CN110653559A - Metal surface with efficient dropwise condensation and preparation method thereof - Google Patents
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- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23P—METAL-WORKING NOT OTHERWISE PROVIDED FOR; COMBINED OPERATIONS; UNIVERSAL MACHINE TOOLS
- B23P9/00—Treating or finishing surfaces mechanically, with or without calibrating, primarily to resist wear or impact, e.g. smoothing or roughening turbine blades or bearings; Features of such surfaces not otherwise provided for, their treatment being unspecified
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K26/00—Working by laser beam, e.g. welding, cutting or boring
- B23K26/02—Positioning or observing the workpiece, e.g. with respect to the point of impact; Aligning, aiming or focusing the laser beam
- B23K26/06—Shaping the laser beam, e.g. by masks or multi-focusing
- B23K26/062—Shaping the laser beam, e.g. by masks or multi-focusing by direct control of the laser beam
- B23K26/0622—Shaping the laser beam, e.g. by masks or multi-focusing by direct control of the laser beam by shaping pulses
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- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K26/00—Working by laser beam, e.g. welding, cutting or boring
- B23K26/352—Working by laser beam, e.g. welding, cutting or boring for surface treatment
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K26/00—Working by laser beam, e.g. welding, cutting or boring
- B23K26/36—Removing material
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F28—HEAT EXCHANGE IN GENERAL
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- F28F13/00—Arrangements for modifying heat-transfer, e.g. increasing, decreasing
- F28F13/18—Arrangements for modifying heat-transfer, e.g. increasing, decreasing by applying coatings, e.g. radiation-absorbing, radiation-reflecting; by surface treatment, e.g. polishing
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- B23K2103/00—Materials to be soldered, welded or cut
- B23K2103/02—Iron or ferrous alloys
- B23K2103/04—Steel or steel alloys
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K2103/00—Materials to be soldered, welded or cut
- B23K2103/08—Non-ferrous metals or alloys
- B23K2103/10—Aluminium or alloys thereof
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K2103/00—Materials to be soldered, welded or cut
- B23K2103/08—Non-ferrous metals or alloys
- B23K2103/12—Copper or alloys thereof
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K2103/00—Materials to be soldered, welded or cut
- B23K2103/08—Non-ferrous metals or alloys
- B23K2103/14—Titanium or alloys thereof
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F28—HEAT EXCHANGE IN GENERAL
- F28F—DETAILS OF HEAT-EXCHANGE AND HEAT-TRANSFER APPARATUS, OF GENERAL APPLICATION
- F28F2245/00—Coatings; Surface treatments
- F28F2245/04—Coatings; Surface treatments hydrophobic
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Abstract
The invention belongs to the technical field of metal surface treatment, and discloses a metal surface with efficient dropwise condensation and a preparation method thereof. The metal surface comprises hydrophilic regions and super-hydrophobic regions; firstly, ablating a metal substrate by adopting pulse laser, and preparing a periodic concave-convex micro-nano structure on the surface of the metal; after the surface is cleaned, modifying the concave-convex micro-nano structure by using a low surface energy substance to obtain a super-hydrophobic metal surface; removing low surface energy substances of the convex parts in the periodic concave-convex micro-nano structure on the super-hydrophobic metal surface by surface precision polishing or pulsed laser ablation to prepare the super-hydrophobic metal surface coating; hydrophilic regions are formed on the surfaces of the convex portions free of the low surface energy substance, and the concave portions coated with the low surface energy substance are super-hydrophobic regions. When the metal surface is coagulated, the coagulated liquid drops are preferentially formed in the hydrophilic area, and the liquid drops are more easily separated from the metal surface due to the limitation of the surrounding super-hydrophobic area, so that the surface is always kept in a drop-shaped coagulation state, and the coagulation efficiency is improved.
Description
Technical Field
The invention belongs to the technical field of metal substrate surface treatment, and particularly relates to a metal bonding surface with efficient dropwise condensation and a preparation method thereof.
Background
The process of water vapor becoming water upon cooling is known as condensation. Coagulation is a key step in industrial processes such as power generation, seawater desalination, thermal management and the like. On the surface of the solid, the condensation process of water vapor includes two forms of drop condensation and film condensation. When the film is condensed, the condensed liquid drops form a water film on the surface, so that the subsequent condensation and heat exchange processes are blocked, and the condensation efficiency is influenced. On the contrary, when the drops are condensed, the condensed liquid leaves the surface when growing to a certain degree, so that the solid surface always has an area in a naked state, thereby improving the efficiency of condensation and heat exchange. The condensation and heat exchange efficiency of the drop condensation is far higher than that of the film condensation.
