CN116333542A - Conductive heavy-duty anticorrosive paint and preparation method thereof - Google Patents
Conductive heavy-duty anticorrosive paint and preparation method thereof Download PDFInfo
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- CN116333542A CN116333542A CN202310167175.0A CN202310167175A CN116333542A CN 116333542 A CN116333542 A CN 116333542A CN 202310167175 A CN202310167175 A CN 202310167175A CN 116333542 A CN116333542 A CN 116333542A
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- 239000003973 paint Substances 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title abstract description 10
- 238000000576 coating method Methods 0.000 claims abstract description 54
- 239000011248 coating agent Substances 0.000 claims abstract description 53
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 49
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 46
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 46
- 238000003756 stirring Methods 0.000 claims description 49
- 239000012767 functional filler Substances 0.000 claims description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 29
- 239000002270 dispersing agent Substances 0.000 claims description 28
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims description 26
- 238000010008 shearing Methods 0.000 claims description 24
- 239000002562 thickening agent Substances 0.000 claims description 24
- 239000008367 deionised water Substances 0.000 claims description 23
- 229910021641 deionized water Inorganic materials 0.000 claims description 23
- 239000006185 dispersion Substances 0.000 claims description 21
- 239000002518 antifoaming agent Substances 0.000 claims description 18
- 239000002002 slurry Substances 0.000 claims description 17
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 14
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 claims description 14
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 14
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 14
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 14
- 239000002109 single walled nanotube Substances 0.000 claims description 14
- 239000006228 supernatant Substances 0.000 claims description 14
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 13
- -1 polysiloxane Polymers 0.000 claims description 13
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 12
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 12
- 239000000839 emulsion Substances 0.000 claims description 12
- 239000000243 solution Substances 0.000 claims description 11
- 239000013530 defoamer Substances 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- 229920001296 polysiloxane Polymers 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 9
- 229940009868 aluminum magnesium silicate Drugs 0.000 claims description 7
- WMGSQTMJHBYJMQ-UHFFFAOYSA-N aluminum;magnesium;silicate Chemical compound [Mg+2].[Al+3].[O-][Si]([O-])([O-])[O-] WMGSQTMJHBYJMQ-UHFFFAOYSA-N 0.000 claims description 7
- 238000005530 etching Methods 0.000 claims description 7
- 229910052909 inorganic silicate Inorganic materials 0.000 claims description 7
- 239000011259 mixed solution Substances 0.000 claims description 7
- 239000000843 powder Substances 0.000 claims description 7
- 239000010936 titanium Substances 0.000 claims description 7
- 239000001038 titanium pigment Substances 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- 239000012153 distilled water Substances 0.000 claims description 6
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- DAZXVJBJRMWXJP-UHFFFAOYSA-N n,n-dimethylethylamine Chemical compound CCN(C)C DAZXVJBJRMWXJP-UHFFFAOYSA-N 0.000 claims description 6
- 239000011347 resin Substances 0.000 claims description 6
- 229920005989 resin Polymers 0.000 claims description 6
- 239000004408 titanium dioxide Substances 0.000 claims description 6
- 239000012498 ultrapure water Substances 0.000 claims description 5
- 229920005646 polycarboxylate Polymers 0.000 claims description 4
- 239000004925 Acrylic resin Substances 0.000 claims description 3
- 229920000178 Acrylic resin Polymers 0.000 claims description 3
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 3
- 229920000142 Sodium polycarboxylate Polymers 0.000 claims description 3
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 3
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 3
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 claims description 3
- 239000003822 epoxy resin Substances 0.000 claims description 3
- 229910000403 monosodium phosphate Inorganic materials 0.000 claims description 3
- 235000019799 monosodium phosphate Nutrition 0.000 claims description 3
- ISRXMEYARGEVIU-UHFFFAOYSA-N n-methyl-n-propan-2-ylpropan-2-amine Chemical compound CC(C)N(C)C(C)C ISRXMEYARGEVIU-UHFFFAOYSA-N 0.000 claims description 3
- 229920000647 polyepoxide Polymers 0.000 claims description 3
- 229920001225 polyester resin Polymers 0.000 claims description 3
- 239000004645 polyester resin Substances 0.000 claims description 3
- 229920000570 polyether Polymers 0.000 claims description 3
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- 239000010703 silicon Substances 0.000 claims description 3
- 229920002545 silicone oil Polymers 0.000 claims description 3
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 claims description 3
