CN116273793B - Hydrophobic material with stable micro-nano composite structure and preparation method thereof - Google Patents
Hydrophobic material with stable micro-nano composite structure and preparation method thereof Download PDFInfo
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- 230000002209 hydrophobic effect Effects 0.000 title claims abstract description 81
- 239000000463 material Substances 0.000 title claims abstract description 66
- 239000002114 nanocomposite Substances 0.000 title claims abstract description 58
- 238000002360 preparation method Methods 0.000 title claims abstract description 34
- 238000002493 microarray Methods 0.000 claims abstract description 43
- 238000007514 turning Methods 0.000 claims abstract description 28
- 239000007769 metal material Substances 0.000 claims abstract description 27
- 239000002082 metal nanoparticle Substances 0.000 claims abstract description 27
- 238000005507 spraying Methods 0.000 claims abstract description 15
- 238000004140 cleaning Methods 0.000 claims abstract description 14
- 238000001035 drying Methods 0.000 claims abstract description 14
- 238000003754 machining Methods 0.000 claims abstract description 8
- XPBBUZJBQWWFFJ-UHFFFAOYSA-N fluorosilane Chemical compound [SiH3]F XPBBUZJBQWWFFJ-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims description 31
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 28
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 28
- 229910052782 aluminium Inorganic materials 0.000 claims description 27
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 22
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 12
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 12
- 239000010949 copper Substances 0.000 claims description 12
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 12
- 239000010931 gold Substances 0.000 claims description 12
- 239000004332 silver Substances 0.000 claims description 12
- 229910052802 copper Inorganic materials 0.000 claims description 11
- 229910052737 gold Inorganic materials 0.000 claims description 11
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- 239000002245 particle Substances 0.000 claims description 6
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- 229910000838 Al alloy Inorganic materials 0.000 claims 1
- 229910001020 Au alloy Inorganic materials 0.000 claims 1
- 229910000881 Cu alloy Inorganic materials 0.000 claims 1
- 229910000640 Fe alloy Inorganic materials 0.000 claims 1
- 229910000990 Ni alloy Inorganic materials 0.000 claims 1
- 238000009827 uniform distribution Methods 0.000 claims 1
- 229910052751 metal Inorganic materials 0.000 abstract description 16
- 239000002184 metal Substances 0.000 abstract description 16
- 239000002086 nanomaterial Substances 0.000 abstract description 16
- 238000005516 engineering process Methods 0.000 abstract description 12
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- 230000002195 synergetic effect Effects 0.000 abstract description 3
- 239000002105 nanoparticle Substances 0.000 description 22
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 10
- 240000002853 Nelumbo nucifera Species 0.000 description 9
- 235000006508 Nelumbo nucifera Nutrition 0.000 description 9
- 235000006510 Nelumbo pentapetala Nutrition 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 230000008569 process Effects 0.000 description 7
- 239000000203 mixture Substances 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 210000001595 mastoid Anatomy 0.000 description 4
- 150000002739 metals Chemical class 0.000 description 4
- 239000007921 spray Substances 0.000 description 4
- 230000003746 surface roughness Effects 0.000 description 4
- VBGGLSWSRVDWHB-UHFFFAOYSA-N 1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-henicosafluorodecyl-tris(trifluoromethoxy)silane Chemical compound FC(F)(F)O[Si](OC(F)(F)F)(OC(F)(F)F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F VBGGLSWSRVDWHB-UHFFFAOYSA-N 0.000 description 3
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- 238000005232 molecular self-assembly Methods 0.000 description 3
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- 238000005406 washing Methods 0.000 description 3
- 239000000956 alloy Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000002923 metal particle Substances 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
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- 238000012986 modification Methods 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 208000033830 Hot Flashes Diseases 0.000 description 1
- 206010060800 Hot flush Diseases 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 238000011949 advanced processing technology Methods 0.000 description 1
- 238000003491 array Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
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- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
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- 230000006872 improvement Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
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- 229910000077 silane Inorganic materials 0.000 description 1
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Classifications
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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
- B05D7/14—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 to metal, e.g. car bodies
-
- 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
- B05D1/00—Processes for applying liquids or other fluent materials
- B05D1/02—Processes for applying liquids or other fluent materials performed by spraying
- B05D1/12—Applying particulate materials
-
- 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
- B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
- B05D3/10—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by other chemical means
