CN117363061A - Super-hydrophobic conductive composite coating for preventing moon dust adhesion and preparation method thereof - Google Patents
Super-hydrophobic conductive composite coating for preventing moon dust adhesion and preparation method thereof Download PDFInfo
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- 238000000576 coating method Methods 0.000 title claims abstract description 83
- 239000011248 coating agent Substances 0.000 title claims abstract description 68
- 239000000428 dust Substances 0.000 title claims abstract description 57
- 239000002131 composite material Substances 0.000 title claims abstract description 48
- 230000003075 superhydrophobic effect Effects 0.000 title claims abstract description 40
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 230000002209 hydrophobic effect Effects 0.000 claims abstract description 39
- 238000004528 spin coating Methods 0.000 claims abstract description 35
- 238000000034 method Methods 0.000 claims abstract description 31
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000011521 glass Substances 0.000 claims abstract description 27
- 239000002105 nanoparticle Substances 0.000 claims abstract description 17
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000003980 solgel method Methods 0.000 claims abstract description 10
- 238000004729 solvothermal method Methods 0.000 claims abstract description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 104
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 56
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 54
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 38
- 238000003756 stirring Methods 0.000 claims description 29
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 27
- 239000002042 Silver nanowire Substances 0.000 claims description 26
- 239000000725 suspension Substances 0.000 claims description 24
- 239000011780 sodium chloride Substances 0.000 claims description 19
- 235000019441 ethanol Nutrition 0.000 claims description 14
- 239000002245 particle Substances 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 13
- 239000000758 substrate Substances 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- 230000008569 process Effects 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 4
- 239000003292 glue Substances 0.000 claims description 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 3
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 claims 3
- 239000000126 substance Substances 0.000 abstract description 6
- 238000012986 modification Methods 0.000 abstract description 5
- 230000004048 modification Effects 0.000 abstract description 5
- 239000006185 dispersion Substances 0.000 abstract description 2
- 239000007788 liquid Substances 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 33
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 29
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 29
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 29
- 230000000052 comparative effect Effects 0.000 description 20
- 238000005411 Van der Waals force Methods 0.000 description 10
- 239000007787 solid Substances 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- 238000005516 engineering process Methods 0.000 description 8
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- 239000012153 distilled water Substances 0.000 description 7
- 230000001133 acceleration Effects 0.000 description 6
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- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 5
- 239000011324 bead Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000002834 transmittance Methods 0.000 description 5
- 229910052726 zirconium Inorganic materials 0.000 description 5
- 238000004140 cleaning Methods 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 230000005684 electric field Effects 0.000 description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000011370 conductive nanoparticle Substances 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 238000010248 power generation Methods 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- JJWKPURADFRFRB-UHFFFAOYSA-N carbonyl sulfide Chemical compound O=C=S JJWKPURADFRFRB-UHFFFAOYSA-N 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 239000002070 nanowire Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/50—Multilayers
- B05D7/52—Two layers
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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
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- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
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Abstract
The invention discloses a super-hydrophobic conductive composite coating for preventing moon dust adhesion and a preparation method thereof, belonging to the technical field of space special functional coatings and preparation thereof. According to the invention, ag NWs are prepared by a solvothermal method, ag NWs conductive grids are arranged on the surface of glass by a Meyer rod coating method, hydrophobic silica sol is prepared by a sol-gel method, and is mixed with AZO nanoparticle dispersion liquid and then spin-coated on the surface of the Ag NWs conductive grids by a spin-coating method, so that a conductive superhydrophobic AgNWs-AZO composite coating is formed. According to the composite coating, the conductive substance is added into the hydrophobic system and combined with the HMDS modification of the low-surface-energy substance to construct the multistage microroughness, and the conductive path is constructed in the super-hydrophobic coating to provide possibility for free movement of electrons, so that the combination of super-hydrophobic and conductive properties is realized, and the purpose of improving the passive protection efficiency of moon dust is achieved.
Description
Technical Field
The invention relates to a super-hydrophobic conductive composite coating for preventing moon dust adhesion and a preparation method thereof, belonging to the technical field of space special functional coatings and preparation thereof.
