CN115323352B - Super-amphiphobic coating with micro-nano composite structure and preparation method thereof - Google Patents
Super-amphiphobic coating with micro-nano composite structure and preparation method thereof Download PDFInfo
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- CN115323352B CN115323352B CN202210982940.XA CN202210982940A CN115323352B CN 115323352 B CN115323352 B CN 115323352B CN 202210982940 A CN202210982940 A CN 202210982940A CN 115323352 B CN115323352 B CN 115323352B
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- 238000000576 coating method Methods 0.000 title claims abstract description 56
- 239000011248 coating agent Substances 0.000 title claims abstract description 54
- 239000002114 nanocomposite Substances 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 238000007740 vapor deposition Methods 0.000 claims abstract description 62
- 238000000034 method Methods 0.000 claims abstract description 25
- 239000002904 solvent Substances 0.000 claims abstract description 24
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 76
- 239000000377 silicon dioxide Substances 0.000 claims description 36
- 235000012239 silicon dioxide Nutrition 0.000 claims description 26
- 238000003860 storage Methods 0.000 claims description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 19
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 17
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 15
- 239000002245 particle Substances 0.000 claims description 14
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 12
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 12
- 238000012986 modification Methods 0.000 claims description 12
- 230000004048 modification Effects 0.000 claims description 12
- 239000000725 suspension Substances 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 6
- 238000001291 vacuum drying Methods 0.000 claims description 6
- 239000003153 chemical reaction reagent Substances 0.000 claims description 5
- 239000007791 liquid phase Substances 0.000 claims description 5
- QTRSWYWKHYAKEO-UHFFFAOYSA-N 1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-henicosafluorodecyl-tris(1,1,2,2,2-pentafluoroethoxy)silane Chemical compound FC(F)(F)C(F)(F)O[Si](OC(F)(F)C(F)(F)F)(OC(F)(F)C(F)(F)F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F QTRSWYWKHYAKEO-UHFFFAOYSA-N 0.000 claims description 4
- AVXLXFZNRNUCRP-UHFFFAOYSA-N trichloro(1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-heptadecafluorooctyl)silane Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)[Si](Cl)(Cl)Cl AVXLXFZNRNUCRP-UHFFFAOYSA-N 0.000 claims description 4
- PYJJCSYBSYXGQQ-UHFFFAOYSA-N trichloro(octadecyl)silane Chemical compound CCCCCCCCCCCCCCCCCC[Si](Cl)(Cl)Cl PYJJCSYBSYXGQQ-UHFFFAOYSA-N 0.000 claims description 4
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims description 3
- YGUFXEJWPRRAEK-UHFFFAOYSA-N dodecyl(triethoxy)silane Chemical compound CCCCCCCCCCCC[Si](OCC)(OCC)OCC YGUFXEJWPRRAEK-UHFFFAOYSA-N 0.000 claims description 3
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 3
- 239000005055 methyl trichlorosilane Substances 0.000 claims description 3
- JLUFWMXJHAVVNN-UHFFFAOYSA-N methyltrichlorosilane Chemical compound C[Si](Cl)(Cl)Cl JLUFWMXJHAVVNN-UHFFFAOYSA-N 0.000 claims description 3
- 238000012806 monitoring device Methods 0.000 claims description 3
- AKIOHULKHAVIMI-UHFFFAOYSA-N trichloro(1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11,12,12,12-pentacosafluorododecyl)silane Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)[Si](Cl)(Cl)Cl AKIOHULKHAVIMI-UHFFFAOYSA-N 0.000 claims description 3
- BNCXNUWGWUZTCN-UHFFFAOYSA-N trichloro(dodecyl)silane Chemical compound CCCCCCCCCCCC[Si](Cl)(Cl)Cl BNCXNUWGWUZTCN-UHFFFAOYSA-N 0.000 claims description 3
- 239000000463 material Substances 0.000 abstract description 8
- 239000003054 catalyst Substances 0.000 abstract description 3
- DCAYPVUWAIABOU-UHFFFAOYSA-N hexadecane Chemical compound CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 description 22
- 238000005507 spraying Methods 0.000 description 21
- 230000003075 superhydrophobic effect Effects 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 239000002105 nanoparticle Substances 0.000 description 8
- 238000010907 mechanical stirring Methods 0.000 description 6
- 238000005303 weighing Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- 235000019441 ethanol Nutrition 0.000 description 4
- QRPMCZNLJXJVSG-UHFFFAOYSA-N trichloro(1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-henicosafluorodecyl)silane Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)[Si](Cl)(Cl)Cl QRPMCZNLJXJVSG-UHFFFAOYSA-N 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000002086 nanomaterial Substances 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 229920002635 polyurethane Polymers 0.000 description 3
- 239000004814 polyurethane Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000005543 nano-size silicon particle Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- 230000003746 surface roughness Effects 0.000 description 2
- 240000002853 Nelumbo nucifera Species 0.000 description 1
- 235000006508 Nelumbo nucifera Nutrition 0.000 description 1
- 235000006510 Nelumbo pentapetala Nutrition 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
- C23C16/40—Oxides
- C23C16/401—Oxides containing silicon
- C23C16/402—Silicon dioxide
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- 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
- C09D1/00—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
-
- 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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/4417—Methods specially adapted for coating powder
Abstract
