CN117431495A - Super-hydrophobic anti-corrosion double-layer structure of metal surface and preparation method thereof - Google Patents
Super-hydrophobic anti-corrosion double-layer structure of metal surface and preparation method thereof Download PDFInfo
- Publication number
- CN117431495A CN117431495A CN202311748683.4A CN202311748683A CN117431495A CN 117431495 A CN117431495 A CN 117431495A CN 202311748683 A CN202311748683 A CN 202311748683A CN 117431495 A CN117431495 A CN 117431495A
- Authority
- CN
- China
- Prior art keywords
- double
- corrosion
- super
- layer structure
- femtosecond laser
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000005260 corrosion Methods 0.000 title claims abstract description 60
- 230000003075 superhydrophobic effect Effects 0.000 title claims abstract description 51
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 45
- 239000002184 metal Substances 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000007769 metal material Substances 0.000 claims abstract description 29
- 238000000137 annealing Methods 0.000 claims abstract description 27
- 230000007797 corrosion Effects 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 14
- 238000011282 treatment Methods 0.000 claims abstract description 13
- 230000001678 irradiating effect Effects 0.000 claims abstract description 10
- 238000004506 ultrasonic cleaning Methods 0.000 claims abstract description 9
- 229910000838 Al alloy Inorganic materials 0.000 claims description 31
- 239000000126 substance Substances 0.000 claims description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- 230000000737 periodic effect Effects 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 6
- 239000002159 nanocrystal Substances 0.000 claims description 5
- 229910001069 Ti alloy Inorganic materials 0.000 claims description 3
- 239000010935 stainless steel Substances 0.000 claims description 3
- 229910001220 stainless steel Inorganic materials 0.000 claims description 3
- 238000007664 blowing Methods 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 27
- 230000002829 reductive effect Effects 0.000 abstract description 9
- 238000012545 processing Methods 0.000 abstract description 8
- 238000002161 passivation Methods 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 5
- 238000005536 corrosion prevention Methods 0.000 abstract description 2
- 239000000523 sample Substances 0.000 description 35
- 230000000052 comparative effect Effects 0.000 description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 238000012360 testing method Methods 0.000 description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 230000010287 polarization Effects 0.000 description 6
- 238000005096 rolling process Methods 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 238000009826 distribution Methods 0.000 description 5
- 238000006056 electrooxidation reaction Methods 0.000 description 5
- 230000005540 biological transmission Effects 0.000 description 4
- 238000001291 vacuum drying Methods 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 230000006399 behavior Effects 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 239000002086 nanomaterial Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000003917 TEM image Methods 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 238000005280 amorphization Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 230000003111 delayed effect Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 230000003628 erosive effect Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000010884 ion-beam technique Methods 0.000 description 2
- 238000013532 laser treatment Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000013535 sea water Substances 0.000 description 2
- 229910001094 6061 aluminium alloy Inorganic materials 0.000 description 1
- 210000004712 air sac Anatomy 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 230000002421 anti-septic effect Effects 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000011664 nicotinic acid Substances 0.000 description 1
- 230000036961 partial effect Effects 0.000 description 1
- 230000005501 phase interface Effects 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- 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
- B23K26/355—Texturing
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- 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
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
- C21D1/06—Surface hardening
- C21D1/09—Surface hardening by direct application of electrical or wave energy; by particle radiation
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
- C21D1/26—Methods of annealing
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D6/00—Heat treatment of ferrous alloys
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/04—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of aluminium or alloys based thereon
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/16—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of other metals or alloys based thereon
- C22F1/18—High-melting or refractory metals or alloys based thereon
- C22F1/183—High-melting or refractory metals or alloys based thereon of titanium or alloys based thereon
-
- 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
- C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C8/06—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases
- C23C8/08—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases only one element being applied
- C23C8/10—Oxidising
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D2201/00—Treatment for obtaining particular effects
- C21D2201/03—Amorphous or microcrystalline structure
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- Mechanical Engineering (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Thermal Sciences (AREA)
- Optics & Photonics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Plasma & Fusion (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
- Laser Beam Processing (AREA)
Abstract
The invention relates to the technical field of laser processing, in particular to a metal surface super-hydrophobic anti-corrosion double-layer structure and a preparation method thereof. Comprising the following steps: fixing a metal material, focusing femtosecond laser pulses to the surface of the metal material by adopting a focusing element to perform grid scanning irradiation; the femtosecond laser pulse is a double-beam femtosecond laser pulse or a multi-beam femtosecond laser pulse; scanning irradiation conditions: the scanning interval is 30-100 mu m, and the scanning speed is 0.1-3mm/s; setting pulse delay time and power ratio parameters between femtosecond laser beams, and scanning and irradiating for 1-6 times; and finishing scanning irradiation, and performing ultrasonic cleaning and annealing treatment on the metal material to obtain the super-hydrophobic anti-corrosion double-layer structure of the metal surface. The advantages are that: the method enhances the high-temperature passivation and amorphous phase generation effect of the material, and realizes double-layer corrosion prevention; the corrosion current of the processed metal sample is obviously reduced, and the corrosion resistance is obviously improved while the material has super-hydrophobic performance.
