CN115466946B - Metal substrate anti-fouling water coating with micro-nano structure surface - Google Patents
Metal substrate anti-fouling water coating with micro-nano structure surface Download PDFInfo
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- CN115466946B CN115466946B CN202211117904.3A CN202211117904A CN115466946B CN 115466946 B CN115466946 B CN 115466946B CN 202211117904 A CN202211117904 A CN 202211117904A CN 115466946 B CN115466946 B CN 115466946B
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- 239000011248 coating agent Substances 0.000 title claims abstract description 52
- 238000000576 coating method Methods 0.000 title claims abstract description 52
- 239000002086 nanomaterial Substances 0.000 title claims abstract description 47
- 239000002184 metal Substances 0.000 title claims abstract description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 239000000758 substrate Substances 0.000 title claims abstract description 30
- 230000003373 anti-fouling effect Effects 0.000 title claims abstract description 16
- 239000010410 layer Substances 0.000 claims abstract description 51
- 230000007704 transition Effects 0.000 claims abstract description 26
- 239000002344 surface layer Substances 0.000 claims abstract description 23
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 16
- -1 polytetrafluoroethylene Polymers 0.000 claims abstract description 14
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims abstract description 14
- 239000004810 polytetrafluoroethylene Substances 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 13
- 239000000463 material Substances 0.000 claims abstract description 8
- 238000004140 cleaning Methods 0.000 claims description 15
- 239000002105 nanoparticle Substances 0.000 claims description 4
- NLSFWPFWEPGCJJ-UHFFFAOYSA-N 2-methylprop-2-enoyloxysilicon Chemical compound CC(=C)C(=O)O[Si] NLSFWPFWEPGCJJ-UHFFFAOYSA-N 0.000 claims description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- 230000001680 brushing effect Effects 0.000 claims description 3
- 238000003486 chemical etching Methods 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 238000005530 etching Methods 0.000 claims description 3
- 238000010329 laser etching Methods 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims description 3
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 claims description 3
- UKRDPEFKFJNXQM-UHFFFAOYSA-N vinylsilane Chemical compound [SiH3]C=C UKRDPEFKFJNXQM-UHFFFAOYSA-N 0.000 claims description 3
- 238000007761 roller coating Methods 0.000 claims description 2
- 239000002245 particle Substances 0.000 abstract description 17
- 239000010865 sewage Substances 0.000 abstract description 16
- 230000008569 process Effects 0.000 abstract description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 8
- 238000000227 grinding Methods 0.000 abstract description 8
- 239000000843 powder Substances 0.000 abstract description 4
- 239000000377 silicon dioxide Substances 0.000 abstract description 4
- 239000007787 solid Substances 0.000 abstract description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 14
- 239000011863 silicon-based powder Substances 0.000 description 14
- 238000010586 diagram Methods 0.000 description 6
- 230000002209 hydrophobic effect Effects 0.000 description 5
- 240000002853 Nelumbo nucifera Species 0.000 description 2
- 235000006508 Nelumbo nucifera Nutrition 0.000 description 2
- 235000006510 Nelumbo pentapetala Nutrition 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- XJKVPKYVPCWHFO-UHFFFAOYSA-N silicon;hydrate Chemical compound O.[Si] XJKVPKYVPCWHFO-UHFFFAOYSA-N 0.000 description 1
- 230000003075 superhydrophobic effect Effects 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
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B08—CLEANING
- B08B—CLEANING IN GENERAL; PREVENTION OF FOULING IN GENERAL
- B08B17/00—Methods preventing fouling
- B08B17/02—Preventing deposition of fouling or of dust
- B08B17/06—Preventing deposition of fouling or of dust by giving articles subject to fouling a special shape or arrangement
- B08B17/065—Preventing deposition of fouling or of dust by giving articles subject to fouling a special shape or arrangement the surface having a microscopic surface pattern to achieve the same effect as a lotus flower
-
- 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
- C09D127/18—Homopolymers or copolymers of tetrafluoroethene
-
- 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
- C23C26/00—Coating not provided for in groups C23C2/00 - C23C24/00
-
- 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
- C23C2222/00—Aspects relating to chemical surface treatment of metallic material by reaction of the surface with a reactive medium
- C23C2222/20—Use of solutions containing silanes
Abstract
The invention discloses a metal substrate anti-fouling water coating with a micro-nano structure surface, which comprises a transition layer and a micro-nano structure surface layer, wherein the transition layer is attached to the metal substrate surface, and the micro-nano structure surface layer is attached to the transition layer surface; the material of the transition layer is a metal-philic silane coupling agent; the micro-nano structure surface layer is made of polytetrafluoroethylene. The middle of the micron-sized strip-shaped structure is hollowed out, the hollowed-out part is of a columnar structure, and the air retaining capacity of the hollowed-out part is increased, so that the contact area with a solid part is reduced when water drops fall on the surface of the micro-nano structure coating, and the water drops flow away more easily. The clearance of the micron-sized strip-shaped structure is 5 mu m, the grain diameter of the silica powder particles generated in the grinding process is about 1-10 mu m, and when sewage with the silica powder particles falls on the coating, most of the particles are clamped in the middle of the clearance of the strip-shaped structure and then are taken away by water drops, so that the coating cannot be polluted.