The invention provides a super-amphiphobic coating with a micro-nano composite structure and a preparation method thereof, belonging to the technical field of super-amphiphobic materials. Compared with the super-amphiphobic coating prepared by the existing method, the super-amphiphobic coating prepared by the method has improved oleophobicity and durability. Meanwhile, the preparation is carried out in a vapor deposition mode, so that the consumption of solvents, catalysts and the like is greatly reduced, the environment-friendly requirement is met, and the method can be suitable for large-scale popularization and application.
Description
Technical Field
The invention belongs to the technical field of super-amphiphobic materials, and particularly relates to a super-amphiphobic coating with a micro-nano composite structure and a preparation method thereof.
Background
In recent years, lotus leaf-like superhydrophobic materials have been rapidly developed because of showing great application prospects in the fields of anti-icing, anti-corrosion, oil-water separation, heat and mass transfer and the like. The super-amphiphobic (hydrophobic and oleophobic) material can not only repel water, but also repel low-surface tension liquid on the basis of the super-hydrophobic material, and shows more applications, such as oil stain prevention, domestic sewage and the like, and has the advantage that the super-hydrophobic surface is difficult to reach in practical application.
However, compared to superhydrophobic materials, the construction of the superhydrophobic materials is more complex, requiring not only complex micro-nano composite fractal structures, but also low surface energy molecular modifications. At present, the traditional preparation method is difficult to form a good micro-nano composite fractal structure, so that the super-amphiphobic effect is poor, the super-amphiphobic effect on low-surface tension liquids such as hexadecane is not ideal, the process is complex, the steps are complicated, the cost is high, a large amount of organic solvents are required to be consumed, the environment is not protected, the large-area preparation is difficult, the requirement on a substrate is high, and the wide application is difficult.
Disclosure of Invention
Aiming at the technical problems existing in the prior art, the invention provides the super-amphiphobic coating with the micro-nano composite structure and the preparation method thereof, and aims to reduce the cost and the consumption of organic solvents while improving the super-amphiphobic effect so as to meet the requirement of large-scale preparation.
In order to achieve the purpose, the invention adopts the following technical scheme:
the preparation method of the sprayable super-amphiphobic coating with the micro-nano composite structure is completed by adopting a vapor deposition device, wherein the vapor deposition device comprises a vapor deposition chamber container and storage chamber containers positioned at two sides of the vapor deposition chamber container, the vapor deposition chamber of the vapor deposition chamber container is communicated with the storage chambers of the storage chamber containers positioned at two sides of the vapor deposition chamber container through pipelines (the communicated vapor deposition chamber and the storage chambers are isolated from the outside), valves are respectively arranged on the pipelines, a stirring device is arranged in the vapor deposition chamber container, and a pressure monitoring device is arranged on the vapor deposition chamber container; the preparation method specifically comprises the following steps:
step A, placing micrometer or nanometer silicon dioxide in a vapor deposition chamber, and respectively adding tetraethyl orthosilicate and ammonia water into storage chambers at two sides of the vapor deposition chamber;
b, opening a valve on the pipeline, vacuumizing by using a vapor deposition chamber, and closing the valve on the pipeline after the vacuum pressure is stabilized to a certain negative pressure value (preferably, the absolute value of the vacuum pressure is about 2kpa at the moment and can be specifically adjusted according to actual production requirements);
step C, starting a stirring device in the vapor deposition chamber to disperse silicon dioxide, and growing the silicon dioxide as a nucleus-induced vapor deposition to form an aggregate with a micro-nano composite structure;
d, after the stirring device is closed for a certain time, releasing the negative pressure state in the container of the vapor deposition chamber, and collecting aggregates which are induced to form a micro-nano composite aggregate structure;
step E, placing the aggregate obtained in the step D in a vacuum drying oven, adding a certain amount of low surface energy modification reagent such as perfluorodecyl trichlorosilane, vacuumizing to a certain negative pressure, keeping the reaction for a certain time, then releasing the negative pressure state in the vacuum drying oven, and taking out the aggregate with the micro-nano composite structure, wherein the low surface energy of the aggregate is modified; or, adopting a liquid phase method to carry out low surface energy modification of the aggregate, namely adding a certain amount of dispersing solvent and low surface energy modification reagent into the aggregate with the micro-nano composite structure obtained in the step D; preferably, vapor deposition is adopted, so that the use of solvents can be reduced;
and F, dispersing the aggregate with the modified low surface energy in the step E in a solvent according to a certain mass concentration to obtain a super-amphiphobic suspension, namely the sprayable super-amphiphobic coating with the micro-nano composite structure.