- 229910000162 sodium phosphate Inorganic materials 0.000 claims description 3
- 239000001488 sodium phosphate Substances 0.000 claims description 3
- 235000011008 sodium phosphates Nutrition 0.000 claims description 3
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 3
- 238000005303 weighing Methods 0.000 claims description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 2
- 238000013019 agitation Methods 0.000 claims 3
- 238000005260 corrosion Methods 0.000 abstract description 31
- 230000007797 corrosion Effects 0.000 abstract description 21
- 239000000463 material Substances 0.000 abstract description 12
- 150000003384 small molecules Chemical class 0.000 abstract description 3
- 239000000945 filler Substances 0.000 abstract description 2
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- 230000035515 penetration Effects 0.000 abstract description 2
- 238000012545 processing Methods 0.000 abstract description 2
- 230000010287 polarization Effects 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000004901 spalling Methods 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000013535 sea water Substances 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
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
-
- 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
- C09D127/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers
- C09D127/02—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
- C09D127/12—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
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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
- C09D5/08—Anti-corrosive paints
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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
- C09D5/24—Electrically-conducting paints
-
- 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
- C08K2201/001—Conductive additives
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
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- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Paints Or Removers (AREA)
Abstract
The invention discloses a conductive heavy-duty coating and a preparation method thereof, wherein an MXene/carbon nano tube filler is added in the conductive heavy-duty coating, wherein the MXene in the MXene/carbon nano tube is a novel two-dimensional sheet material and has the characteristics of large specific surface energy, good flexibility, high strength and the like, and the MXene is added into a coating system, so that a compact physical shielding layer can be formed by utilizing a special two-dimensional lamellar structure of the MXene, the penetration of corrosion factors to a base material is slowed down, the corrosion resistance of the coating to a base material is improved, and the corrosion rate of the material in a severe corrosion environment is greatly reduced; the carbon nano tube has excellent conductivity and larger length-diameter ratio, and can form a conductive network in the coating of the coating after a small amount of carbon nano tube is added, so that small molecules can be prevented from entering, and the compactness of the coating is improved; the conductive heavy-duty anticorrosive paint has simple preparation process, no need of special processing and special environment, and is suitable for large-scale production and application.
Description
Technical Field
The invention discloses the technical field of anti-corrosion materials, and particularly relates to a conductive heavy anti-corrosion coating and a preparation method thereof.
Background
The marine corrosive environment is very demanding, with the greatest hazard being the salt corrosion factors contained in seawater and marine air. Corrosion and protection of marine engineering structures are extremely serious problems facing future marine industry development.
The marine engineering anticorrosive paint is also called heavy-duty anticorrosive paint, because the paint has excellent protective performance far higher than that of common anticorrosive paint, and is mainly applied to the fields of offshore resource exploitation, offshore facility construction and the like. Although research on heavy-duty coating has been conducted by researchers, there is still a problem of high corrosion rate in some severe corrosion environments.
Therefore, how to develop a novel conductive heavy-duty coating to reduce the corrosion speed thereof becomes a problem to be solved urgently.
Disclosure of Invention
In view of the above, the invention provides a conductive heavy anti-corrosion coating and a preparation method thereof, so as to reduce the corrosion speed of the anti-corrosion coating.
In one aspect, the invention provides a conductive heavy-duty anticorrosive coating, which comprises the following components in parts by weight: 130-150 parts of dispersoid, 4-8 parts of inorganic thickener, 2-8 parts of dispersant, 1-4 parts of defoamer, 1-4 parts of pH regulator, 200-300 parts of titanium dioxide, 30-100 parts of precipitated barium sulfate, 400-600 parts of emulsion, 2-8 parts of thickener and functional filler;
wherein the functional filler is MXene/carbon nano tube slurry, and the weight content of the functional filler in the coating is 0.05-3%.