The conventional means for forming drop-shaped coagulation is to perform hydrophobic modification on the surface of the material, weaken the wetting and spreading of the coagulation liquid drop on the surface and enable the coagulation liquid drop to leave the surface more easily. However, it is difficult to maintain the state of dropwise coagulation for a long time in practical use by conventional hydrophobic modification. In recent years, with the development of nanotechnology, a super-hydrophobic surface with a lotus effect has attracted much attention due to its extremely strong water repellency. When the super-hydrophobic surface is applied to condensation, water vapor can partially enter the surface microstructure, so that the super-hydrophobic surface is partially failed, the liquid is prevented from being separated, and the condensation performance of the super-hydrophobic surface is influenced. Thus, some techniques accelerate the detachment of the liquid by additional means. For example, patent CN 102269539B discloses a method for controlling the diameter of drops when they fall off by applying a wide frequency vibration to a superhydrophobic surface. However, these techniques are relatively complex and costly to apply. How to accelerate the separation of liquid and maintain efficient drop-shaped condensation by treating the surface per se has urgent practical significance.
Disclosure of Invention
To address the above-discussed deficiencies and drawbacks of the prior art, it is a primary object of the present invention to provide a metal surface having highly efficient droplet condensation.
It is another object of the present invention to provide a method for preparing the above metal surface with highly efficient droplet condensation. The method comprises the steps of preparing a conical periodic surface micro-nano structure on a metal surface by using pulse laser, matching with surface hydrophobic modification to realize a super-hydrophobic matrix, and removing the top of the conical structure by surface fine grinding or selective laser ablation to obtain a micron-sized local hydrophilic region. In the condensation process, condensation preferentially occurs in the hydrophilic region, and is limited by the surrounding sunken super-hydrophobic region in the growing process, so that the condensed liquid drops quickly leave the surface, the falling of the condensed liquid drops on the surface is accelerated, and the condensation efficiency is finally improved.
The purpose of the invention is realized by the following technical scheme:
a metal surface having highly efficient droplet condensation, said metal surface comprising hydrophilic regions and superhydrophobic regions; firstly, ablating a metal substrate by adopting pulse laser, and preparing a periodic concave-convex micro-nano structure on the surface of the metal; after the surface is cleaned, modifying the concave-convex micro-nano structure by using a low surface energy substance to obtain a super-hydrophobic metal surface; removing low surface energy substances of the convex parts in the periodic concave-convex micro-nano structure on the super-hydrophobic metal surface by surface precision polishing or pulsed laser ablation to prepare the super-hydrophobic metal surface coating; hydrophilic regions are formed on the surfaces of the raised portions that are free of low surface energy species, while the recessed portions coated with low surface energy species are superhydrophobic regions.
Preferably, the metal substrate is copper, a copper alloy, aluminum, an aluminum alloy, steel or a titanium alloy.
Preferably, the pulsed laser may be a nanosecond laser, a picosecond laser, or a femtosecond laser; the pulse width of the pulse laser is 200 femtoseconds to 10 nanoseconds; the laser in the pulse laser is infrared light, visible light or ultraviolet light, and the laser wavelength in the pulse laser is 300-1100 nm; the pulse repetition frequency of the pulse laser is 10 kHz-2 MHz.
Preferably, the period of the concave-convex periodic micro-nano structure is 1-100 μm, the convex part in the concave-convex periodic micro-nano structure is in a cone shape, a trapezoid shape, a mastoid shape or a convex block, and the concave part is in an inverted triangle shape, an inverted trapezoid shape or a groove.
Preferably, the height of the convex part in the concave-convex periodic micro-nano structure is 1-50 μm.
Preferably, particles generated by laser ablation are further attached to the surface of the super-hydrophobic region, and the particle size of the particles is 10-1000 nm.
Preferably, the low surface energy substance is a substance with a surface energy of less than 25mJ/m2Is less than 25 mN/m.
More preferably, the low surface energy material is one or more of siloxane, fluorosilane, or fatty acid.
Preferably, the water surface contact angle of the hydrophilic region is 0.1-90 degrees, and the area of the hydrophilic region is 0.1-500 mu m2(ii) a The water surface contact angle of the super-hydrophobic area is 150-180 degrees; the thickness of the protruding part for removing the periodic concave-convex micro-nano structure is 0.1-5 mu m.