Description
Technical Field
The invention relates to the technical field of laser processing, in particular to a metal surface super-hydrophobic anti-corrosion double-layer structure and a preparation method thereof.
Background
The aluminum alloy material is widely applied in the field of marine equipment in China due to the characteristics of easy processing, light weight, high strength and the like. However, considering extreme conditions of the marine environment, such as high salinity and high humidity, more severe demands are placed on the corrosion resistance of marine equipment.
In recent years, the construction of a bionic structure with superhydrophobic corrosion resistance on a metal surface has become a widely-noted hot spot for researchers. The key point of the technology is that the surface of the material is constructed with rich rough structures, and simultaneously, organic substances with low surface energy characteristics are coated. The antiseptic mechanism is as follows: on one hand, the contact area between erosion ions in water and the solid metal surface is reduced by utilizing a plurality of tiny air sac effects provided by the rough structure of the material surface; on the other hand, the surface energy of materials is reduced by a method of applying an organic coating so as to realize the super-hydrophobic property. However, the coating method has various problems of complicated operation procedure, poor binding force, easy falling off and the like, so that the method is limited in practical application. In order to solve the problem, researchers adopt a laser technology to generate a micro-nano structure on the surface of a material, and then the surface energy of the material is reduced in a thermal annealing treatment mode, so that the super-hydrophobic effect of the surface of the material without a coating is successfully realized. Chinese patent publication No. CN115786652A, publication date 2023, 3 and 14, and invention name of "an intrinsic superhydrophobic material, preparation method and application thereof" discloses an intrinsic superhydrophobic material with low energy state amorphous-nanocrystalline mosaic structure prepared on aluminum alloy surface by femtosecond laser, and has excellent superhydrophobic performance.
However, when the metal material with the superhydrophobic surface is soaked in a seawater environment, the loss of air in the micro-nano structure on the surface of the material is accelerated due to fluid flow, static pressure, soaking time and the like, and finally the contact area between the surrounding seawater and the metal surface is increased. B. The Zhang et al found through experiments and simulations that the amorphous-nanocrystalline mosaic structure exhibited high-energy state characteristics of irregular atomic arrangement at the phase interface, provided a convenient path for etching ions, and increased the risk of metal corrosion. In contrast, an amorphous structure without crystal defects has a stronger barrier effect against erosive ions. However, long-range disorder of the amorphous phase atomic arrangement causes an increase in entropy value thereof, and low surface energy and superhydrophobic characteristics cannot be obtained. Therefore, a novel processing method is sought to prepare a double-layer anti-corrosion protection structure with an upper layer composed of low-energy-state nanocrystalline and amorphous phase mosaic and a lower layer composed of uniform and compact amorphous phase, which has important significance for corrosion prevention of metal materials in the ocean. However, due to the complex processes of high temperature, rapid cooling, energy relaxation and the like required by the double-layer anti-corrosion structure, the preparation of the double-layer anti-corrosion structure is very difficult for a person skilled in the art, and no effective way for realizing the preparation of the double-layer anti-corrosion structure is found at present.
Disclosure of Invention
The invention provides a super-hydrophobic anti-corrosion double-layer structure of a metal surface and a preparation method thereof.