Background
Solar photovoltaic power generation is the only energy source for supporting space exploration tasks, and the stability of power generation efficiency directly influences success and failure of deep space exploration tasks. Moon is a focus of current deep space exploration, and is a key step of the human civilization to the universe, however, difficulties are necessarily present in the lunar exploration process. The moon surface is covered with a layer of fine particulate weathering material having an average particle size of about 70 μm, known as moon dust. Due to the effects of cosmic rays, solar wind and meteor impact, the surface of moon dust has a certain charge and sharp edges, and the moon dust is easily attached to the surface of a protective cover of a solar cell panel, so that the solar cell panel is prevented from absorbing light, the photovoltaic conversion efficiency is seriously reduced, and the task of lunar exploration is failed. Therefore, development of effective lunar dust protection technology is a necessary measure for promoting development of lunar exploration engineering.
At present, the technology of moon dust protection can be divided into active protection technology and passive protection technology, wherein the active technology aims at cleaning a surface or protecting the surface from dust deposition by using external force, and mainly comprises methods of fluid cleaning, mechanical cleaning, electric field force cleaning and the like. Due to the space environment limitation of high vacuum and low gravity of moon, the dust removal efficiency of fluid removal is very low; while mechanical dust removal methods include brush brushing, adhesion, and ultrasonic methods, the former two methods require manual operations and are prone to damage to the surface being removed, ultrasonic methods are not suitable for instruments with large surface areas, and therefore, mechanical dust removal methods are not suitable for practical use. The electric field force is utilized to remove the moon dust with high dust removal efficiency, but the device is complex and has the risk of mechanical failure, so that the electric field force cannot be applied on a large scale.
The passive technology refers to a technology of carrying out physical or chemical pretreatment in a laboratory to reduce dust attraction, and no external force is used after installation, and has the characteristics of low cost and high reliability, thus becoming a hot spot for technical development of lunar dust protection. Passive protection mainly uses surface modification to reduce adhesion between a dust layer and a protected surface, thereby achieving the effect of dust reduction. The adhesion between dust and the surface is divided into three types, namely Van der Waals force, electrostatic force and capillary force, and moon dust has the characteristics of small particle size and high surface energy, and has extremely large Van der Waals force and extremely strong adhesion when contacting with the solid surface; the space irradiation and popular impact cause the moon dust surface to have obvious static charge, and the moon dust surface is extremely easy to adhere to the solid surface under the action of static force; due to the high vacuum environment of the lunar surface, the action of capillary force can be ignored when studying passive protection of the lunar dust. Therefore, when studying passive protection technology of moon dust, researchers usually consider reducing van der Waals force and electrostatic force, but in the prior art, only one acting force is considered to be reduced, and dust removal efficiency is limited, so that a method of reducing van der Waals force and simultaneously reducing electrostatic force can be considered to improve dust removal efficiency of moon dust.
The conductive super-hydrophobic composite coating has super-hydrophobic performance and excellent conductive performance, and can effectively eliminate electrostatic acting force between dust particles and the coating while realizing low van der Waals force effect. On one hand, the surface of the conductive super-hydrophobic composite coating has a certain rough structure, the contact area between dust particles and the surface of the coating can be reduced by constructing a slightly convex surface structure, and as the solid surface energy is lower, the dust and the surface have lower van der Waals force, and compared with a flat surface, the surface can show lower dust adhesion; on the other hand, the conductive super-hydrophobic composite coating has low surface resistance, can rapidly conduct static dissipation, prevents static accumulation and furthest reduces dust deposition. The surface of the solid can be kept clean under the combination of the conductive and super-hydrophobic properties of the coating. However, the conventionally used super-hydrophobic coating material is often an insulator, has very small conductivity, cannot realize static dissipation, is unfavorable for reducing the design of adhesion of moon dust, and therefore, the design of a coating combining conductivity and super-hydrophobicity has great value for realizing effective passive protection of moon dust.
Disclosure of Invention
The invention provides a super-hydrophobic conductive composite coating for preventing moon dust adhesion and a preparation method thereof, aiming at solving the technical problems in the prior art.