- B05D3/107—Post-treatment of applied coatings
-
- 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
- B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
- B05D3/12—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by mechanical means
-
- 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
- B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23P—METAL-WORKING NOT OTHERWISE PROVIDED FOR; COMBINED OPERATIONS; UNIVERSAL MACHINE TOOLS
- B23P15/00—Making specific metal objects by operations not covered by a single other subclass or a group in this subclass
-
- 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
- B05D2202/00—Metallic substrate
- B05D2202/10—Metallic substrate based on Fe
-
- 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
- B05D2202/00—Metallic substrate
- B05D2202/20—Metallic substrate based on light metals
- B05D2202/25—Metallic substrate based on light metals based on Al
-
- 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
- B05D2202/00—Metallic substrate
- B05D2202/40—Metallic substrate based on other transition elements
-
- 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
- B05D2202/00—Metallic substrate
- B05D2202/40—Metallic substrate based on other transition elements
- B05D2202/45—Metallic substrate based on other transition elements based on Cu
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- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Powder Metallurgy (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
Abstract
The application provides a hydrophobic material with a stable micro-nano composite structure and a preparation method thereof, wherein the preparation method comprises the following steps: step 1, cleaning the surface of a metal material, and machining a micro array structure on the surface of the metal material by adopting turning; step 2, spraying metal nano particles on the surface of the micro array structure; step 3, after standing and drying, scanning a micro-array structure with a surface covered with metal nano particles by using femtosecond laser to obtain a micro-nano composite structure with the bonded and connected metal nano particles and the micro-array structure; and step 4, carrying out fluorosilane treatment on the micro-nano composite structure to obtain the hydrophobic material of the micro-nano composite structure. The application effectively combines three processing technologies of turning, spraying technology and laser irradiation, prepares the lotus-leaf-like metal hydrophobic material with stable structure under the synergistic effect, and the prepared micro-nano structure has high appearance precision and higher consistency of the hydrophobic performance of each part of the metal hydrophobic material.
Description
Technical Field
The application belongs to the technical field of hydrophobic materials, and particularly relates to a hydrophobic material with a stable micro-nano composite structure and a preparation method thereof.
Background
With the characteristics of ice resistance, corrosion resistance, self-cleaning, bacteriostasis, drag reduction and the like of the hydrophobic material, the hydrophobic material has great application value in the fields of daily life, industrial production, scientific research and the like of people. Lotus leaf is a natural hydrophobic material, and a natural secondary micro-nano structure (a micro-mastoid structure is combined with a mastoid surface to cover a nano-structure) and a chemical state with low surface energy are main factors for causing the hydrophobicity of the lotus leaf, so that the industry and academia widely lift hot flashes for simulating the lotus leaf to prepare the hydrophobic material.
The current methods for preparing the hydrophobic material by simulating lotus leaves mainly comprise a laser etching method, a template method, an electroplating method, a chemical deposition method, a molecular self-assembly method and the like. For example, both Chinese patent CN113278958A and patent CN104498957A adopt a laser etching method to prepare the hydrophobic micro-nano structure. However, the morphology features of the hydrophobic structure prepared by laser etching are greatly different under the micrometer scale, so that the contact angles of water drops at different parts of the hydrophobic structure are also different, and the hydrophobic consistency is poor. There are documents in which a soft film structure excellent in hydrophobic property is prepared by a template method. However, the template method is difficult to prepare the micro-nano structure with complex shape and has low efficiency. Chinese patent CN110684994a adopts an electroplating method to prepare a wide metal template with a hydrophobic structure, but the electroplating method has a significant risk of environmental pollution. The Chinese patent CN103588164A sequentially adopts a chemical deposition method and a molecular self-assembly method to prepare the micro-nano multi-stage hydrophobic structure, but the process of preparing the micro-nano structure by the chemical deposition method and the molecular self-assembly method is not easy to control, and the prepared surface micro-nano structure has strong randomness and large structure difference. At present, a preparation method of a hydrophobic material with a simple preparation method and a uniform and stable structure is not available.
Accordingly, there is a need to provide an improved solution to the above-mentioned deficiencies of the prior art.
Disclosure of Invention
The application aims to provide a hydrophobic material with a stable micro-nano composite structure and a preparation method thereof, so as to solve the problems that the existing preparation method of the hydrophobic material is complex, the micro-nano structure of the surface of the obtained material is unstable, and the difference of hydrophobic consistency is large.