Preferably, in step A, the silica used has a particle size in the range from 1nm to 10. Mu.m, preferably from 10nm to 5. Mu.m.
Preferably, in step E, the low surface energy modification agent may be perfluorooctyl trichlorosilane, perfluorododecyl trichlorosilane, perfluorodecyl triethoxysilane, methyltrichlorosilane, dodecyl trichlorosilane, octadecyl trichlorosilane, dodecyl triethoxysilane.
Preferably, in step E, the aggregate may be modified to reduce its surface energy by co-placing it in a vacuum drier or in a solvent such as ethanol, ethyl acetate, or the like, together with a quantity of a low surface energy modifying agent.
Preferably, in step F, the mass concentration of the resulting super-amphiphobic suspension is in the range of 1-500mg/mL, preferably 10-200 mg/mL.
Preferably, the solvent in the step F can be one or a mixture of more of ethanol, ethyl acetate, butyl acetate and n-hexane.
As a further preferred embodiment, the invention also applies the preparation method of the sprayable super-amphiphobic coating with the micro-nano composite structure to the preparation of the super-amphiphobic coating.
Preferably, when the super-amphiphobic coating is prepared, the sprayable super-amphiphobic coating is directly sprayed on the surface of a workpiece to be processed.
It is further preferred that before the sprayable super-amphiphobic coating is sprayed on the surface of the workpiece, the method further comprises the steps of preparing a primer solution and spraying the primer solution on the surface of the workpiece.
Compared with the prior art, the invention has the beneficial effects that:
the vacuum volatilized tetraethyl orthosilicate and ammonia gas are utilized to grow a micro-nano composite scale secondary surface coarse structure on the surface of silicon dioxide in situ to form a complex micro-nano composite fractal structure, the preparation method of the micro-nano structure is simple, does not need solvents, is environment-friendly, the stability and durability of the prepared micro-nano structure with the secondary surface coarse structure are enhanced, the super-amphiphobic effect of the prepared super-amphiphobic coating is obviously improved compared with that of the traditional super-amphiphobic coating by adopting a solvent configuration mode, and the solvent is not used in the micro-nano structure forming process, so that the solvent used in the whole process is greatly reduced compared with that of the traditional preparation method. The ammonia water and the tetraethyl orthosilicate are combined with the micron or nano silicon dioxide in a volatile line form, compared with the traditional method of directly adopting a liquid phase solvent for preparation, the dosage of chemical materials such as the catalyst and the like is obviously reduced, the introduction of impurities is reduced, the preparation is successful in one step, and the performances of super amphiphobicity, oil stain resistance, corrosion resistance, adhesion resistance, acid and alkali resistance and the like of the prepared coating are improved.
Drawings
FIG. 1 is a field emission Scanning Electron Microscope (SEM) image of a coating obtained in accordance with an embodiment of the present invention;
FIG. 2 is a schematic diagram showing the static water contact angle of the coating obtained in the first embodiment of the present invention when dropped in water;
FIG. 3 is a graph showing static hexadecane contact angles at hexadecane for the coating obtained in example one of the present invention;
FIG. 4 is a schematic view of a vapor deposition apparatus used in the present invention.
Detailed Description
The technical scheme of the invention is further described below with reference to a plurality of embodiments and drawings. It should be noted that the following examples and terms are intended to facilitate understanding of the present invention, and are not intended to be limiting in any way.