The technical scheme of the invention is as follows:
the invention aims at providing a preparation method of a super-hydrophobic conductive composite coating, which specifically comprises the following steps:
s1, silver nitrate, PVP, ethylene glycol and sodium chloride are used as raw materials, and AgNWs are prepared by a solvothermal method;
s2, coating AgNWs on a glass substrate for a plurality of times by using a Meyer rod to obtain an Ag NWs grid;
s3, dispersing AZO nano particles in the hydrophobic silica sol to obtain a glue solution;
and S4, spin-coating the glue solution on the AgNWs grid, and heating and drying to obtain the composite coating.
Further defined, the specific operation process of S1 is:
(1) Dissolving sodium chloride and PVP in glycol to obtain a solution A;
(2) Silver nitrate solution is put in glycol to obtain solution B;
(3) Mixing the solution A and the solution B, uniformly stirring, placing the mixture in a hydrothermal kettle for hydrothermal reaction, and cooling to room temperature after the reaction is finished to obtain Ag NWs suspension;
(4) And (3) centrifugally washing the Ag NWs suspension by using ethanol to obtain Ag NWs, and storing the Ag NWs in ethanol for later use.
Further limited, the hydrothermal reaction temperature in the step (3) is 140-180 ℃ and the time is 4-8 h.
Further defined, the hydrothermal reaction temperature in step (3) is 150-170 ℃.
Further defined, the hydrothermal reaction temperature in step (3) is 160 ℃.
Further limited, the hydrothermal reaction time in the step (3) is 5-7 h.
Further defined, the hydrothermal reaction time in step (3) is 6 hours.
Further defined, the molar ratio of silver nitrate to PVP in S1 (1 to 16): 8.
further defined, the molar ratio of silver nitrate to PVP in S1 is 2:1, 1:1, 1:2, 1:4 or 1:8.
Further, the number of coating times in S2 is 10 to 50.
Further defined, the number of applications in S2 is 10, 20, 30, 40 or 50.
Further defined, the particle size of the AZO nanoparticles in S3 is 20 to 100nm.
Further defined, the particle size of the AZO nanoparticles in S3 is 20nm, 40nm, 60nm, 80nm or 100nm.
Further defined, the mass ratio of the hydrophobic silica sol to the AZO nano particles in S3 is (1-20): 1.
Further defined, the mass ratio of hydrophobic silica sol to AZO nanoparticles in S3 is 20:1, 15:1, 10:1 or 5:1, 1:1.
Further limiting, the hydrophobic silica sol in S3 is prepared from TEOS, HMDS, absolute ethyl alcohol and water serving as raw materials by a sol-gel method.
Further defined, the preparation method of the hydrophobic silica sol in S3 comprises the following steps: TEOS is dissolved in absolute ethyl alcohol, HMDS and distilled water are added, and the mixture is stirred to obtain hydrophobic silica sol.
Further defined, the spin-coating speed in S4 is 500 to 4500rmp.
Still further defined, the spin speed in S4 is 500rmp, 1500rmp, 2500rmp, 3500rmp or 4500rmp.
Further defined, the drying temperature in S4 is 60 ℃ for 5min.
The second object of the invention is to provide a super-hydrophobic conductive composite coating prepared by the method, wherein the composite coating has super-hydrophobicity and conductivity.
The invention further provides an application of the super-hydrophobic conductive composite coating, which is particularly used for preventing moon dust from adhering.