In order to achieve the above object, the present application provides the following technical solutions:
a preparation method of a hydrophobic material with a stable micro-nano composite structure, which comprises the following steps:
step 1, cleaning the surface of a metal material, and machining a micro array structure on the surface of the metal material by adopting turning;
step 2, spraying metal nano particles on the surface of the micro array structure;
step 3, after standing and drying, scanning a micro-array structure with a surface covered with metal nano particles by using femtosecond laser to obtain a micro-nano composite structure with the bonded and connected metal nano particles and the micro-array structure;
and step 4, carrying out fluorosilane treatment on the micro-nano composite structure to obtain the hydrophobic material of the micro-nano composite structure.
In the preparation method of the hydrophobic material with the stable micro-nano composite structure as described above, preferably, in the step 1, the metal material is one or more of a mixture of elemental metals of gold, silver, copper, iron, aluminum and nickel, or one or more of an alloy material of gold, silver, copper, iron, aluminum and nickel.
In the preparation method of the hydrophobic material with the stable micro-nano composite structure, the feeding speed during turning is preferably 5-25 mm/s.
In the preparation method of the hydrophobic material with the stable micro-nano composite structure, preferably, the shape of the micro-array structure comprises one or more of uniformly distributed columnar, conical and spherical mixtures.
In the preparation method of the hydrophobic material with the stable micro-nano composite structure, the height of the micro-array structure is preferably 100-300 μm.
In the preparation method of the hydrophobic material with the stable micro-nano composite structure, preferably, the center-to-center distance between any adjacent shapes of the micro-array structure is 100-600 μm, and the projection length of any shape is 90-300 μm.
In the preparation method of the hydrophobic material with the stable micro-nano composite structure as described above, preferably, in the step 2, the metal nanoparticles are made of one or more of gold, silver, copper, iron, aluminum and nickel elemental metals; or one or more of gold, silver, copper, iron, aluminum and nickel.
In the preparation method of the hydrophobic material with the stable micro-nano composite structure as described above, preferably, in the step 2, the particle size of the metal nanoparticles is 20-100 nm.
In the preparation method of the hydrophobic material with the stable micro-nano composite structure, preferably, in the step 3, the scanning speed of the femtosecond laser is 2000-4000 mm/s, the laser power is 5-20 mW, the laser frequency is 30-50 KHz, and the spot diameter is 20-80 μm.
The hydrophobic material with the stable micro-nano composite structure is prepared by adopting the preparation method.
The beneficial effects are that:
according to the hydrophobic material with the stable micro-nano composite structure and the preparation method thereof, the regular micro-array structure is processed on the metal surface through turning; and combining a spraying process method, uniformly covering nano-scale metal particles on the surface of the micro-array structure; the laser irradiation process is adopted to effectively connect the micro array structure and the nano particles, so that the firmness is high and the structure is stable.
The application effectively combines three processing technologies of turning, spraying technology and laser irradiation, and prepares the lotus leaf-like metal hydrophobic material with stable structure under the synergistic effect.
The preparation method disclosed by the application is simple in procedure, the prepared micro-nano structure is high in morphology precision, and the hydrophobic performance of each part of the metal hydrophobic material is high in consistency.
Drawings
The accompanying drawings, which are included to provide a further understanding of the application and are incorporated in and constitute a part of this specification, illustrate embodiments of the application and together with the description serve to explain the application. Wherein:
FIG. 1 is a preparation flow chart of a preparation method of a hydrophobic material with a stable micro-nano composite structure according to an embodiment of the application;
FIG. 2 is a scanning electron microscope image of Ag nanoparticles according to example 1 of this application;
FIG. 3 is a schematic diagram of the structure of a microcolumn with surface-coated nanoparticles prepared in example 1 of the present application;
FIG. 4 is a schematic view of the surface-coated nanoparticles prepared in examples 3 and 4 of the present application;
fig. 5 is a schematic diagram of the water drop contact angle of the hydrophobic material prepared in example 3 of the present application.
In the figure: the device comprises a 101-beaker, a 102-washing solution, a 103-metal material, a 104-turning device, a 105-micrometer array structure, a 106-spray head, 107-metal nano particles, a 108-femtosecond laser device and 109-micro-nano composite structure.
Detailed Description
The following description of the technical solutions in the embodiments of the present application will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present application, but not all embodiments. All other embodiments, which are derived by a person skilled in the art based on the embodiments of the application, fall within the scope of protection of the application.