Description
Technical Field
The invention relates to the technical field of antifouling of metal substrates, in particular to an antifouling water coating of a metal substrate with a micro-nano structure surface.
Background
The sewage on the inner wall of the grinding machine is accumulated for a long time to form dirt, and the dirt falls onto a machined workpiece after falling off to influence the surface quality of the machined workpiece, so that the maintenance cost of the machine tool is increased. The waterproof coating is widely applied in the fields of aerospace, building industry and the like, mainly utilizes the hydrophobic principle of lotus effect, and can retain air between micro-nano structures, so that the contact area between water drops and the surface is reduced, the water drops can not infiltrate the low-surface-energy surface, and the self-cleaning function is realized. Therefore, the coating structure can be designed according to the component characteristics (silicon powder and water) of the ground sewage to prevent the sewage from staying on the inner wall of the grinding chamber, so that the aim of self-cleaning the inner wall of the grinding chamber is fulfilled.
At present, two main modes exist for constructing a super-hydrophobic surface, namely, a hydrophobic coating with low surface energy is constructed on a rough surface with a surface micro-nano structure, and a micro-nano structure is constructed on the surface with low surface energy; the hydrophobic micro-nano structure commonly used in the second mode comprises the following three types: the structure shown in fig. 3 is a layer ridge structure, and consists of a micron-sized base layer at the bottom and triangular pointed projections on the base layer; the structure shown in fig. 4 is a square column structure, and is composed of a micron-sized base layer at the bottom and a nano-sized square column structure on the base layer; the structure shown in fig. 5 is a hemispherical structure, consisting of a base layer of micrometer scale and a hemispherical structure of nanometer scale thereon; all three structures can realize the aim of water repellency, but the self-cleaning function is poor for sewage, especially sewage mixed with silicon powder.
Disclosure of Invention
In order to solve the problems in the prior art, the invention designs the metal substrate anti-fouling water coating with the micro-nano structure surface, which can realize the self-cleaning function of the sewage mixed with the silicon powder.
In order to achieve the above object, the technical scheme of the present invention is as follows: the metal substrate anti-fouling water coating with the micro-nano structure surface comprises a transition layer and a micro-nano structure surface layer, wherein the transition layer is attached to the metal substrate surface, and the micro-nano structure surface layer is attached to the transition layer surface;
the material of the transition layer is a metal-philic silane coupling agent;
the micro-nano structure surface layer is made of polytetrafluoroethylene.
Further, the thickness of the transition layer is 10-100 μm; the micro-nano structured surface layer has a thickness of 30-100 μm and a contact angle with water of 150 °.
Further, the micro-nano structure of the micro-nano structure surface layer consists of a micro-scale strip structure and a nano-scale layer ridge structure, wherein the middle of the micro-scale strip structure is hollowed, and the layer ridge structure is positioned on the strip structure; the width of the strip-shaped structures is 5 mu m, the height of the strip-shaped structures is 10 mu m, the gap between the two strip-shaped structures is 5 mu m, and the hollow part in the middle of the strip-shaped structures is a cylindrical structure with the diameter of 10 mu m; the layer ridge structure is a triangular strip structure with the width of 4nm and the height of 5nm, and the gap between the ridges is 5nm.
Further, the silane coupling agent includes vinyl silane, amino silane or methacryloxy silane.
Further, the preparation method of the metal substrate anti-fouling water coating with the micro-nano structure surface comprises the following steps:
A. wiping and cleaning the surface of the metal substrate with absolute ethyl alcohol, and then airing;
B. preparing a silane coupling agent into a dilute solution with the mass concentration of 0.5% -1%, coating a transition layer with the thickness of 10-100 mu m on the surface of the cleaned metal substrate, and airing;
C. and (3) coating polytetrafluoroethylene on the surface of the silane coupling agent, airing to form a polytetrafluoroethylene coating, and etching a micron-sized strip structure and a nano-sized layer ridge structure on the polytetrafluoroethylene coating by using a laser etching or chemical etching method to form a micro-nano structure surface layer, wherein the directions of the strip structure and the layer ridge structure are all vertical and downward.
Further, the transition layer is formed by coating a silane coupling agent on a metal substrate in a brushing or roller coating mode and then drying the metal substrate to form a film.