The invention has the beneficial effects that:
according to the invention, ag NWs are prepared by a solvothermal method, ag NWs conductive grids are arranged on the surface of glass by a Meyer rod coating method, hydrophobic silica sol is prepared by a sol-gel method, and is mixed with AZO nanoparticle dispersion liquid and then spin-coated on the surface of the Ag NWs conductive grids by a spin-coating method, so that a conductive superhydrophobic AgNWs-AZO composite coating is formed. According to the composite coating, the conductive substance is added into the hydrophobic system and combined with the HMDS modification of the low-surface-energy substance to construct the multistage microroughness, and the conductive path is constructed in the super-hydrophobic coating to provide possibility for free movement of electrons, so that the combination of super-hydrophobic and conductive properties is realized, and the purpose of improving the passive protection efficiency of moon dust is achieved. Compared with the prior art, the method has the following beneficial effects:
(1) The composite coating provided by the invention realizes passive moon dust protection by reducing the Van der Waals force and the electrostatic force simultaneously, and reduces the contact area between dust particles and the surface of the coating by utilizing the rough structure and the micro-convex structure of the surface of the composite coating, and the van der Waals force between the dust and the surface is lower due to the lower surface energy of the composite coating, so that the low moon dust adhesion is shown; on the other hand, the conductive super-hydrophobic composite coating has low surface resistance, can rapidly perform static dissipation, prevents dust adhesion caused by static accumulation, and realizes a dust reduction result by utilizing the synergistic effect of super-hydrophobic and conductive properties. Solves the problem that the traditional Si-based insulating super-hydrophobic material cannot consider the influence of static electricity on passive protection of moon dust when reducing Van der Waals force between solid and moon dust.
(2) According to the invention, the conductive nano particles and the nano wires prepared by the solvothermal method are mutually crosslinked to form a grid to form a conductive path, so that the charge transmission path in the coating is enhanced, the conductive nano particles participate in the formation of micro-nano coarse structures modified by low-surface energy substances on the surface of the coating, the wettability of the coating is reserved to the greatest extent while the conductivity is enhanced, the synergistic effect of Van der Waals force and electrostatic force is fully considered, the dust removal performance is greatly improved, the stable performance of the hydrophobic performance and the conductive performance can be kept under space conditions (pressure, temperature and irradiation), the practical use value is realized, and the method has far-reaching significance in the development of moon dust protection materials for aerospace tasks.
Drawings
FIG. 1 is an XRD pattern of an Ag NWS-AZO composite coating prepared in example 1 of the invention;
FIG. 2 is an SEM photograph of an Ag NWS-AZO composite coating prepared in example 1 of the invention;
FIG. 3 shows AFM test results of AgNWs-AZO composite coatings prepared in example 1 of the present invention;
FIG. 4 shows the transmittance test results of the Ag NWs-AZO composite coatings and glass substrates prepared in experimental examples 1 to 4 of the present invention;
FIG. 5 is a comparative graph showing the results of resistivity tests of the composite coatings prepared in examples 1 to 4 and comparative examples 1 to 2 according to the present invention;
FIG. 6 shows the water contact angle test results of composite coatings prepared from the glass substrates and experimental examples 1 to 4 and comparative examples 1 to 2 according to the present invention;
FIG. 7 shows the results of dust removal tests of the composite coatings and glass substrates prepared in examples 1 to 4 and comparative examples 1 to 2 according to the present invention.
Detailed Description
The present invention will be described in further detail with reference to the following examples in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
The experimental methods used in the following examples are conventional methods unless otherwise specified. The materials, reagents, methods and apparatus used, without any particular description, are those conventional in the art and are commercially available to those skilled in the art.
Example 1
1. AgNWs were prepared using solvothermal method:
3.5mg of sodium chloride and 1.3438g of polyvinylpyrrolidone (PVP) are dissolved in 50ml of ethylene glycol, and the mixture is stirred for 15min to obtain an ethylene glycol solution of PVP containing sodium chloride;
0.5g of silver nitrate solid (the molar ratio of silver nitrate to PVP is 1:4) is dissolved in 30ml of ethylene glycol solution to obtain ethylene glycol solution of silver nitrate;
mixing ethylene glycol solution containing PVP of sodium chloride and ethylene glycol solution containing silver nitrate, stirring uniformly, adding into a hydrothermal kettle, controlling the reaction temperature to 140 ℃, finishing the reaction after the hydrothermal reaction for 6 hours, and cooling to room temperature to obtain Ag NWs suspension;
and (3) centrifugally washing the Ag NWs suspension by using ethanol to finally obtain pure Ag NWs, and storing the pure Ag NWs in ethanol.
2. An AgNWs conductive grid was placed on the glass surface using a meyer rod:
after 20 times coating the Ag NWs on the glass substrate using a meyer rod, an Ag NWs grid with a thickness of 0.5mm was obtained.