The present application will be described in detail with reference to examples. It should be noted that, without conflict, the embodiments of the present application and features of the embodiments may be combined with each other.
According to the hydrophobic material with the stable micro-nano composite structure and the preparation method thereof, provided by the application, the micron column is prepared on the surface of the metal material, and is used for simulating the mastoid structure and the nanosphere of lotus leaves and is used for simulating the nanoscale structure covered on the surface of the mastoid of the lotus leaves. The preparation method disclosed by the application is simple in procedure, and the prepared micro-nano structure is reliable.
The micron structure prepared by turning has the same morphological characteristics and consistent size, and is regular in layout. The spraying technology adopted on the micro-array structure has the advantages of large-area operation, uniform spraying and the like, and uniform metal nano particles can be sprayed on the micro-array structure. Femtosecond laser is an important advanced processing technology, and has the advantages of extremely short pulse width, ultrahigh peak power, controllable energy and the like. When the nano material is irradiated by the femtosecond laser, the femtosecond laser can generate a strong surface plasmon effect, and the nondestructive effect of the base material is achieved, namely the micrometer structure and the nano material are effectively connected on the premise of not damaging the appearance of the nano material, so that the firmness is high and the structure is stable. The application effectively combines the three processing technologies of the turning technology, the spraying technology and the femtosecond laser irradiation technology, and the three processing technologies are cooperated to obtain the metal hydrophobic material with stable structure and good hydrophobic performance.
The application provides a preparation method of a hydrophobic material with a stable micro-nano composite structure, which comprises the following steps:
and step 1, cleaning the surface of the metal material, and machining a micro array structure on the surface of the metal material by adopting turning.
In the specific embodiment of the application, acetone and alcohol are adopted to sequentially clean the surface of the metal material, and a turning process is adopted after the surface is cleaned.
In the specific embodiment of the present application, in step 1, the metal material is one or more mixtures of elemental metals of gold, silver, copper, iron, aluminum and nickel, or one or more mixtures of alloy materials of gold, silver, copper, iron, aluminum and nickel.
In a specific embodiment of the application, the feed speed during turning is 5-25 mm/s (e.g. 6mm/s, 8mm/s, 10mm/s, 12mm/s, 15mm/s, 20mm/s, 22mm/s, 24 mm/s). When the turning speed is greater than 25mm/s, the prepared micron-sized structures are different in height and size, and the surface roughness values of the micron-sized arrays are inconsistent. Different roughness values result in different hydrophobic properties of the portions of the metallic material; secondly, the machining speed is too high, the cutter is easy to damage, the surface roughness value of the later machined micron-sized structure is higher and higher, and the hydrophobic performance of each part of the metal material is different. When the turning speed is less than 5mm/s, the efficiency of preparing the micron-sized structure is lower, the surface roughness value of the micron-sized structure prepared under the speed condition is smaller, and the hydrophobicity of each part of the metal material is not obviously improved.
In particular embodiments of the present application, the microarray structure shape includes a mixture of one or more of uniformly distributed pillars, cones, and spheres. In particular, the microarray structure may be square, cylindrical or triangular pyramid in shape. Preferably, the same shape with uniform shape and equidistant interval, i.e. the shape of the micro array structure is a plurality of evenly distributed squares, or a cylinder or a triangle cone, is processed on the metal material substrate by a turning process, so as to simulate the mastoid structure of lotus leaf.
In embodiments of the application, the height of the microarray structure is 100 to 300 μm (e.g., 150 μm, 200 μm, 250 μm). The center-to-center spacing between any adjacent shapes of the microarray structure is 100 to 600 μm (e.g., 200 μm, 250 μm, 300 μm, 350 μm, 400 μm, 450 μm, 500 μm, 550 μm), and the projected length of any shape is 90 to 300 μm (e.g., 100 μm, 150 μm, 200 μm, 250 μm). The projected length of any shape can be understood as: the diameter of the projection in a circular shape may be the length of the maximum side length of the projection in a square shape. The three functions of the distance, the height and the gap between the shapes in the micro array structure can influence the surface roughness of the material, change the actual contact area of solid and liquid and the contact area of liquid and gas, and further influence the hydrophobicity of the material.
And 2, spraying metal nano particles on the surface of the micro-array structure.
In the specific embodiment of the application, the metal nano-particles are made of one or more of gold, silver, copper, iron, aluminum and nickel elementary metals; or one or more of gold, silver, copper, iron, aluminum and nickel.
