amount of titanium (IV) isopropoxide and vinyl Polysilazane (PVSZ) uniformly, transferring the mixture into a round-bottomed flask, heating in a water bath, replacing air in the flask with nitrogen, and carrying out oil bath at a high temperature to obtain the Polysilazane (PTSZ); adding a certain amount of ethanol into the poly-titanium silazane (PTSZ) and uniformly mixing to prepare 10% poly-titanium silazane ethanol solution;
(2) Ultrasonically treating multi-wall carbon nanotubes (MWCNTs) in acid, washing with deionized water, ultrasonically dispersing the centrifugally dried MWCNTs, and slowly dripping AgNO 3 After magnetic stirring, the solution was filtered and the remaining AgNO was extracted with ethanol 3 Obtaining multi-wall carbon nanotubes (Ag-MWCNTs) attached with Ag particles;
(3) Adding the Ag-MWCNTs obtained in the step (2) into the 10% poly-titanium silazane ethanol solution obtained in the step (1), adding Sodium Dodecyl Sulfate (SDS) and polyvinylpyrrolidone (PVP), and performing ultrasonic vibration dispersion mixing to obtain the antibacterial poly-titanium silazane coating composition.
5. The method of preparing an antimicrobial poly (titanium-nitrogen-alkane) coating composition according to claim 4, wherein the water bath heating in step (1) is performed at 80 ℃ for 30min, and the oil bath at high temperature is performed at 160 ℃ for 8h.
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