3. Preparing hydrophobic silica sol by a sol-gel method, and spin-coating AZO hydrophobic sol on the surface of the AgNWs conductive grid by a spin coating method:
dissolving 4.2ml of TEOS in 60ml of absolute ethyl alcohol, stirring to obtain a mixed solution, adding 4ml of HMDS and 6ml of distilled water, and stirring to obtain hydrophobic silica sol;
dispersing 0.2g of AZO nano particles with the particle size of 20nm in 8g of absolute ethyl alcohol, and fully stirring for 30min to obtain AZO suspension;
adding 6g of hydrophobic silica sol into AZO suspension, adding a proper amount of zirconium beads, and fully stirring for 4 hours to obtain AZO conductive super-hydrophobic coating;
spin-coating AZO conductive super-hydrophobic coating on 3cm×3cm glass sheet with AgNWs conductive grid by using spin coater at 2500rmp and acceleration of 800rmp/s 2 The time is 15s, the spin coating is carried out, and the spin coating is carried out for 5min at 60 ℃ by a heating table, thus obtaining
The XRD spectrum of the Ag NWs-AZO composite coating prepared in this example is shown in fig. 1, and as can be seen from fig. 1, all peaks of (111), (200), (220), (311) and (222) in the XRD spectrum are marked as fcc structure of silver, and no other peaks of any impurity are detected, which indicates the formation of high purity silver nanowires.
SEM photographs of different magnifications of the Ag NWs-AZO composite coating prepared in this example are shown in fig. 2, and as can be seen from fig. 2, the surface of the AgNWs-AZO conductive superhydrophobic composite coating has a micro-nano coarse structure formed by hydrophobic sol and AZO nanoparticles, and the bottom is an Ag NWs conductive grid formed by meyer rod coating.
The AFM test results of the Ag NWs-AZO composite coating prepared in this example are shown in FIG. 3, and it can be seen from FIG. 3 that the average roughness (R q ) 11.2nm.
Example 2
1. AgNWs were prepared using solvothermal method:
3.5mg of sodium chloride and 1.3438g of polyvinylpyrrolidone (PVP) are dissolved in 50ml of ethylene glycol, and the mixture is stirred for 15min to obtain an ethylene glycol solution of PVP containing sodium chloride;
0.5g of silver nitrate solid (the molar ratio of silver nitrate to PVP is 1:4) is dissolved in 30ml of ethylene glycol solution to obtain ethylene glycol solution of silver nitrate;
mixing ethylene glycol solution containing PVP of sodium chloride and ethylene glycol solution containing silver nitrate, stirring uniformly, adding into a hydrothermal kettle, controlling the reaction temperature to be 180 ℃, finishing the reaction after 5 hours of hydrothermal reaction, and cooling to room temperature to obtain Ag NWs suspension;
and (3) centrifugally washing the Ag NWs suspension by using ethanol to finally obtain pure Ag NWs, and storing the pure Ag NWs in ethanol.
2. An AgNWs conductive grid was placed on the glass surface using a meyer rod:
after 20 times coating the Ag NWs on the glass substrate using a meyer rod, an Ag NWs grid with a thickness of 0.5mm was obtained.
3. Preparing hydrophobic silica sol by a sol-gel method, and spin-coating AZO hydrophobic sol on the surface of the AgNWs conductive grid by a spin coating method:
dissolving 4.2ml of TEOS in 60ml of absolute ethyl alcohol, stirring to obtain a mixed solution, adding 4ml of HMDS and 6ml of distilled water, and stirring to obtain hydrophobic silica sol;
dispersing 0.2g of AZO nano particles with the particle size of 20nm in 8g of absolute ethyl alcohol, and fully stirring for 30min to obtain AZO suspension;
adding 6g of hydrophobic silica sol into AZO suspension, adding a proper amount of zirconium beads, and fully stirring for 4 hours to obtain AZO conductive super-hydrophobic coating;
spin-coating AZO conductive super-hydrophobic coating on 3cm×3cm glass sheet with AgNWs conductive grid by using spin coater at 2500rmp and acceleration of 800rmp/s 2 The time is 15s, and the spin coating is followed by heating for 5min at 60 ℃.