The preparation method of the metal surface with efficient dropwise condensation comprises the following specific steps:
s1, ablating a metal base material by using pulse laser to obtain a convex-concave periodic surface micro-nano structure on the surface of the metal base material;
s2, modifying the metal surface of the concave-convex periodic surface micro-nano structure by using a low-surface-energy substance to obtain a super-hydrophobic concave-convex micro-nano structure;
s3, removing low surface energy substances of the convex part of the periodic concave-convex micro-nano structure through surface precision polishing or pulse laser ablation to obtain the material; hydrophilic regions are formed on the surfaces of the raised portions that are free of low surface energy species, while the recessed portions coated with low surface energy species are superhydrophobic regions.
The laser ablation removal in the preparation method provided by the invention means that when the energy density of the pulse laser exceeds the ablation threshold of a certain material, the evaporation and melting phenomena occur on the surface of the material in a laser action area to remove the formed material, and the removal amount depends on laser parameters.
Compared with the prior art, the invention has the following beneficial effects:
1. the method comprises the steps of preparing a concave-convex periodic surface micro-nano structure on a metal surface by pulse laser, matching surface modification of low free energy substances to obtain a super-hydrophobic metal surface, and removing the top of the concave-convex periodic surface micro-nano structure by surface precision grinding or selective pulse laser ablation to obtain the metal surface with the concave-convex micro-nano structure with the convex part having hydrophilicity and the periphery having super-hydrophobicity. In the condensation process, the metal surface prepared by the method can accelerate the separation of condensation liquid drops and improve the condensation efficiency.
2. According to the invention, the concave-convex periodic surface micro-nano structure is formed by ablating the surface of the metal material by using laser, the prepared structure is stable, and the period and the depth of the micro-nano structure can be adjusted, so that the final condensation effect can be adjusted, and the method has great flexibility and designability.
3. The invention removes the convex part of the concave-convex periodic surface micro-nano structure by surface precision grinding or selective pulse laser ablation, and the removal depth can be better controlled, thereby realizing the distribution of hydrophilic and super-hydrophobic areas with different proportions.
4. The invention promotes the condensation process by the concave-convex micro-nano structure with hydrophilic convex part and super-hydrophobic periphery. The hydrophilic convex area is beneficial to rapid nucleation of steam to form micron-sized liquid drops, the existence of the surrounding super-hydrophobic area inhibits the interconnection of micron-sized condensed liquid drops, and the formation of large condensed liquid drops is avoided. Meanwhile, the micron-sized liquid drops are more easily dropped from the surface under the constraint of the surrounding super-hydrophobic matrix, so that the coagulation process is accelerated. Compared with the common super-hydrophobic surface, even if the super-hydrophobic part is partially ineffective, because the raised hydrophilic area is higher than the surrounding super-hydrophobic area, and the area of the hydrophilic area is small, the condensed liquid drops still can be separated from the surface more easily under the action of gravity.
Drawings
Fig. 1 is an electron micrograph of the aluminum metal surface with highly efficient droplet condensation in example 1.
Fig. 2 is a schematic diagram of the contact angle of a droplet on the surface of aluminum metal with highly efficient droplet-like condensation in example 1.
Fig. 3 is a photograph comparing the coagulation of the aluminum metal surface with the highly efficient droplet coagulation in example 1 and a general aluminum metal surface.
Detailed Description
The following examples are presented to further illustrate the present invention and should not be construed as limiting the invention. Unless otherwise specified, the technical means used in the examples are conventional means well known to those skilled in the art. Reagents, methods and apparatus used in the present invention are conventional in the art unless otherwise indicated.
Example 1
1. Preparation of the metal substrate: grinding the surface of the aluminum sheet by a mechanical processing method, and cleaning and drying the aluminum sheet for later use;
2. laser processing: femtosecond laser with the pulse width of 800 femtosecond (the repetition frequency is 40kHz, the average power is 10W) is adopted, and the laser is focused into a light spot with the diameter of 40 mu m by matching with an X-Y scanning galvanometer and a plane field lens, so that the laser beam ablates the aluminum surface row by row at the speed of 100mm/s, and the scanning distance of each row and each column is 40 mu m. After laser treatment, a periodic micro-nano structure of a mastoid microstructure, namely, periodically distributed conical micro-protrusions and nano-particles (products of laser ablation) protruding on the surface are formed on the surface of the aluminum, the period of the micro-protrusions is about 40 μm, and the depth of the micro-protrusions is about 30 μm.