Preferably, in the MXene/carbon nano tube slurry, the weight ratio of the carbon nano tube to the MXene is 1:0.2-5.
Further preferably, the functional filler is prepared by the following method:
1) Ti is mixed with 3 AlC 2 Slowly adding the powder into a mixed solution of lithium fluoride and hydrochloric acid for etching, magnetically stirring at room temperature, washing with deionized water, centrifuging until the pH value of the supernatant is 6, and centrifuging by using a centrifuge to obtain black supernatant which is MXene;
2) Mixing a single-wall carbon nanotube, polyvinylpyrrolidone and N-methylpyrrolidone, adding the mixture into deionized water, carrying out ultrasonic stirring treatment, then carrying out high-speed shearing, adding the MXene prepared in the step 1), and carrying out high-speed dispersion and uniform stirring to obtain the functional filler.
Further preferably, in the step 2), the ultrasonic power of the ultrasonic stirring is 100-300W, the ultrasonic stirring time is 0.5-2h, and the mode of ultrasonic stirring is continuous ultrasonic or pulsed ultrasonic;
and/or the shearing rate of the high-speed shearing is 5-100 m/s, and the shearing time is 5-7h;
and/or the stirring speed of the high-speed dispersing and stirring is 1000-5000rpm/min, and the high-speed dispersing and stirring time is 40-1 h.
Further preferably, in the step 2), the weight ratio of the single-walled carbon nanotube, polyvinylpyrrolidone, N-methylpyrrolidone and deionized water is (0.5 to 1): (2-10): (2-10): (100-200).
Further preferably, the dispersion is one of deionized water, distilled water, high purity water;
and/or, the inorganic thickener is an inorganic silicate;
and/or the dispersing agent is one or more of ammonium polycarboxylate dispersing agent, organosilicon modified polysiloxane dispersing agent, sodium polycarboxylate dispersing agent and quaternary ammonium salt dispersing agent;
and/or the defoaming agent is one or more of polysiloxane defoaming agent, organic silicon defoaming agent, silicone oil defoaming agent and polyether defoaming agent;
and/or the PH regulator is one or more of triethylamine, dimethylethylamine, N-methyl diisopropylamine, ammonium sulfate, sodium phosphate, disodium hydrogen phosphate and sodium dihydrogen phosphate.
Further preferably, the emulsion is one of an aqueous acrylic resin, an epoxy resin, a polyester resin or an aqueous fluorocarbon resin;
and/or the thickener is hydrated aluminum magnesium silicate.
On the other hand, the invention also provides a preparation method of the conductive heavy-duty anticorrosive paint, which comprises the following steps:
s1: respectively weighing dispersoid, inorganic thickener, dispersant, defoamer, pH regulator, titanium pigment, precipitated barium sulfate, emulsion, thickener and functional filler according to weight ratio for standby;
s2: mixing the dispersion, the inorganic thickener, the dispersing agent, the defoaming agent, the pH regulator, the titanium pigment, the precipitated barium sulfate and the functional filler, and then uniformly dispersing at a high speed to obtain a uniformly dispersed solution;
s3: and adding emulsion and thickener into the uniformly dispersed solution, and uniformly dispersing at a high speed to obtain the conductive heavy-duty anticorrosive coating.
Preferably, the rotation speed of the high-speed dispersion in the step S2 and the step S3 is 1000-5000rpm/min, and the dispersion time is 30-60min.