Compared with the existing coating structure, the invention has the following beneficial effects:
1. the micro-nano structure surface designed by the invention is based on the 'lotus leaf effect' hydrophobic principle, and the micro-nano structure is constructed on the polytetrafluoroethylene with low surface energy material, and the hydrophobic effect is realized by utilizing the micron-level strip structure and the nano-level layer ridge structure on the micron-level strip structure.
2. The middle of the micron-sized strip-shaped structure is hollowed out, the hollowed-out part is of a columnar structure, and the air retaining capacity of the hollowed-out part is increased, so that the contact area with a solid part is reduced when water drops fall on the surface of the micro-nano structure coating, and the water drops flow away more easily.
3. The clearance of the micron-sized strip-shaped structure is 5 mu m, the grain diameter of the silica powder particles generated in the grinding process is about 1-10 mu m, and when sewage with the silica powder particles falls on the coating, most of the particles are clamped in the middle of the clearance of the strip-shaped structure and then are taken away by water drops, so that the coating cannot be polluted.
4. The directions of the micron-level strip-shaped structure and the nano-level layer ridge structure are vertical downward, and when silicon powder particles fall into gaps of the strip-shaped structure, the silicon powder particles are more easily taken away by water drops due to the action of gravity, so that the self-cleaning function of the coating is realized.
Drawings
Fig. 1 is a schematic structural view of the coating of the present invention.
FIG. 2 is a schematic diagram of the micro-nano structure surface layer structure of the present invention.
Fig. 3 is a micro-nano structure schematic diagram of a layer ridge structure.
Fig. 4 is a schematic diagram of a micro-nano structure of a square column structure.
Fig. 5 is a schematic diagram of a micro-nano structure of a hemispherical structure.
FIG. 6 is a schematic diagram of a process of implementing the self-cleaning function of the present invention.
FIG. 7 is a schematic diagram of a self-cleaning process according to the present invention.
FIG. 8 is a three-dimensional schematic view of the process of implementing the self-cleaning function of the present invention.
In the figure: 1. metal base material 2, transition layer 3, micro-nano structure surface layer 31, micrometer level strip structure 32, nanometer level layer ridge structure.
Detailed Description
The invention is further described below with reference to the accompanying drawings. As shown in fig. 1-2, the metal substrate anti-fouling water coating with the micro-nano structure surface comprises a transition layer 2 and a micro-nano structure surface layer 3, wherein the transition layer 2 is attached to the surface of the metal substrate 1, and the micro-nano structure surface layer 3 is attached to the surface of the transition layer 2;
the material of the transition layer 2 is a metal-philic silane coupling agent;
the micro-nano structure surface layer 3 is made of polytetrafluoroethylene.
Further, the thickness of the transition layer 2 is 10-100 μm; the micro-nano structured surface layer 3 has a thickness of 30-100 μm and a contact angle with water of 150 deg..
Further, the micro-nano structure of the micro-nano structure surface layer 3 is composed of a micro-scale strip structure and a nano-scale layer ridge structure 32, wherein the middle of the micro-scale strip structure is hollowed, and the layer ridge structure is positioned on the strip structure; the width of the strip-shaped structures is 5 mu m, the height of the strip-shaped structures is 10 mu m, the gap between the two strip-shaped structures is 5 mu m, and the hollow part in the middle of the strip-shaped structures is a cylindrical structure with the diameter of 10 mu m; the layer ridge structure is a triangular strip structure with the width of 4nm and the height of 5nm, and the gap between the ridges is 5nm.
Further, the silane coupling agent includes vinyl silane, amino silane or methacryloxy silane.
Further, the preparation method of the metal substrate anti-fouling water coating with the micro-nano structure surface comprises the following steps:
A. wiping and cleaning the surface of the metal substrate 1 with absolute ethyl alcohol, and then airing;
B. preparing a silane coupling agent into a dilute solution with the mass concentration of 0.5% -1%, coating a transition layer 2 with the thickness of 10-100 mu m on the surface of the cleaned metal substrate 1, and airing;
C. and (3) coating polytetrafluoroethylene on the surface of the silane coupling agent, airing to form a polytetrafluoroethylene coating, and etching a micron-sized strip-shaped structure 31 and a nano-sized layer ridge structure 32 on the polytetrafluoroethylene coating by using a laser etching or chemical etching method to form the micro-nano structure surface layer 3, wherein the directions of the strip-shaped structure and the layer ridge structure are all vertical and downward.
Further, the transition layer 2 is formed by coating a silane coupling agent on the metal substrate 1 by brushing or rolling and then drying.