The first aim of the invention is to provide a preparation method of a metal surface super-hydrophobic anti-corrosion double-layer structure, which comprises the following steps:
s1, fixing a metal material, and focusing femtosecond laser pulses to the surface of the metal material by adopting a focusing element to perform grid scanning irradiation; the femtosecond laser pulse is a double-beam femtosecond laser pulse or a multi-beam femtosecond laser pulse; the scanning irradiation conditions are as follows: the scanning interval is 30-100 mu m, and the scanning speed is 0.1-3mm/s;
s2, setting pulse delay time and power ratio parameters between femtosecond laser beams, scanning and irradiating for 1-6 times, and forming a periodic micro-nano groove structure on the surface of the metal material;
and S3, finishing scanning irradiation, and performing ultrasonic cleaning and annealing treatment on the metal material to obtain the super-hydrophobic anti-corrosion double-layer structure of the metal surface.
Preferably, the femtosecond laser pulse is a two-beam femtosecond laser pulse.
Preferably, the femtosecond laser pulse conditions are: the laser pulse width is 0.03-1 ps, and the frequency is 1-50kHz; the pulse time delay adjustment range between the two light beams is 5-100ps, the laser power range is 100-1000mW, and the power ratio range of the two light beams is 1:1.1-5.
Preferably, the pulse time delay between the two light beams is 10-50 ps, and the power ratio range of the two laser beams is 3: 5-9.
Preferably, step S3 further includes: blowing with nitrogen before annealing treatment; the annealing conditions are as follows: the annealing temperature is 180-220 ℃, and the annealing time is 3-8 h.
Preferably, the metal material is an aluminum alloy, a titanium alloy or stainless steel.
Preferably, the focusing element is a plano-convex lens.
The second aim of the invention is to provide a metal surface super-hydrophobic anti-corrosion double-layer structure, which is prepared by a preparation method of the metal surface super-hydrophobic anti-corrosion double-layer structure, wherein the upper layer of the double-layer structure is a periodic micro-nano groove structure, and the groove structure has the depth of 30-70 um and the width of 30-100 um and is formed by embedding nanocrystalline and amorphous phase; the lower layer substance of the double-layer structure is composed of uniform and compact amorphous phase.
Preferably, the average size of the nanocrystals is 5.5nm, encapsulated by the amorphous phase and no grain boundaries are present.
Preferably, the metal material is an aluminum alloy; in the super-hydrophobic anti-corrosion double-layer structure of the metal surface, the nanocrystalline is gamma-Al 2 O 3 A substance having an amorphous phase of Al 2 O 3 A substance.
Compared with the prior art, the invention has the following beneficial effects:
(1) The invention utilizes the strong thermodynamic correlation of the pulse time delay adjustable femtosecond laser and the substance in the action process to promote the high-efficiency absorption and the energy space local distribution of the material surface to the delayed light beam, thereby enhancing the high-temperature passivation and the amorphous phase generation effect of the material and realizing a double-layer anti-corrosion protection structure;
(2) In the prepared metal surface super-hydrophobic anti-corrosion double-layer structure, an upper layer substance is formed by embedding nanocrystalline and amorphous phase, the nanocrystalline is wrapped by the amorphous phase and no grain boundary exists, so that the surface super-hydrophobic property is endowed; the lower layer material is composed of uniform and compact amorphous phase, has the characteristics of intrinsic high corrosion resistance, and has strong and uniform passivation behaviors in double-layer structures; the corrosion current of the aluminum alloy sample after femtosecond laser processing can be reduced to 1.1X10 -10 A cm -2 The corrosion resistance of the material is obviously improved.
Drawings
Fig. 1 is a flowchart of a preparation method of a super-hydrophobic anti-corrosion double-layer structure of a metal surface, which is provided by an embodiment of the invention.
FIG. 2 is a microscopic image of the micro-nano structure formed on the metal surface after the femtosecond laser processing provided in comparative example 2 and example 1 according to the present invention, and atomic number ratio of the measured elements; a-b: comparative example 2; c-d: example 1.
FIG. 3 is an experimental graph of contact angle of a metal surface not subjected to laser treatment according to the present invention, and an experimental graph of contact angle and rolling angle of a droplet measured under the super-hydrophobic condition obtained when different laser pulse delay time to power ratios are adopted as provided in comparative examples 1 to 2 and examples 1 to 3; (a) untreated sample (comparative example 1); (b) single beam femtosecond laser treatment (comparative example 2); (c) example 1; (d) example 2; (e) example 3.