As shown in fig. 1 to 4, the invention provides a preparation method of a sprayable super-amphiphobic coating with a micro-nano composite structure, which is completed by adopting a set of vapor deposition device shown in fig. 4, wherein the vapor deposition device comprises a vapor deposition chamber container and storage chamber containers positioned at two sides of the vapor deposition chamber container, the vapor deposition chamber of the vapor deposition chamber container is communicated with the storage chambers of the storage chamber containers positioned at two sides of the storage chamber container through pipelines (the communicated vapor deposition chamber and the storage chambers are isolated from the outside), valves are respectively arranged on the pipelines, a stirring device is arranged in the vapor deposition chamber container, and a pressure monitoring device is arranged on the vapor deposition chamber container; the preparation method specifically comprises the following steps:
step A, placing micrometer or nanometer silicon dioxide in a vapor deposition chamber, and respectively adding tetraethyl orthosilicate (TEOS) and ammonia water into storage chambers at two sides of the vapor deposition chamber;
b, opening a valve on the pipeline, vacuumizing by using a vapor deposition chamber, and closing the valve on the pipeline after the vacuum pressure is stabilized to a certain negative pressure value (preferably, the absolute value of the vacuum pressure is about 2kpa at the moment and can be specifically adjusted according to actual production requirements);
step C, starting a mechanical stirring device in the vapor deposition chamber to disperse silicon dioxide, and growing the silicon dioxide as a nucleus-induced vapor deposition to form an aggregate with a micro-nano composite structure;
d, after the stirrer is turned off for a certain time, releasing the negative pressure state in the container of the vapor deposition chamber, and collecting aggregates which are induced to form a micro-nano composite aggregate structure;
step E, placing the aggregate obtained in the step D in a vacuum drying oven, adding a certain amount of low surface energy modification reagent such as perfluorodecyl trichlorosilane, vacuumizing to a certain negative pressure, keeping the reaction for a certain time, then releasing the negative pressure state in the vacuum drying oven, and taking out the aggregate with the micro-nano composite structure, wherein the low surface energy of the aggregate is modified; alternatively, the low surface energy modification of the aggregate is performed by a liquid phase method, that is, a certain amount of dispersion solvent such as absolute ethyl alcohol and low surface energy modifying agent such as perfluorodecyl trichlorosilane are added into the aggregate with micro-nano composite structure obtained in the step D; preferably, vapor deposition is adopted, so that the use of solvents can be reduced;
and F, dispersing the aggregate with the modified low surface energy in the step E in a solvent according to a certain mass concentration to obtain a super-amphiphobic suspension, namely the sprayable super-amphiphobic coating with the micro-nano composite structure.
Preferably, in step A, the silica used has a particle size in the range from 1nm to 10. Mu.m, preferably from 10nm to 5. Mu.m.
Preferably, in step E, the low surface energy modification agent may be perfluorooctyl trichlorosilane, perfluorododecyl trichlorosilane, perfluorodecyl triethoxysilane, methyltrichlorosilane, dodecyl trichlorosilane, octadecyl trichlorosilane, or dodecyl triethoxysilane.
Preferably, in step E, the aggregate structure may be co-placed with a certain amount of a low surface energy modification agent in a vacuum dryer or in a solvent such as ethanol, ethyl acetate, etc., to modify to reduce its surface energy.
Preferably, in step F, the mass concentration of the resulting super-amphiphobic suspension is in the range of 1-500mg/mL, preferably 10-200 mg/mL.
Preferably, the solvent in the step F can be one or a mixture of more of ethanol, ethyl acetate, butyl acetate and n-hexane.
As a further preferable technical scheme, the preparation method of the sprayable super-amphiphobic coating with the micro-nano composite structure is also applied to the preparation of the super-amphiphobic coating.
Preferably, the sprayable super-amphiphobic coating is sprayed on the surface of a workpiece (such as a glass sheet) to be processed when the super-amphiphobic coating is prepared.
It is further preferred that before the sprayable super-amphiphobic coating is sprayed on the surface of the workpiece, the method further comprises the steps of preparing a primer solution and spraying the primer solution on the surface of the workpiece.
In order to describe the technical solution of the present invention in more detail, the following examples of the present invention will be given in connection with specific experimental operations and processes for preparing super-amphiphobic coatings, as it will be understood by those skilled in the art that the parameter data involved are laboratory data only and do not limit the present invention in any way, and the corresponding parameters will be adjusted accordingly if they are used for practical mass production.