And 3, after standing and drying, scanning a micro-array structure with the surface covered with the metal nano-particles by using femtosecond laser to obtain a micro-nano composite structure with the bonded and connected metal nano-particles and the micro-array structure.
In a specific embodiment of the present application, the metal nanoparticles have a particle size of 20 to 100nm (e.g., 30nm, 40nm, 50nm, 60nm, 70nm, 80nm, 90 nm). The metal nano particles can be sprayed on the surface of the micro-array structure in the form of metal nano solution, and the metal nano particles are obtained after standing and drying and are covered on the surface of the micro-array structure.
In a specific embodiment of the application, the scanning speed of the femtosecond laser is 2000-4000 mm/s (such as 2500mm/s, 3000mm/s and 3500 mm/s), the laser power is 5-20 mW (such as 6mW, 8mW, 10mW, 12mW, 14mW, 16mW and 18 mW), the laser frequency is 30-50 KHz (such as 35KHz, 40KHz and 45 KHz), and the spot diameter is 20-80 mu m (such as 30 mu m, 40 mu m, 50 mu m, 60 mu m, 70 mu m and 80 mu m).
The femto-second laser scanning is adopted, so that the metal nano particles and the metal micro-array structure can be bonded and connected, the metal nano particles are firmly fixed on the surface of the micro-array structure, and the micro-nano composite structure with stable hydrophobic material surface is formed.
And step 4, carrying out fluorosilane treatment on the micro-nano composite structure to obtain the hydrophobic material of the micro-nano composite structure.
In the specific embodiment of the application, the fluorosilane treatment is to soak the micro-nano composite structure by adopting a fluorine-containing silane solution, and then dry the micro-nano composite structure to reduce the surface energy of the hydrophobic material.
The turning feed speed in the examples of the present application and the comparative example was 15mm/s, unless otherwise specified.
Example 1
The preparation method of the hydrophobic material with the stable micro-nano composite structure provided by the embodiment comprises the following steps:
s1, pouring 50ml of acetone (washing solution 102) into a beaker 101, and cleaning organic impurities on the surface of an aluminum sheet of a metal material 103; pouring 20ml of alcohol (washing solution 102) into the beaker 101, and cleaning the residual acetone on the surface of the aluminum sheet material of the metal material 103; after the cleaning is finished, N is used for 2 Drying the aluminum sheet;
s2, machining a columnar array structure (a micro array structure 105) with the diameter of 100 microns, the height of 150 microns and the center-to-center distance of 300 microns on the surface of a metal material 103 aluminum sheet by using a turning tool (turning equipment 104);
s3, uniformly spraying 0.1mg/ml of Ag nano particle (metal nano particle 107) solution (the particle size of the Ag nano particles is 20 nm) on the surface of the columnar array structure by adopting a spray head 106;
s4, standing the aluminum sheet and the Ag nano particle solution on the surface in air at room temperature, and drying;
s5, after standing, irradiating the columnar array structure and Ag nano particles coated on the surface of the columnar array structure by using a femtosecond laser device 108 to obtain a micro-nano composite structure 109; setting the power of the femtosecond laser to be 5mW, the laser frequency to be 40KHz, the irradiation speed to be 3000mm/s, the spot size to be 30 mu m, and the center-to-center distance of a scanning path to be 30 mu m;
s6, after femtosecond laser scanning, placing the micro-nano composite structure 109 in 40ml of perfluoro decyl trimethoxy silane solution (the concentration of the solution is 25 mol/L) for 8 hours, and then drying the micro-nano composite structure in a vacuum drying oven at room temperature for 2 hours;
after the fluorosilane is treated, the micro-nano composite structure hydrophobic material with the surface uniformly covered with the nano particles can be obtained, and the hydrophobic material has low surface energy.
FIG. 1 is a preparation flow chart of a preparation method of a hydrophobic material with a stable micro-nano composite structure in an embodiment of the application; FIG. 2 is a scanning electron microscope image of Ag nanoparticles; fig. 3 is a schematic diagram of a columnar array structure of Ag nanoparticles with surface coverage prepared in this example, from which we can see that the morphology of the columnar array structure is identical, the size is uniform, and the arrangement is regular.
The micro-nano composite structure prepared in this example was subjected to a hydrophobic property test using a contact angle measuring instrument, and the contact angle of the water drop in this example was found to be 150.1 °.