Fig. 6-8 show the process of realizing the self-cleaning function of the invention, fig. 6 shows the gap of the strip-shaped structure with part of silicon powder particles staying in the micron level after the sewage containing silicon powder flows through the clean coating surface, fig. 7 shows the process of taking away the silicon powder particles staying on the coating surface before along the gap of the strip-shaped structure due to the action of gravity by water drops when the subsequent sewage flows through the coating surface again, and fig. 8 shows the process of taking away the silicon powder particles on the coating surface by water drops, and the coating surface is restored to a clean state again, so that the self-cleaning function of the coating surface is realized.
In the concrete implementation, the placing direction of the metal base material 1 is the same as the direction of the micro-nano structure, and the metal base material is placed along the vertical direction, and as the self-cleaning coating of the inner wall of the grinding chamber is mainly aimed at, the sewage generated in the grinding process is mainly deionized water sewage containing silicon powder particles, and the particle size of the silicon powder particles generated in the grinding process is between 1 and 10 mu m. Therefore, when the sewage containing the silicon powder particles is sputtered onto the surface of the coating, as the two sides of the strip-shaped structure are hollowed, the air retention capacity is increased, the contact area between the sewage and the surface of the coating is reduced, a part of sewage directly flows away, and a small part of silicon powder particles can stay in the gaps of the layered structure, as the strip-shaped structure and the ridge structure are all along the vertical direction, the silicon powder particles staying in the gaps are reduced and taken away by the follow-up sewage due to the self-gravity factor, so that the self-cleaning function of the surface of the coating is realized.
While specific embodiments of the invention have been described above, it will be appreciated by those skilled in the art that the specific embodiments described are illustrative only and not intended to limit the scope of the invention, and that equivalent modifications and variations of the invention in light of the spirit of the invention will be covered by the claims of the present invention.
Claims (5)
1. A metal substrate anti-fouling water coating with a micro-nano structure surface is characterized in that: the micro-nano structure comprises a transition layer (2) and a micro-nano structure surface layer (3), wherein the transition layer (2) is attached to the surface of a metal substrate (1), and the micro-nano structure surface layer (3) is attached to the surface of the transition layer (2);
the material of the transition layer (2) is a metal-philic silane coupling agent;
the micro-nano structure surface layer (3) is made of polytetrafluoroethylene;
the micro-nano structure of the micro-nano structure surface layer (3) consists of a micro-scale strip structure with a hollow middle and a nano-scale layer ridge structure (32), and the layer ridge structure is positioned on the strip structure; the width of the strip-shaped structures is 5 mu m, the height of the strip-shaped structures is 10 mu m, the gap between the two strip-shaped structures is 5 mu m, and the hollow part in the middle of the strip-shaped structures is a cylindrical structure with the diameter of 10 mu m; the layer ridge structure is a triangular strip structure with the width of 4nm and the height of 5nm, and the gap between the ridges is 5nm.
2. A metal substrate anti-fouling water coating having a micro-nano structured surface according to claim 1, wherein: the thickness of the transition layer (2) is 10-100 mu m; the micro-nano structured surface layer (3) has a thickness of 30-100 μm and a contact angle with water of 150 deg..
3. A metal substrate anti-fouling water coating having a micro-nano structured surface according to claim 1, wherein: the silane coupling agent comprises vinyl silane, amino silane or methacryloxy silane.
4. A metal substrate anti-fouling water coating having a micro-nano structured surface according to claim 1, wherein: the preparation method of the metal substrate anti-fouling water coating with the micro-nano structure surface comprises the following steps:
A. wiping and cleaning the surface of the metal substrate (1) with absolute ethyl alcohol, and then airing;
B. preparing a silane coupling agent into a dilute solution with the mass concentration of 0.5% -1%, coating a transition layer (2) with the thickness of 10-100 mu m on the surface of the cleaned metal substrate (1), and airing;
C. and (3) coating polytetrafluoroethylene on the surface of the silane coupling agent, airing to form a polytetrafluoroethylene coating, and etching a micron-sized strip structure (31) and a nano-sized layer ridge structure (32) on the polytetrafluoroethylene coating by using a laser etching or chemical etching method to form a micro-nano structure surface layer (3), wherein the directions of the strip structure and the layer ridge structure are all vertical and downward.
5. The metal substrate anti-fouling water coating having a micro-nano structured surface of claim 4, wherein: the transition layer (2) is formed by coating a silane coupling agent on the metal substrate (1) in a brushing or roller coating mode and then drying.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202211117904.3A CN115466946B (en) | 2022-09-14 | 2022-09-14 | Metal substrate anti-fouling water coating with micro-nano structure surface |
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| CN202211117904.3A CN115466946B (en) | 2022-09-14 | 2022-09-14 | Metal substrate anti-fouling water coating with micro-nano structure surface |
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| CN115466946B true CN115466946B (en) | 2024-01-05 |
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| CN115466946A (en) | 2022-12-13 |
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