FIG. 4 is a cross-sectional transmission electron micrograph image and an oxygen content distribution diagram of a super-hydrophobic corrosion protection structure for a metal surface according to comparative example 2 and example 1 of the present invention, wherein upper and lower ends of a and c virtual lines are respectively divided into upper and lower portions of a passivation layer; a-b: comparative example 2; c-d: example 1.
FIG. 5 is a high definition transmission electron micrograph of the metal surface super-hydrophobic corrosion protection structure provided in comparative example 2 and example 1 at the upper and lower layers of the cross section according to the present invention; a. b is the upper and lower layers of comparative example 2, respectively; c. d is the upper and lower layers of example 1, respectively.
Fig. 6 is an X-ray diffraction pattern according to comparative example 2 and example 1 of the present invention.
Fig. 7 is a polarization curve obtained by performing electrochemical tests with different laser delay times versus power ratios provided by the non-laser treated metal according to the present invention (comparative example 1) and comparative example 2 and examples 1-3.
Detailed Description
Hereinafter, embodiments of the present invention will be described with reference to the accompanying drawings. In the following description, like modules are denoted by like reference numerals. In the case of the same reference numerals, their names and functions are also the same. Therefore, a detailed description thereof will not be repeated.
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be further described in detail with reference to the accompanying drawings and specific embodiments. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not to be construed as limiting the invention.
The invention provides a preparation method of a metal surface super-hydrophobic anti-corrosion double-layer structure, which specifically comprises the following steps:
s1, fixing a metal material, and focusing femtosecond laser pulses to the surface of the metal material by adopting a focusing element to perform grid scanning irradiation; the femtosecond laser pulse is a double-beam femtosecond laser pulse or a multi-beam femtosecond laser pulse;
s2, setting pulse delay time and power proportioning parameters between femtosecond laser beams, and scanning and irradiating for 1-6 times;
and S3, finishing scanning irradiation, and performing ultrasonic cleaning and annealing treatment on the metal material to obtain the super-hydrophobic anti-corrosion double-layer structure of the metal surface.
Specifically, the femtosecond laser pulse is a double-beam femtosecond laser pulse.
Specifically, the femtosecond laser pulse conditions are: the laser pulse width is 0.03-1 ps, and the frequency is 1-50kHz; the pulse time delay adjustment range between the two light beams is 5-100ps, the laser power range is 100-1000mW, and the power ratio range of the two laser beams is 1:1.1-5; in a specific embodiment, the laser pulse width is 40fs, the pulse time delay between the two beams is 10-50 ps, and the power ratio range of the two beams of laser is 3: 5-9.
Specifically, the scanning irradiation conditions are as follows: the scanning interval is 30-100 mu m, and the scanning speed is 0.1-3mm/s; in a specific embodiment, the scanning pitch is 50 μm and the scanning speed is 1mm/s.
Specifically, the ultrasonic cleaning time is 15-25 min; in a specific embodiment, the time of ultrasonic cleaning is 20 minutes.
Specifically, the annealing treatment conditions are as follows: the annealing temperature is 180-220 ℃ and the annealing time is 3-5 h; in a specific embodiment, the annealing temperature is 200 ℃ and the annealing time is 3h.
Specifically, the focusing element is a plano-convex lens.
Specifically, the metal material is aluminum alloy, titanium alloy or stainless steel.
The metal surface super-hydrophobic anti-corrosion double-layer structure prepared by the method has the advantages that the upper layer material is formed by embedding nanocrystalline and amorphous phase, and the lower layer material is formed by uniform and compact amorphous phase;
specifically, the average size of the nanocrystalline is 5.5nm, and the nanocrystalline is wrapped by the amorphous phase and has no grain boundary;
specifically, the metal material is aluminum alloy; in the super-hydrophobic anti-corrosion double-layer structure of the metal surface, the nanocrystalline is gamma-Al 2 O 3 A substance having an amorphous phase of Al 2 O 3 A substance.
Example 1
The preparation method of the super-hydrophobic anti-corrosion double-layer structure of the metal surface specifically comprises the following steps:
s1, fixing a metal material aluminum alloy, focusing and irradiating a double-beam femtosecond laser pulse with a pulse width of 40fs onto the surface of the aluminum alloy by adopting a plano-convex lens with a focal length of 200 mm, and performing grid scanning irradiation on the surface of a sample for 1-6 times by controlling a three-dimensional moving platform through a computer, wherein the scanning speed is 1mm/S, and the interval between scanning lines, namely the scanning interval, is 50 mu m.