Example 2
S1, pouring 50ml of acetone into a beaker 101, and cleaning organic impurities on the surface of a metal material 103 aluminum sheet; pouring 20ml of alcohol into the beaker 101, and cleaning the residual acetone on the surface of the aluminum sheet material of the metal material 103; after the cleaning is finished, N is used for 2 Drying the aluminum sheet;
s2, machining a square array structure (a micro array structure 105) with the diameter of 150 mu m, the height of 200 mu m and the center-to-center distance of 350 mu m on the surface of the aluminum sheet of the metal material 103 by using a turning tool (turning equipment 104);
s3, uniformly spraying 0.1mg/ml Fe nano particle (metal nano particle 107) solution (the particle size of the Fe nano particles is 100 nm) on the surface of the square array structure by adopting a spray head 106;
s4, standing the aluminum sheet and the Fe nanoparticle solution on the surface in air at room temperature, and drying;
s5, after standing, irradiating the square array structure and Fe nano particles coated on the surface of the square array structure by using a femtosecond laser device 108 to obtain a micro-nano composite structure 109; setting the power of the femtosecond laser as 10mW, the laser frequency as 40KHz, the irradiation speed as 3000mm/s, the spot size as 20 μm and the center-to-center distance of the scanning path as 30 μm;
s6, after femtosecond laser scanning, placing the micro-nano composite structure 109 in 40ml of perfluoro decyl trimethoxy silane solution (the concentration of the solution is 25 mol/L) for soaking for 8 hours, and then drying for 2 hours in a vacuum drying oven at room temperature to obtain the micro-nano composite structure hydrophobic material.
The hydrophobic performance test is performed on the micro-nano composite structure prepared in the embodiment by adopting a contact angle measuring instrument, and the contact angle of the water drop in the embodiment is 146.0 degrees.
Example 3
The preparation method of the hydrophobic material with the stable micro-nano composite structure provided by the embodiment comprises the following steps:
s1, pouring 40ml of acetone into a beaker 101, and cleaning organic impurities on the surface of a metal material 103 aluminum sheet; pouring 15ml of alcohol into the beaker 101, and cleaning the residual acetone on the surface of the aluminum sheet material of the metal material 103; after the cleaning is finished, N is used for 2 Drying the aluminum sheet;
s2, machining a conical array structure (a micro array structure 105) with the diameter of 90 mu m, the height of 100 mu m and the center-to-center distance of 100 mu m on the surface of a metal material 103 aluminum sheet by using a turning tool (turning equipment 104);
s3, uniformly spraying 0.2mg/ml of Ag nano particle (metal nano particle 107) solution (the particle size of the Ag nano particle is 40 nm) on the surface of the conical array structure by adopting a spray head 106;
s4, standing the aluminum sheet and the Ag nano particle solution on the surface in air at room temperature, and drying;
s5, after standing, irradiating the columnar array structure and Ag nano particles coated on the surface of the columnar array structure by using a femtosecond laser device 108 to obtain a micro-nano composite structure 109; setting the power of the femtosecond laser to be 10mW, the laser frequency to be 40KHz, the irradiation speed to be 3000mm/s, the spot size to be 40 mu m, and the center-to-center distance of a scanning path to be 40 mu m;
s6, after femtosecond laser scanning, placing the micro-nano composite structure 109 in 40ml of perfluoro decyl trimethoxy silane solution (the concentration of the solution is 25 mol/L) for soaking for 8 hours, and then drying for 2 hours in a vacuum drying oven at room temperature to obtain the micro-nano composite structure hydrophobic material.
Fig. 4 is a schematic diagram of a conical array structure of Ag nanoparticles with a surface coating prepared in this example, from which we can see that the conical array structure has identical morphology, uniform size, and uniform layout.
As shown in fig. 5, the contact angle of the water drop of the hydrophobic material prepared in this embodiment is shown, and the hydrophobic performance test is performed on the hydrophobic structure of the micro-nano composite structure prepared in this embodiment by using a contact angle measuring instrument, where the contact angle of the water drop in this embodiment is 155.3 °.
Example 4
This embodiment differs from embodiment 3 in that: the center-to-center spacing of the tapered array structure machined by the turning tool in step S2 was changed, and the center-to-center spacing of the shape of the tapered array structure was 200 μm, in the same manner as in example 1.