3. Surface modification: and (3) washing and drying the aluminum sheet treated in the step (2) by using water, and then putting the aluminum sheet into a closed container dropwise added with perfluorooctyltrimethoxysilane. And putting the container into an oven at 100 ℃ and placing for 1h to obtain the super-hydrophobic aluminum surface.
4. Grinding the surface; and (3) carrying out surface grinding on the super-hydrophobic aluminum surface treated in the step (3) by using a precision grinder, and removing the surface with the depth of 1 mu m to obtain the aluminum surface with efficient dropwise condensation.
FIG. 1 is an electron micrograph of the highly effective droplet-like coagulated metallic aluminum surface in example 1, wherein A is a raised hydrophilic region (within a black dashed frame) after being ground flat and B is a super-hydrophobic region of a recess; as can be seen from fig. 1, the area of the raised hydrophilic region can be controlled by parameters, and the unaffected region still maintains superhydrophobicity. The surface contact angle of the prepared surface water is shown in fig. 2. As can be seen from fig. 2, the contact angle was 149.4 °. The surface coagulation of the prepared aluminum surface when used in the coagulation test (surface temperature 10 ℃, ambient temperature 25 ℃, relative humidity 80%) is shown in fig. 3. Compared with the surface of the aluminum after ordinary polishing, the surface of the aluminum alloy is smaller in condensed liquid drop and easier to roll off from the surface, and the weight of the condensed liquid drop collected in unit time is 2 times that of the ordinary surface.
Example 2
1. Preparation of the metal substrate: firstly, grinding the surface of an aluminum sheet by a mechanical processing method, and cleaning and drying the aluminum sheet for later use;
2. laser processing: the femtosecond pulse laser (wavelength 532nm, pulse width 300 femtosecond, repetition frequency 40kHz, average power 10W) is adopted, and the focusing light spot is 30 μm by matching with an X-Y scanning galvanometer and a plane field lens. The copper surface was ablated row by row and column by column, the pitch of each row and column being 30 μm. The laser beam scanning speed was 60 mm/s. After laser treatment, a periodic micro-nano structure of a mastoid microstructure, namely, periodically distributed micron-sized protrusions and nanoparticles (products of laser ablation) on the surfaces of the protrusions, is formed on the surface of the copper. The periods of the micron-sized protrusions are all about 30 μm, and the depth of the micron-sized structures is about 25 μm;
3. surface modification: and (4) cleaning and drying the copper surface treated in the step (2). Putting the copper substrate into an ethanol solution dissolved with 1% mass fraction of lauric acid, taking out after 2h, and drying in an oven at 60 ℃ for 1h to obtain the super-hydrophobic copper surface.
4. Selective surface removal; and (3) placing the treated super-hydrophobic copper surface in the step (3) on a workbench, accurately positioning the super-hydrophobic copper surface to the top of a certain micron protrusion through a visual positioning system, and scanning a dot matrix with the surface spacing of 30 microns by using the laser system in the step (2) to partially remove the top of the micron structure. Thus obtaining the copper surface with efficient drop-shaped condensation.
Example 3
1. Preparation of the metal substrate: firstly, grinding the surface of a titanium alloy sheet by a machining method, and cleaning and drying the titanium alloy sheet for later use;
2. laser processing: the femtosecond pulse laser (wavelength 532nm, pulse width 300 femtosecond, repetition frequency 40kHz, average power 10W) is adopted, and the focusing light spot is 30 μm by matching with an X-Y scanning galvanometer and a plane field lens. The copper surface was ablated row by row and column by column, the pitch of each row and column being 30 μm. The laser beam scanning speed was 60 mm/s. After laser treatment, a periodic micro-nano structure of a mastoid microstructure, namely, periodically distributed micron-sized protrusions and nanoparticles (products of laser ablation) on the surfaces of the protrusions, is formed on the surface of the titanium alloy. The periods of the micron-sized protrusions are all about 100 μm, and the depth of the micron-sized structures is about 50 μm;
3. surface modification: and (4) cleaning and drying the copper surface treated in the step (2). Putting the titanium alloy into an ethanol solution dissolved with 1% mass fraction of lauric acid, taking out after 2h, and drying in a drying oven at 60 ℃ for 1h to obtain the super-hydrophobic titanium alloy surface.