Firstly, weighing 5g of hydrophilic silica nanoparticles with the diameter of about 12nm, placing the hydrophilic silica nanoparticles in a vapor deposition chamber, respectively adding 20mL of tetraethyl orthosilicate and 28% ammonia water by mass fraction into a storage chamber, vacuumizing to the absolute value of vacuum pressure of about 2kpa, closing a valve on a pipeline, starting a mechanical stirring device in the vapor deposition chamber, and keeping the stirring speed at 500r/min for 4 hours at normal temperature; then, the stirring device is closed, the negative pressure is released, and the mixture is kept stand for 1 hour, and about 8g of micro-nano composite aggregate silicon dioxide particles are obtained through collection; then, the collected micro-nano composite aggregate silicon dioxide particles and perfluoro decyl trichlorosilane are placed in a vacuum dryer together, the vacuum is pumped to about 2kpa room temperature and kept for 2 hours, the silicon dioxide is taken out, and absolute ethyl alcohol is used for preparing a suspension with the concentration of 50mg/mL, so that the spray-coating super-amphiphobic coating with a micro-nano composite structure is obtained;
after the sprayable super-amphiphobic coating with the micro-nano composite structure is obtained, measuring 4mL of the sprayable super-amphiphobic coating, controlling the spraying pressure to be 0.3MPa, and directly spraying the sprayable super-amphiphobic coating on the surface of a glass sheet at a spraying distance of about 15 cm;
contact and roll angles were measured with 5uL water and hexadecane, respectively: the water contact angle was 163 °, the roll angle was 1.6 °; the hexadecane contact angle was 154 deg., and the roll angle was 6.5 deg..
Weighing 5g of hydrophilic silica nanoparticles with the diameter of about 20nm, placing the hydrophilic silica nanoparticles in a vapor deposition chamber, respectively adding 20mL of tetraethyl orthosilicate and 28% ammonia water by mass fraction into a storage chamber, vacuumizing to the absolute value of vacuum pressure of about 2kpa, closing a valve on a pipeline, starting a mechanical stirring device in the vapor deposition chamber, and keeping the stirring speed at 500r/min for 4 hours at normal temperature; then, the stirring device is closed, the negative pressure is released, and the mixture is kept stand for 1 hour, and about 8g of micro-nano composite aggregate silicon dioxide particles are obtained through collection; then, the collected micro-nano composite aggregate silicon dioxide particles and perfluorodecyl triethoxysilane are placed in a vacuum dryer together, the vacuum is pumped to about 2kpa, the room temperature is kept for 2 hours, the silicon dioxide is taken out, and the ethyl acetate is used for preparing a suspension with the concentration of 50mg/mL, so that the spray-coated super-amphiphobic coating with a micro-nano composite structure is obtained;
after the sprayable super-amphiphobic coating with the micro-nano composite structure is obtained, preparing 150mg/mL of polyurethane primer solution, measuring 4mL of primer solution, controlling the spraying pressure to be 0.3MPa, and spraying the coating on the surface of a glass sheet at a spraying distance of about 15 cm; after the primer is solidified for twenty minutes, measuring 4mL of the sprayable super-amphiphobic coating, controlling the spraying pressure to be 0.3MPa, spraying the surface of the semi-solidified primer layer at a spraying distance of about 15cm, and solidifying for 24 hours at room temperature to obtain a stable super-amphiphobic coating; the primer solution is sprayed to enhance the mechanical stability of the coating;
contact and roll angles were measured with 5uL water and hexadecane, respectively: the water contact angle is 162 degrees, and the rolling angle is 2.2 degrees; the hexadecane contact angle was 156 deg., and the roll angle was 5.7 deg..