The conductive heavy-duty anticorrosive paint provided by the invention is characterized in that MXene/carbon nano tube slurry is added in the paint, wherein the MXene in the MXene/carbon nano tube slurry is a novel two-dimensional flaky material and has the characteristics of large specific surface energy, good flexibility, high strength and the like, and the MXene is added in a paint system, and a dense physical shielding layer can be formed by utilizing a special two-dimensional lamellar structure of the MXene to slow down the penetration of corrosion factors to a matrix material, so that the corrosion resistance of the coating to the matrix material is greatly improved, and the corrosion rate of the material in a severe corrosion environment is greatly reduced; the carbon nano tube in the MXene/carbon nano tube slurry has excellent conductivity and larger length-diameter ratio, and a small amount of carbon nano tube can form a conductive network in the coating of the coating after being added, so that the entry of small molecules is prevented, and the compactness of the coating is improved; in addition, the carbon nano tube can also adjust the potential of the coating, improve the thermoelectric performance of the coating and enhance the corrosion resistance of the coating. Therefore, after the MXene/carbon nano tube slurry is added into the paint as the functional filler, the conductive performance of the paint can be endowed, the anti-corrosion performance of the paint can be improved, and the paint finally formed by the paint has the advantages of good compactness, high flexibility, strong adhesive force, difficult spalling and the like.
The conductive heavy-duty anticorrosive paint provided by the invention has the advantages of simple preparation process, no need of special processing and special environment, and suitability for large-scale production and application.
It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory only and are not restrictive of the disclosure of the invention as claimed.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate embodiments consistent with the invention and together with the description, serve to explain the principles of the invention.
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are required to be used in the description of the embodiments or the prior art will be briefly described below, and it will be obvious to those skilled in the art that other drawings can be obtained from these drawings without inventive effort.
FIG. 1 is a scanning electron microscope image of an MXene/carbon nanotube slurry filler provided in accordance with the disclosed embodiment 1;
fig. 2 is a polarization graph of a conductive heavy duty coating formed from the conductive heavy duty coating provided in example 2, in accordance with the present disclosure.
Detailed Description
Reference will now be made in detail to exemplary embodiments, examples of which are illustrated in the accompanying drawings. When the following description refers to the accompanying drawings, the same numbers in different drawings refer to the same or similar elements, unless otherwise indicated. The implementations described in the following exemplary examples do not represent all implementations consistent with the invention. Rather, they are merely examples of methods consistent with aspects of the invention as detailed in the accompanying claims.
In order to reduce the corrosion speed of the anticorrosive paint, the embodiment firstly proposes to add MXene/carbon nano tube slurry as a functional filler into the paint, and specifically, the conductive heavy-duty anticorrosive paint comprises the following components in parts by weight: 130-150 parts of dispersoid, 4-8 parts of inorganic thickener, 2-8 parts of dispersant, 1-4 parts of defoamer, 1-4 parts of pH regulator, 200-300 parts of titanium dioxide, 30-100 parts of precipitated barium sulfate, 400-600 parts of emulsion, 2-8 parts of thickener and functional filler;
wherein the functional filler is MXene/carbon nano tube slurry, and the weight content of the functional filler in the coating is 0.05-3%.
Wherein the dispersion can be one of deionized water, distilled water and high-purity water; the inorganic thickener can be inorganic silicate; the dispersing agent can be one or more of polycarboxylate ammonium salt dispersing agent, organosilicon modified polysiloxane dispersing agent, sodium polycarboxylate dispersing agent and quaternary ammonium salt dispersing agent; the defoaming agent can be one or more of polysiloxane defoaming agent, organic silicon defoaming agent, silicone oil defoaming agent and polyether defoaming agent; the pH regulator can be one or more of triethylamine, dimethylethylamine, N-methyl diisopropylamine, ammonium sulfate, sodium phosphate, disodium hydrogen phosphate and sodium dihydrogen phosphate; the emulsion can be one of aqueous acrylic resin, epoxy resin, polyester resin or aqueous fluorocarbon resin; the thickener is hydrated aluminum magnesium silicate.