The micro-nano composite structure prepared in this example was subjected to a hydrophobic property test using a contact angle measuring instrument, and the contact angle of the water drop in this example was found to be 145.3 °.
Comparative example 1
The difference between the present comparative example and example 1 is that the femto-second laser scanning is not adopted in step S6, and the micro-nano structure is connected by heating, and other steps are the same as those of the method and example 1, and are not repeated here.
The hydrophobic material prepared in this comparative example had poor hydrophobic property, and the contact angle of the water drop was 135 °.
Comparative example 2
The difference between the comparative example and the example 1 is that the columnar structure processed on the surface of the aluminum sheet by the turning equipment in the step S2 is uneven, and is not an array structure, and other steps are the same as the method and the example 1, and are not repeated here.
The hydrophobic materials prepared in this comparative example were different in drop contact angle from place to place, and were poor in uniformity of hydrophobic properties.
Comparative example 3
The difference between the comparative example and the example 1 is that in the step S5, the columnar array structure and Ag nanoparticles covered on the surface thereof are irradiated by the femtosecond laser, the power of the femtosecond laser is set to 4mW, the irradiation speed is 3000mm/S, the spot size is 18 μm, and other steps are the same as those of the method and the example 1, and are not repeated here.
The hydrophobic material prepared in this comparative example had poor hydrophobic properties and the drop contact angle was 130 °.
To sum up: according to the hydrophobic material with the stable micro-nano composite structure and the preparation method thereof, the regular micro-array structure is processed on the metal surface through turning; and combining a spraying process method, uniformly covering nano-scale metal particles on the surface of the micro-array structure; the laser irradiation process is adopted to effectively connect the micro array structure and the nano particles, so that the firmness is high and the structure is stable.
The application effectively combines three processing technologies of turning, spraying technology and laser irradiation, and prepares the lotus leaf-like metal hydrophobic material with stable structure under the synergistic effect.
The preparation method disclosed by the application is simple in procedure, the prepared micro-nano structure is reliable, and the hydrophobic performance of each part of the metal hydrophobic material is high in consistency.
The above description is only of the preferred embodiments of the present application and is not intended to limit the present application, but various modifications and variations can be made to the present application by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present application should be included in the protection scope of the present application.
Claims (6)
1. The preparation method of the hydrophobic material with the stable micro-nano composite structure is characterized by comprising the following steps of:
step 1, cleaning the surface of a metal material, and machining a micro array structure on the surface of the metal material by adopting turning; the feeding speed during turning is 5-25 mm/s; the height of the micro array structure is 100-300 mu m; the center distance between any adjacent shapes of the micro array structure is 100-600 mu m, and the projection length of any shape is 90-300 mu m;
step 2, spraying metal nano particles on the surface of the micro array structure;
step 3, after standing and drying, scanning a micro-array structure with a surface covered with metal nano particles by using femtosecond laser to obtain a micro-nano composite structure with the bonded and connected metal nano particles and the micro-array structure;
the scanning speed of the femtosecond laser is 2000-4000 mm/s, the laser power is 5-20 mW, the laser frequency is 30-50 KHz, and the spot diameter is 20-80 mu m;
and step 4, carrying out fluorosilane treatment on the micro-nano composite structure to obtain the hydrophobic material of the micro-nano composite structure.
2. The method for preparing a hydrophobic material with a stable micro-nano composite structure according to claim 1, wherein in the step 1, the metal material is one or more of gold, silver, copper, iron, aluminum and nickel, or one or more of gold, silver, copper, iron, aluminum and nickel alloy.
3. The method of claim 1, wherein the microarray structure comprises a uniform distribution of one or more of columnar, tapered, and spherical shapes.
4. The method for preparing a hydrophobic material with a stable micro-nano composite structure according to claim 1, wherein in the step 2, the metal nanoparticles are made of one or more of gold, silver, copper, iron, aluminum and nickel; or one or more of gold, silver, copper, iron, aluminum and nickel.
5. The method for preparing a hydrophobic material with a stable micro-nano composite structure according to claim 1, wherein in the step 2, the particle size of the metal nanoparticles is 20-100 nm.
6. A hydrophobic material with a stable micro-nano composite structure, which is characterized in that the hydrophobic material is prepared by the preparation method according to any one of claims 1 to 5.
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| CN114749350A (en) * | 2022-03-07 | 2022-07-15 | 吉林大学 | Preparation method of antibacterial super-hydrophobic bionic surface on stainless steel substrate |
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