4. Selective surface removal; and (3) placing the treated super-hydrophobic copper surface in the step (3) on a workbench, accurately positioning the super-hydrophobic copper surface to the top of a certain micron protrusion through a visual positioning system, and scanning a dot matrix with the surface spacing of 30 microns by using the laser system in the step (2) to partially remove the top of the micron structure. Thus obtaining the titanium alloy surface with efficient dropwise condensation.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations and simplifications are intended to be included in the scope of the present invention.
Claims (10)
1. A metal surface having highly efficient droplet condensation, wherein the metal surface comprises hydrophilic regions and superhydrophobic regions; firstly, ablating a metal substrate by adopting pulse laser, and preparing a periodic concave-convex micro-nano structure on the surface of the metal; after the surface is cleaned, modifying the concave-convex micro-nano structure by using a low surface energy substance to obtain a super-hydrophobic metal surface; removing low surface energy substances of the convex parts in the periodic concave-convex micro-nano structure on the super-hydrophobic metal surface by surface precision grinding or pulsed laser ablation to prepare the super-hydrophobic metal surface coating; hydrophilic regions are formed on the surfaces of the raised portions that are free of low surface energy species, while the recessed portions coated with low surface energy species are superhydrophobic regions.
2. The metal surface with high efficiency of droplet condensation according to claim 1, wherein the metal substrate is copper, copper alloy, aluminum alloy, steel or titanium alloy.
3. The metal surface with efficient droplet condensation according to claim 1, wherein the pulsed laser can be a nanosecond laser, a picosecond laser, or a femtosecond laser; the pulse width of the pulse laser is 200 femtoseconds to 10 nanoseconds; the laser in the pulse laser is infrared light, visible light or ultraviolet light, and the laser wavelength in the pulse laser is 300-1100 nm; the pulse repetition frequency of the pulse laser is 10 kHz-2 MHz.
4. The metal surface with efficient dropwise condensation according to claim 1, wherein the period of the concave-convex periodic micro-nano structure is 1-100 μm; the convex part in the concave-convex periodic micro-nano structure is in a conical shape, a trapezoid shape, a mastoid shape or a convex block, and the concave part is in an inverted triangle shape, an inverted trapezoid shape or a groove.
5. The metal surface with high efficiency drop-shaped condensation according to claim 4, wherein the height of the raised part in the concavo-convex periodic micro-nano structure is 1-50 μm.
6. The metal surface with efficient droplet coagulation as claimed in claim 1, wherein the surface of the super-hydrophobic region is further attached with particles generated by laser ablation, and the particle size of the particles is 10-1000 nm.
7. The method of claim 1 wherein the low surface energy material is a material having a surface energy of less than 25mJ/m2Is less than 25 mN/m.
8. The metal surface with efficient droplet coagulation of claim 7, wherein the low surface energy material is one or more of a siloxane, fluorosilane, or fatty acid.
9. The metal surface with highly effective droplet coagulation as claimed in claim 1, wherein the hydrophilic region has a water surface contact angle of 0.1 to 90 ° and an area of 0.1 to 500 μm2(ii) a The water surface contact angle of the super-hydrophobic area is 150-180 degrees; the thickness of the protruding part for removing the periodic concave-convex micro-nano structure is 0.1-5 mu m.
10. The method for preparing a metal surface with efficient droplet condensation according to any of claims 1-9, characterized by comprising the following specific steps:
s1, ablating a metal base material by using pulse laser to obtain a convex-concave periodic surface micro-nano structure on the surface of the metal base material;
s2, modifying the metal surface of the concave-convex periodic surface micro-nano structure by using a low-surface-energy substance to obtain a super-hydrophobic concave-convex micro-nano structure;
s3, removing low surface energy substances of the convex part of the periodic concave-convex micro-nano structure through surface precision grinding or pulse laser ablation to obtain the material; hydrophilic regions are formed on the surfaces of the raised portions that are free of low surface energy species, while the recessed portions coated with low surface energy species are superhydrophobic regions.
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CN111318053A (en) * | 2020-02-28 | 2020-06-23 | 广州大学 | Super-hydrophobic aluminum alloy filter screen and preparation method and application thereof |
CN111318053B (en) * | 2020-02-28 | 2022-02-11 | 广州大学 | Super-hydrophobic aluminum alloy filter screen and preparation method and application thereof |
CN112899734A (en) * | 2021-01-21 | 2021-06-04 | 长春理工大学 | Method for processing silicon carbide-nickel composite corrosion-resistant coating on surface of metal substrate |
CN114619148A (en) * | 2022-03-01 | 2022-06-14 | 南京理工大学 | Method for changing surface wettability of invar alloy through femtosecond laser |
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