The MXene/carbon nano tube slurry is prepared by taking MXene and carbon nano tubes as main materials, and because MXene is a novel two-dimensional sheet material, the MXene has the characteristics of large specific surface energy, good flexibility, high strength and the like, and is added into a coating system, a compact physical shielding layer can be formed by utilizing a special two-dimensional sheet structure of the MXene, so that permeation of corrosion factors to a base material is slowed down, corrosion resistance of the coating to the base material is greatly improved, and the corrosion rate of the material in a severe corrosion environment is greatly reduced; because the carbon nano tube has excellent conductivity and larger length-diameter ratio, a conductive network can be formed in the coating of the coating after a small amount of carbon nano tube is added, and small molecules are prevented from entering the coating, so that the compactness of the coating is improved; in addition, the carbon nano tube can also adjust the potential of the coating, improve the thermoelectric performance of the coating and enhance the corrosion resistance of the coating. Therefore, after the MXene/carbon nano tube slurry is added into the paint as the functional filler, the conductive performance of the paint can be endowed, the anti-corrosion performance of the paint can be improved, and the paint finally formed by the paint has the advantages of good compactness, high flexibility, strong adhesive force, difficult spalling and the like.
The MXene/carbon nanotube slurry is generally prepared from carbon nanotubes and MXene in a weight ratio of 1:0.2-5.
In the research and development process, how to uniformly disperse functional fillers in a coating is always a technical difficulty, and a great amount of researches are carried out by the technicians to find that: it is added to the paint in the liquid form of the MXene/carbon nano tube slurry, which is more beneficial to the dispersion of the MXene/carbon nano tube slurry in the paint.
The specific preparation steps of the MXene/carbon nano tube slurry are as follows:
1) Ti is mixed with 3 AlC 2 Slowly adding the powder into a mixed solution of lithium fluoride and hydrochloric acid for etching, magnetically stirring at room temperature, washing with deionized water, centrifuging until the pH value of the supernatant is 6, and centrifuging with a centrifuge to obtain black supernatant which is Mxene;
2) Mixing a single-wall carbon nanotube, polyvinylpyrrolidone and N-methylpyrrolidone, adding the mixture into deionized water, carrying out ultrasonic stirring treatment, then carrying out high-speed shearing, adding the Mxene prepared in the step 1), and carrying out high-speed dispersion and uniform stirring to obtain the functional filler.
Wherein, in order to further improve the dispersibility of MXene in the ultrasonic stirring device, as an improvement of the technical scheme, the ultrasonic power of ultrasonic stirring is 100-300W, the ultrasonic stirring time is 0.5-2h, and the ultrasonic stirring mode is continuous ultrasonic or pulsed ultrasonic; the shearing rate of high-speed shearing is 5-100 m/s, and the shearing time is 5-7h; the stirring speed of high-speed dispersing and stirring is 1000-5000rpm/min, and the high-speed dispersing and stirring time is 40min-1h.
In the step 2), the weight ratio of the single-walled carbon nanotube, polyvinylpyrrolidone, N-methylpyrrolidone and deionized water is (0.5-1): (2-10): (2-10): (100-200).
The preparation method of the conductive heavy-duty coating comprises the following steps:
s1: respectively weighing dispersoid, inorganic thickener, dispersant, defoamer, pH regulator, titanium pigment, precipitated barium sulfate, emulsion, thickener and functional filler according to weight ratio for standby;
s2: mixing the dispersion, the inorganic thickener, the dispersing agent, the defoaming agent, the pH regulator, the titanium pigment, the precipitated barium sulfate and the functional filler, and then uniformly dispersing at a high speed to obtain a uniformly dispersed solution;
s3: and adding emulsion and thickener into the uniformly dispersed solution, and uniformly dispersing at a high speed to obtain the conductive heavy-duty anticorrosive coating.
Wherein, the rotating speed of the high-speed dispersion in the step S2 and the step S3 is 1000-5000rpm/min, and the dispersion time is 30-60min.
The invention is further illustrated by the following examples, which are not intended to limit the scope of the invention.