Example 3
1. AgNWs were prepared using solvothermal method:
3.5mg of sodium chloride and 1.3438g of polyvinylpyrrolidone (PVP) are dissolved in 50ml of ethylene glycol, and the mixture is stirred for 15min to obtain an ethylene glycol solution of PVP containing sodium chloride;
0.5g of silver nitrate solid (the molar ratio of silver nitrate to PVP is 1:4) is dissolved in 30ml of ethylene glycol solution to obtain ethylene glycol solution of silver nitrate;
mixing ethylene glycol solution containing PVP of sodium chloride and ethylene glycol solution containing silver nitrate, stirring uniformly, adding into a hydrothermal kettle, controlling the reaction temperature to 140 ℃, finishing the reaction after the hydrothermal reaction for 6 hours, and cooling to room temperature to obtain Ag NWs suspension;
and (3) centrifugally washing the Ag NWs suspension by using ethanol to finally obtain pure Ag NWs, and storing the pure Ag NWs in ethanol.
2. An AgNWs conductive grid was placed on the glass surface using a meyer rod:
after coating the Ag NWs on the glass substrate 40 times using a meyer rod, an Ag NWs grid with a thickness of 0.7mm was obtained.
3. Preparing hydrophobic silica sol by a sol-gel method, and spin-coating AZO hydrophobic sol on the surface of the AgNWs conductive grid by a spin coating method:
dissolving 4.2ml of TEOS in 60ml of absolute ethyl alcohol, stirring to obtain a mixed solution, adding 4ml of HMDS and 6ml of distilled water, and stirring to obtain hydrophobic silica sol;
dispersing 0.2g of AZO nano particles with the particle size of 20nm in 8g of absolute ethyl alcohol, and fully stirring for 30min to obtain AZO suspension;
adding 6g of hydrophobic silica sol into AZO suspension, adding a proper amount of zirconium beads, and fully stirring for 4 hours to obtain AZO conductive super-hydrophobic coating;
spin-coating AZO conductive super-hydrophobic coating on 3cm×3cm glass sheet with AgNWs conductive grid by using spin coater at 2500rmp and acceleration of 800rmp/s 2 The time is 15s, and the spin coating is followed by heating for 5min at 60 ℃.
Example 4
1. AgNWs were prepared using solvothermal method:
3.5mg of sodium chloride and 1.3438g of polyvinylpyrrolidone (PVP) are dissolved in 50ml of ethylene glycol, and the mixture is stirred for 15min to obtain an ethylene glycol solution of PVP containing sodium chloride;
0.5g of silver nitrate solid (the molar ratio of silver nitrate to PVP is 1:4) is dissolved in 30ml of ethylene glycol solution to obtain ethylene glycol solution of silver nitrate;
mixing ethylene glycol solution containing PVP of sodium chloride and ethylene glycol solution containing silver nitrate, stirring uniformly, adding into a hydrothermal kettle, controlling the reaction temperature to 140 ℃, finishing the reaction after the hydrothermal reaction for 6 hours, and cooling to room temperature to obtain Ag NWs suspension;
and (3) centrifugally washing the Ag NWs suspension by using ethanol to finally obtain pure Ag NWs, and storing the pure Ag NWs in ethanol.
2. An AgNWs conductive grid was placed on the glass surface using a meyer rod:
after 20 times coating the Ag NWs on the glass substrate using a meyer rod, an Ag NWs grid with a thickness of 0.5mm was obtained.
3. Preparing hydrophobic silica sol by a sol-gel method, and spin-coating AZO hydrophobic sol on the surface of the AgNWs conductive grid by a spin coating method:
dissolving 4.2ml of TEOS in 60ml of absolute ethyl alcohol, stirring to obtain a mixed solution, adding 4ml of HMDS and 6ml of distilled water, and stirring to obtain hydrophobic silica sol;
dispersing 0.4g of AZO nano particles with the particle size of 20nm in 8g of absolute ethyl alcohol, and fully stirring for 30min to obtain AZO suspension;
adding 6g of hydrophobic silica sol into AZO suspension, adding a proper amount of zirconium beads, and fully stirring for 4 hours to obtain AZO conductive super-hydrophobic coating;
spin-coating AZO conductive super-hydrophobic coatingThe coater is used for spin coating film on a 3cm multiplied by 3cm glass sheet with AgNWs conductive grid, the spin coating speed is 2500rmp, and the acceleration is 800rmp/s 2 The time is 15s, and the spin coating is followed by heating for 5min at 60 ℃.