Example III
Weighing 5g of hydrophilic silica nanoparticles with the diameter of about 20nm, placing the hydrophilic silica nanoparticles in a vapor deposition chamber, respectively adding 20mL of tetraethyl orthosilicate and 28% ammonia water by mass fraction into a storage chamber, vacuumizing to the absolute value of vacuum pressure of about 2kpa, closing a valve on a pipeline, starting a mechanical stirring device in the vapor deposition chamber, and keeping the stirring speed at 500r/min for 4 hours at normal temperature; then, the stirring device is closed, the negative pressure is released, and the mixture is kept stand for 1 hour, and about 8g of micro-nano composite aggregate silicon dioxide particles are obtained through collection; then, weighing 0.4g of the collected micro-nano composite aggregate silicon dioxide particles, placing the silicon dioxide particles in a vacuum dryer, adding 0.4mL of perfluorooctyl trichlorosilane, vacuumizing to the absolute value of vacuum pressure of about 2kpa, and standing at normal temperature for 2 hours; taking out after 2 hours, dissolving in 20mL of absolute ethyl alcohol to obtain a sprayable super-amphiphobic suspension, namely the sprayable super-amphiphobic coating with a micro-nano composite structure;
after the sprayable super-amphiphobic coating with the micro-nano composite structure is obtained, preparing 150mg/mL of polyolefin primer solution, measuring 4mL of primer solution, controlling the spraying pressure to be 0.3MPa, and spraying the coating on the surface of a glass sheet at a spraying distance of about 15 cm; after the primer is solidified for thirty minutes, measuring 4mL of the sprayable super-amphiphobic coating, controlling the spraying pressure to be 0.3MPa, and spraying the surface of the semi-solidified primer layer at a spraying distance of about 15 cm; solidifying for 24 hours at room temperature to obtain a stable super-amphiphobic coating; the primer solution is sprayed to enhance the mechanical stability of the coating;
contact and roll angles were measured with 5uL water and hexadecane, respectively: the water contact angle was 161.8 ° and the roll angle was 2.5 °; the hexadecane contact angle was 154 deg., and the roll angle was 6.5 deg..
Example IV
Weighing 5g of hydrophilic silica nanoparticles with the diameter of about 20nm, placing the hydrophilic silica nanoparticles in a vapor deposition chamber, respectively adding 20mL of tetraethyl orthosilicate and 28% ammonia water by mass fraction into a storage chamber, vacuumizing to the absolute value of vacuum pressure of about 2kpa, closing a valve on a pipeline, starting a mechanical stirring device in the vapor deposition chamber, and keeping the stirring speed at 500r/min for 4 hours at normal temperature; then, the stirring device is closed, the negative pressure is released, and the mixture is kept stand for 1 hour, and about 8g of micro-nano composite aggregate silicon dioxide particles are obtained through collection; then, weighing 0.4g of the collected micro-nano composite aggregate silicon dioxide particles, dissolving the particles in 20mL of absolute ethyl alcohol, adding 0.4mL of octadecyl trichlorosilane, and stirring at room temperature for 2 hours to obtain a sprayable super-hydrophobic suspension, namely the sprayable super-hydrophobic coating with a micro-nano composite structure;
after the sprayable super-hydrophobic coating with the micro-nano composite structure is obtained, preparing polyurethane solution with the same mass concentration, mixing the sprayable super-hydrophobic coating with the polyurethane solution in an equal volume to obtain sprayable blend super-hydrophobic solution, measuring 5mL of the blend super-hydrophobic solution, controlling the spraying pressure to be 0.3MPa, spraying the mixture on the surface of a glass sheet at a spraying distance of about 15cm, and curing at room temperature for 12 hours to obtain a super-hydrophobic coating;
contact and roll angles were measured with 5uL water and hexadecane, respectively: the water contact angle was 159 ° and the roll angle was 3.4 °; the hexadecane contact angle was 18 °.
The working principle of the invention is as follows:
after micron or nanometer silicon dioxide, tetraethyl orthosilicate and ammonia water are placed, vacuumizing is carried out by utilizing a vapor deposition chamber, in the process, tetraethyl orthosilicate and ammonia water are volatilized continuously, when vacuumizing is carried out until the absolute value of the vacuum pressure is about 2kpa, the volatilization of the tetraethyl orthosilicate and the ammonia water in a storage chamber tends to be stable, because vacuumizing is carried out from the vapor deposition chamber, the volatilized tetraethyl orthosilicate and ammonia gas are partially mixed in the vapor deposition chamber, at the moment, a valve on a pipeline is closed, a mechanical stirring device (a stirrer) in the vapor deposition chamber is started, and the stirring device is utilized to disperse the micron or nanometer silicon dioxide as a nucleus to induce and generate an aggregate of a micro-nano composite structure, namely, a micro-nano composite scale secondary surface roughness structure grows on the surface of the micron or nanometer silicon dioxide in situ; the generated secondary surface roughness structure enhances the stability and durability, the super-amphiphobic effect of the prepared sprayable super-amphiphobic coating is obviously improved compared with the traditional method of directly adopting solvent configuration, and the solvent is not used in the process of forming the micro-nano composite aggregate structure, so that the solvent used in the whole process is greatly reduced compared with the solvent used in the traditional preparation method. The ammonia water and tetraethyl orthosilicate are combined with micron or nano silicon dioxide in a volatile line form, and compared with the traditional method of directly adopting a liquid phase solvent for preparation, the method reduces the dosage of catalysts and the like and the introduction of impurities, can successfully prepare the coating in one step, and improves the performances of super amphiphobicity, oil stain resistance, corrosion resistance, adhesion resistance, acid and alkali resistance and the like of the prepared coating.