Example 1
Ti is mixed with 3 AlC 2 Slowly adding the powder into a mixed solution of lithium fluoride and hydrochloric acid for etching, magnetically stirring at room temperature, washing with deionized water, centrifuging until the pH value of the supernatant is 6, and centrifuging by using a centrifuge to obtain black supernatant which is MXene; mixing single-walled carbon nanotubes with polyvinylpyrrolidone and N-methylpyrrolidone, and adding the mixture into deionized water, wherein the single-walled carbon nanotubes are as follows: polyvinylpyrrolidone: n-methylpyrrolidone: the weight ratio of deionized water is 0.5:2:2:100, carrying out continuous ultrasonic stirring, wherein the ultrasonic power is 100W, and the time is 0.5h. Then high-speed shearing is carried out, the shearing rate is 5m/s, and the shearing time is 7h; and adding MXene, performing high-speed dispersion stirring at a stirring speed of 1000rpm/min for 1h, and uniformly stirring to obtain the MXene/carbon nano tube functional filler.
130 parts of deionized water, 4 parts of inorganic silicate, 2 parts of polycarboxylate dispersant, 1 part of polysiloxane defoamer, 1 part of triethylamine, 200 parts of titanium pigment and 30 parts of precipitated barium sulfate are added according to 0.05 percent of MXene/carbon nano tube functional filler (wherein the weight ratio of the carbon nano tube to the MXene is 1:2), and the mixture is dispersed at a high speed of 1000rpm/min for 60min to obtain a uniformly dispersed solution; and adding 400 parts of aqueous acrylic acid and 2 parts of hydrated aluminum magnesium silicate, and uniformly stirring to obtain the conductive heavy-duty anticorrosive paint.
And (3) carrying out scanning electron microscope observation on the prepared MXene/carbon nano tube functional filler, wherein a scanning electron microscope image is shown in fig. 1, and the composite of the MXene and the carbon nano tube in the sheet layer can be seen through fig. 1, and the carbon nano tube has no agglomeration phenomenon.
Example 2
Ti is mixed with 3 AlC 2 Slowly adding the powder into a mixed solution of lithium fluoride and hydrochloric acid for etching, magnetically stirring at room temperature, washing with deionized water, centrifuging until the pH value of the supernatant is 6, and centrifuging by using a centrifuge to obtain black supernatant which is MXene; mixing single-walled carbon nanotubes with polyvinylpyrrolidone and N-methylpyrrolidone, and adding the mixture into deionized water, wherein the single-walled carbon nanotubes are as follows: polyvinylpyrrolidone: n-methylpyrrolidone: the weight ratio of deionized water is 1:10:10:200, carrying out continuous ultrasonic stirring, wherein the ultrasonic power is 300W, and the time is 2h. Then high-speed shearing is carried out, the shearing rate is 100m/s, and the shearing time is 5h; and adding MXene, performing high-speed dispersion stirring at a stirring speed of 5000rpm/min for 30min, and uniformly stirring to obtain the MXene/carbon nano tube functional filler.
150 parts of distilled water, 8 parts of inorganic silicate, 8 parts of organosilicon modified polysiloxane dispersing agent, 4 parts of organosilicon defoamer, 4 parts of dimethylethylamine, 300 parts of titanium dioxide, 100 parts of precipitated barium sulfate and 0.2% of MXene/carbon nano tube functional filler (wherein the weight ratio of the carbon nano tube to the MXene is 1:1) are added, and the mixture is dispersed at a high speed for 30min at 5000rpm/min to obtain a uniformly dispersed solution; and adding 600 parts of fluorocarbon resin and 8 parts of hydrated aluminum magnesium silicate, and uniformly stirring to obtain the conductive heavy-duty anticorrosive coating.
The conductive middle anti-corrosion coating prepared in example 2 is sprayed on Q235 steel, and the anti-corrosion performance of the conductive middle anti-corrosion coating is tested by adopting an electrochemical workstation, the polarization curve is shown in fig. 2, the results are shown in the following table 1, and the anti-corrosion performance of the coating added with the functional filler is superior to that of blank Q235 steel by comparison.