Comparative example 1
The difference between this comparative example and example 1 is: in step 3, AZO nanoparticles were not incorporated, and the remaining parameter settings and process steps were the same as in example 1.
The specific method for preparing the composite coating according to the comparative example is as follows:
1. AgNWs were prepared using solvothermal method:
3.5mg of sodium chloride and 1.3438g of polyvinylpyrrolidone (PVP) are dissolved in 50ml of ethylene glycol, and the mixture is stirred for 15min to obtain an ethylene glycol solution of PVP containing sodium chloride;
0.5g of silver nitrate solid (the molar ratio of silver nitrate to PVP is 1:4) is dissolved in 30ml of ethylene glycol solution to obtain ethylene glycol solution of silver nitrate;
mixing ethylene glycol solution containing PVP of sodium chloride and ethylene glycol solution containing silver nitrate, stirring uniformly, adding into a hydrothermal kettle, controlling the reaction temperature to 140 ℃, finishing the reaction after the hydrothermal reaction for 6 hours, and cooling to room temperature to obtain Ag NWs suspension;
and (3) centrifugally washing the Ag NWs suspension by using ethanol to finally obtain pure Ag NWs, and storing the pure Ag NWs in ethanol.
2. An AgNWs conductive grid was placed on the glass surface using a meyer rod:
after 20 times coating the Ag NWs on the glass substrate using a meyer rod, an Ag NWs grid with a thickness of 0.5mm was obtained.
3. Preparing hydrophobic silica sol by a sol-gel method, and spin-coating the hydrophobic silica sol on the surface of the AgNWs conductive grid by a spin-coating method:
dissolving 4.2ml of TEOS in 60ml of absolute ethyl alcohol, stirring to obtain a mixed solution, adding 4ml of HMDS and 6ml of distilled water, and stirring to obtain hydrophobic silica sol;
spin-coating hydrophobic silica sol on 3cm×3cm glass sheet with Ag NWs conductive mesh with spin-coating speed of 2500rmp and acceleration of 800rmp/s 2 The time is 15s, and the spin coating is followed by heating for 5min at 60 ℃.
Comparative example 2
The difference between this comparative example and example 1 is: the Ag NWs conductive grids were not included and the remaining parameter settings and process steps were the same as in example 1.
The specific method for preparing the composite coating according to the comparative example is as follows:
1. preparing hydrophobic silica sol by a sol-gel method, and spin-coating AZO hydrophobic sol on the surface of a glass substrate by a spin coating method:
dissolving 4.2ml of TEOS in 60ml of absolute ethyl alcohol, stirring to obtain a mixed solution, adding 4ml of HMDS and 6ml of distilled water, and stirring to obtain hydrophobic silica sol;
dispersing 0.4g of AZO nano particles with the particle size of 20nm in 8g of absolute ethyl alcohol, and fully stirring for 30min to obtain AZO suspension;
adding 6g of hydrophobic silica sol into AZO suspension, adding a proper amount of zirconium beads, and fully stirring for 4 hours to obtain AZO conductive super-hydrophobic coating;
spin-coating the AZO conductive super-hydrophobic coating on a glass sheet with the thickness of 3cm multiplied by 3cm by a spin coater to form a film, wherein the spin-coating speed is 2500rmp, the acceleration is 800rmp/s2, the time is 15s, and the film is heated for 5min at the temperature of 60 ℃ by a heating table after spin-coating.
Effect example
(1) As shown in fig. 4, the transmittance test was performed on the Ag NWs-AZO composite coatings and the glass substrates prepared in examples 1 to 4, and it is clear from fig. 4 that the composite coatings prepared in examples 1 to 4 all have higher transmittance, wherein the transmittance of the prepared composite coating is maximum and the average transmittance thereof is about 85% under the process parameters of experimental example 3.