While the foregoing embodiments have been described in detail in connection with the embodiments of the invention, it should be understood that the foregoing embodiments are merely illustrative of the invention and are not intended to limit the invention, and any modifications, additions, substitutions and the like made within the principles of the invention are intended to be included within the scope of the invention.
Claims (9)
1. The preparation method of the sprayable super-amphiphobic coating with the micro-nano composite structure is completed by adopting a vapor deposition device, wherein the vapor deposition device comprises a vapor deposition chamber container and storage chamber containers positioned at two sides of the vapor deposition chamber container, the vapor deposition chamber of the vapor deposition chamber container is communicated with the storage chambers of the storage chamber containers positioned at two sides of the vapor deposition chamber container through pipelines, the pipelines are respectively provided with a valve, a stirring device is arranged in the vapor deposition chamber container, and a pressure monitoring device is arranged on the vapor deposition chamber container; the preparation method is characterized by specifically comprising the following steps of:
step A, placing micrometer or nanometer silicon dioxide in a vapor deposition chamber, and respectively adding tetraethyl orthosilicate and ammonia water into storage chambers at two sides of the vapor deposition chamber;
step B, opening two valves on the pipeline, vacuumizing by using a vapor deposition chamber, and closing the two valves on the pipeline after the vacuum pressure is stabilized to a certain negative pressure value;
step C, starting a stirring device in the vapor deposition chamber to disperse the silicon dioxide, and growing the silicon dioxide as a nucleus-induced vapor deposition to form an aggregate with a micro-nano composite structure;
d, after the stirring device is closed for a certain time, releasing the negative pressure state in the container of the vapor deposition chamber, and collecting and obtaining the aggregate which is induced to form the micro-nano composite structure;
step E, placing the aggregate obtained in the step D in a vacuum drying oven, adding a certain amount of low-surface-energy modifying reagent, vacuumizing to a certain negative pressure, keeping the reaction for a certain time, then removing the negative pressure state in the vacuum drying oven, and taking out the aggregate with the micro-nano composite structure modified by the low-surface energy; or, adopting a liquid phase method to carry out low surface energy modification of the aggregate, namely adding a certain amount of dispersing solvent and low surface energy modification reagent into the aggregate with the micro-nano composite structure obtained in the step D;
and F, dispersing the aggregate with the modified low surface energy in the step E in a solvent according to a certain mass concentration to obtain a super-amphiphobic suspension, namely the sprayable super-amphiphobic coating with the micro-nano composite structure.
2. The process according to claim 1, wherein in step A, the silica used has a particle size in the range of 1nm to 10. Mu.m.
3. The process according to claim 2, wherein in step A, the silica used has a particle size in the range of 10nm to 5. Mu.m.
4. The method of claim 1, wherein in step E, the low surface energy modifying agent is selected from the group consisting of perfluorooctyl trichlorosilane, perfluorododecyl trichlorosilane, perfluorodecyl triethoxysilane, methyltrichlorosilane, dodecyl trichlorosilane, octadecyl trichlorosilane, and dodecyl triethoxysilane.
5. The process according to claim 1, wherein the solvent in step F is one or a mixture of ethanol, ethyl acetate, butyl acetate and n-hexane.
6. The process according to claim 1, wherein in step F, the concentration of the super-amphiphobic suspension obtained is in the range of 1 to 500mg/mL by mass.
7. The process according to claim 6, wherein in step F, the mass concentration of the super-amphiphobic suspension obtained is in the range of 10 to 200mg/mL.
8. Sprayable super-amphiphobic coatings prepared by the preparation process according to one of claims 1 to 7.
9. The use of a sprayable super-amphiphobic coating of claim 8 for the preparation of a super-amphiphobic coating.
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