Table 1: polarization curve fitting data for coatings
Example 3
Ti is mixed with 3 AlC 2 Slowly adding the powder into a mixed solution of lithium fluoride and hydrochloric acid for etching, magnetically stirring at room temperature, washing with high-purity water, centrifuging until the pH value of the supernatant is 6, and centrifuging by using a centrifuge to obtain black supernatant which is MXene; mixing single-walled carbon nanotubes with polyvinylpyrrolidone and N-methylpyrrolidone, and adding the mixture into deionized water, wherein the single-walled carbon nanotubes are as follows: polyvinylpyrrolidone: n-methylpyrrolidone: the weight ratio of deionized water is 0.6:8:8:150, carrying out continuous ultrasonic stirring, wherein the ultrasonic power is 200W, and the time is 1.5h. Then high-speed shearing is carried out, the shearing rate is 80m/s, and the shearing time is 6h; and adding MXene, performing high-speed dispersion stirring at a stirring speed of 3000rpm/min for 60min, and uniformly stirring to obtain the MXene/carbon nano tube functional filler.
140 parts of distilled water, 6 parts of inorganic silicate, 4 parts of organosilicon modified polysiloxane dispersing agent, 3 parts of organosilicon defoamer, 2 parts of dimethyl ethylamine, 250 parts of titanium dioxide, 70 parts of precipitated barium sulfate and 1 part of MXene/carbon nano tube functional filler (wherein the weight ratio of carbon nano tube to MXene is 1:0.2), and carrying out high-speed dispersion at 3000rpm/min for 40min to obtain a uniformly dispersed solution; and adding 500 parts of fluorocarbon resin and 6 parts of hydrated aluminum magnesium silicate, and uniformly stirring to obtain the conductive heavy-duty anticorrosive coating.
Example 4
Ti is mixed with 3 AlC 2 Slowly adding the powder into a mixed solution of lithium fluoride and hydrochloric acid for etching, magnetically stirring at room temperature, washing with high-purity water, centrifuging until the pH value of the supernatant is 6, and centrifuging by using a centrifuge to obtain black supernatant which is MXene; mixing single-walled carbon nanotubes with polyvinylpyrrolidone and N-methylpyrrolidone, and adding the mixture into deionized water, wherein the single-walled carbon nanotubes are as follows: polyvinylpyrrolidone: n (N)-methyl pyrrolidone: the weight ratio of deionized water is 0.2:4:6:120, carrying out continuous ultrasonic stirring, wherein the ultrasonic power is 150W, and the time is 1h. Then high-speed shearing is carried out, the shearing rate is 60m/s, and the shearing time is 5h; and adding MXene, performing high-speed dispersion stirring at the stirring speed of 4000rpm/min for 50min, and uniformly stirring to obtain the MXene/carbon nano tube functional filler.
150 parts of distilled water, 5 parts of inorganic silicate, 5 parts of organosilicon modified polysiloxane dispersing agent, 4 parts of organosilicon defoamer, 3 parts of dimethylethylamine, 300 parts of titanium dioxide, 60 parts of precipitated barium sulfate and 5 parts of MXene/carbon nano tube functional filler (wherein the weight ratio of the carbon nano tube to the MXene is 1:5), and dispersing at a high speed of 4000rpm/min for 50min to obtain a uniformly dispersed solution; and adding 600 parts of fluorocarbon resin and 4 parts of hydrated aluminum magnesium silicate, and uniformly stirring to obtain the conductive heavy-duty anticorrosive coating.
Other embodiments of the invention will be apparent to those skilled in the art from consideration of the specification and practice of the invention disclosed herein. This application is intended to cover any variations, uses, or adaptations of the invention following, in general, the principles of the invention and including such departures from the present disclosure as come within known or customary practice within the art to which the invention pertains. It is intended that the specification and examples be considered as exemplary only, with a true scope and spirit of the invention being indicated by the following claims.
It will be understood that the invention is not limited to what has been described above and that various modifications and changes may be made without departing from the scope thereof. The scope of the invention is limited only by the appended claims.
Claims (9)
1. The conductive heavy-duty anticorrosive paint is characterized by comprising the following components in parts by weight: 130-150 parts of dispersoid, 4-8 parts of inorganic thickener, 2-8 parts of dispersant, 1-4 parts of defoamer, 1-4 parts of pH regulator, 200-300 parts of titanium dioxide, 30-100 parts of precipitated barium sulfate, 400-600 parts of emulsion, 2-8 parts of thickener and functional filler;
wherein the functional filler is MXene/carbon nano tube slurry, and the weight content of the functional filler in the coating is 0.05-3%.