(2) The composite coatings prepared in examples 1 to 4 and comparative examples 1 to 2 were subjected to resistivity tests, and as shown in fig. 5, as can be seen from fig. 5, comparative example 1 showed that the conductivity of the composite coating was reduced by about 10 times due to the presence of AZO conductive particles; compared with comparative example 2, the existence of the constructed Ag NWs conductive network greatly reduces the resistivity of the coating, and the sheet resistivity is reduced by about 10000 times.
(3) The composite coatings prepared in examples 1 to 4 and comparative examples 1 to 2 and the glass substrates were subjected to water contact angle test, and as shown in fig. 6, as can be seen from fig. 6, the conductive superhydrophobic composite coatings of comparative example 1, comparative example 2 and AgNWs-AZO all have good hydrophobicity.
(4) The composite coatings prepared in examples 1 to 4 and comparative examples 1 to 2 were subjected to an electric dust removal test by uniformly scattering charged dust on the surface of a sample first, then fixing the dust-paved sample on the surface of a stage, and slowly moving until the dust slips off, and recording the angle of inclination at the time of slip. As shown in fig. 7, it can be seen from fig. 7 that the comparative bare glass sheet, comparative example 1, comparative example 2 and Ag NWs-AZO conductive superhydrophobic composite coating all have improved dust removal performance, wherein the Ag NWs-AZO conductive superhydrophobic composite coating has the most excellent dust removal performance, and the dust removal angle is about 50 °.
The above description is merely a preferred embodiment of the present invention, and since the person skilled in the art can make appropriate changes and modifications to the above-described embodiment, the present invention is not limited to the above-described embodiment, and some modifications and changes of the present invention should fall within the scope of the claims of the present invention.
Claims (10)
1. The preparation method of the super-hydrophobic conductive composite coating is characterized by comprising the following steps of:
s1, silver nitrate, PVP, ethylene glycol and sodium chloride are used as raw materials, and AgNWs are prepared by a solvothermal method;
s2, coating AgNWs on a glass substrate for a plurality of times by using a Meyer rod to obtain an Ag NWs grid;
s3, dispersing AZO nano particles in the hydrophobic silica sol to obtain a glue solution;
and S4, spin-coating the glue solution on the AgNWs grid, and heating and drying to obtain the composite coating.
2. The preparation method according to claim 1, wherein the specific operation process of S1 is:
(1) Dissolving sodium chloride and PVP in glycol to obtain a solution A;
(2) Silver nitrate solution is put in glycol to obtain solution B;
(3) Mixing the solution A and the solution B, uniformly stirring, placing the mixture in a hydrothermal kettle for hydrothermal reaction, and cooling to room temperature after the reaction is finished to obtain Ag NWs suspension;
(4) And (3) centrifugally washing the Ag NWs suspension by using ethanol to obtain Ag NWs, and storing the Ag NWs in ethanol for later use.
3. The process according to claim 2, wherein (3) the hydrothermal reaction temperature is 140 to 180 ℃ for 4 to 8 hours.
4. The preparation method according to claim 1, wherein the molar ratio of silver nitrate to PVP in S1 is (1 to 16): 8.
5. the method according to claim 1, wherein the number of coating times in S2 is 10 to 50.
6. The preparation method according to claim 1, wherein the particle size of AZO nanoparticles in S3 is 20 to 100nm; the hydrophobic silica sol is prepared from TEOS, HMDS, absolute ethyl alcohol and water by a sol-gel method.
7. The preparation method according to claim 1, wherein the mass ratio of the hydrophobic silica sol to the AZO nanoparticles in S3 is (1-20): 1.
8. The method according to claim 1, wherein the spin-coating speed in S4 is 500 to 4500rmp; the drying temperature was 60℃and the time was 5min.
9. A superhydrophobic conductive composite coating prepared according to the method of any one of claims 1-8, characterized by superhydrophobicity and conductivity.
10. Use of the superhydrophobic conductive composite coating of claim 9 for preventing adhesion of moon dust.
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