2. The conductive heavy duty coating of claim 1, wherein the weight ratio of carbon nanotubes to MXene in the MXene/carbon nanotube slurry is 1:0.2 to 5.
3. The conductive heavy duty anticorrosive coating according to claim 1, wherein the functional filler is prepared by the following method:
1) Ti is mixed with 3 AlC 2 Slowly adding the powder into a mixed solution of lithium fluoride and hydrochloric acid for etching, magnetically stirring at room temperature, washing with deionized water, centrifuging until the pH value of the supernatant is 6, and centrifuging by using a centrifuge to obtain black supernatant which is MXene;
2) Mixing a single-wall carbon nanotube, polyvinylpyrrolidone and N-methylpyrrolidone, adding the mixture into deionized water, carrying out ultrasonic stirring treatment, then carrying out high-speed shearing, adding the MXene prepared in the step 1), and carrying out high-speed dispersion and uniform stirring to obtain the functional filler.
4. The conductive heavy-duty anticorrosive coating according to claim 3, wherein in step 2), the ultrasonic power of the ultrasonic agitation is 100-300W, the ultrasonic agitation time is 0.5-2h, and the mode of ultrasonic agitation is continuous ultrasonic or pulsed ultrasonic;
and/or the shearing rate of the high-speed shearing is 5-100 m/s, and the shearing time is 5-7h;
and/or the stirring speed of the high-speed dispersing and stirring is 1000-5000rpm/min, and the high-speed dispersing and stirring time is 40-1 h.
5. The conductive heavy duty coating of claim 3, wherein in step 2), the weight ratio of single-walled carbon nanotubes, polyvinylpyrrolidone, N-methylpyrrolidone, and deionized water is (0.5 to 1): (2-10): (2-10): (100-200).
6. The electrically conductive heavy duty coating of claim 1, wherein said dispersion is one of deionized water, distilled water, high purity water;
and/or, the inorganic thickener is an inorganic silicate;
and/or the dispersing agent is one or more of ammonium polycarboxylate dispersing agent, organosilicon modified polysiloxane dispersing agent, sodium polycarboxylate dispersing agent and quaternary ammonium salt dispersing agent;
and/or the defoaming agent is one or more of polysiloxane defoaming agent, organic silicon defoaming agent, silicone oil defoaming agent and polyether defoaming agent;
and/or the PH regulator is one or more of triethylamine, dimethylethylamine, N-methyl diisopropylamine, ammonium sulfate, sodium phosphate, disodium hydrogen phosphate and sodium dihydrogen phosphate.
7. The electrically conductive heavy duty coating of claim 1, wherein said emulsion is one of an aqueous acrylic resin, an epoxy resin, a polyester resin, or an aqueous fluorocarbon resin;
and/or the thickener is hydrated aluminum magnesium silicate.
8. A method for preparing the conductive heavy-duty coating according to any one of claims 1 to 7, comprising the steps of:
s1: respectively weighing dispersoid, inorganic thickener, dispersant, defoamer, pH regulator, titanium pigment, precipitated barium sulfate, emulsion, thickener and functional filler according to weight ratio for standby;
s2: mixing the dispersion, the inorganic thickener, the dispersing agent, the defoaming agent, the pH regulator, the titanium pigment, the precipitated barium sulfate and the functional filler, and then uniformly dispersing at a high speed to obtain a uniformly dispersed solution;
s3: and adding emulsion and thickener into the uniformly dispersed solution, and uniformly dispersing at a high speed to obtain the conductive heavy-duty anticorrosive coating.
9. The method for preparing a conductive heavy-duty coating according to claim 1, wherein the high-speed dispersion in step S2 and step S3 is performed at a rotation speed of 1000 to 5000rpm/min and the dispersion time is 30 to 60min.
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