S2, setting pulse time delay between two light beams to be 50ps, wherein the power of the front and rear laser beams is 200 mW and 600 mW respectively (power ratio is 1:3); scanning and irradiating for 1-6 times, and finally processing the surface of the material to form the periodic micro-nano groove structure with the depth of 55 mu m and the width of 50 mu m. The oxygen and aluminum atomic contents of the material surface were measured to be 56.54% and 43.46%, respectively, and the oxygen content ratio was increased by 4.47% as compared with comparative example 2, as shown in fig. 2 (c-d).
And S3, finishing scanning irradiation, carrying out ultrasonic cleaning on the surface of the aluminum alloy sample by using deionized water for 20min, drying by using nitrogen, and then placing the aluminum alloy sample in a vacuum drying oven with the temperature of 200 ℃ for annealing for 3h to obtain the super-hydrophobic anti-corrosion double-layer structure of the metal surface.
After the annealing treatment was completed, the contact angle of the water drop on the sample surface was measured to be 151 ° and the rolling angle was measured to be 3 °, as compared with 82 ° (fig. 3 (a)) on the surface of the sample material unprocessed by the laser, and the hydrophobicity was improved as shown in fig. 3 (c).
A slice of the sample was then cut at the ridge of the trench using focused ion beam techniques and its cross-sectional structure was observed using a transmission electron microscope, as shown in FIG. 4 (c). In this case, the region of loose structure is referred to as the upper layer, the region of dense structure is referred to as the lower layer, and the lower layer has a high and uniform oxidation degree as a whole, as shown in fig. 4 (d), as is apparent from the oxygen content distribution chart. Then, high-definition transmission electron test is performed, wherein the upper layer is formed by embedding nano-crystals and amorphous phases, and the lower layer is formed by embedding amorphous phases, as shown in fig. 5 (c-d). Further, by performing an X-ray diffraction test, it was found that the amorphous peak was remarkable, indicating that the degree of amorphization of the material was high, as shown in fig. 6.
Then, the electrochemical corrosion test was performed on the aluminum alloy sample processed by the double-beam femtosecond laser, and the corrosion current value was found to be 1.1X10 from the polarization curve -10 A cm -2 At least 3 orders of magnitude lower than the laser unprocessed sample and at least 1 order of magnitude lower than the sample of comparative example 2, as shown in fig. 7.
Example 2
The preparation method of the super-hydrophobic anti-corrosion double-layer structure of the metal surface specifically comprises the following steps:
s1, fixing a metal material aluminum alloy, focusing and irradiating a double-beam femtosecond laser pulse with a pulse width of 40fs onto the surface of the aluminum alloy by adopting a plano-convex lens with a focal length of 200 mm, and performing grid scanning irradiation on the surface of a sample by controlling a three-dimensional moving platform through a computer, wherein the scanning speed is 1mm/S, and the interval between scanning lines, namely the scanning interval, is 50 mu m.
S2, setting pulse time delay between two light beams to be 10ps, wherein the power of the front and rear laser beams is 200 mW and 600 mW (power ratio is 1:3), scanning and irradiating for 1-6 times, and forming a periodic micro-nano groove structure on the surface of the metal material.
And S3, finishing scanning irradiation, carrying out ultrasonic cleaning on the surface of the aluminum alloy sample by using deionized water for 20min, drying by using nitrogen, and then placing the aluminum alloy sample in a vacuum drying oven with the temperature of 200 ℃ for annealing for 3h to obtain the super-hydrophobic anti-corrosion double-layer structure of the metal surface.
After the annealing treatment was completed, the contact angle of the water drop on the surface of the sample was measured to be 150 ° and the rolling angle was measured to be 5 °, as shown in fig. 3 (d).
Then, the electrochemical corrosion test is carried out on the aluminum alloy sample processed by the double-beam femtosecond laser with the parameter, and the corrosion current value is 1.9x10 from the polarization curve -10 Acm -2 Reduced by 3 orders of magnitude compared to the laser unprocessed sample and by 1 order of magnitude compared to the sample of comparative example 2, as shown in fig. 7.
Example 3
The preparation method of the super-hydrophobic anti-corrosion double-layer structure of the metal surface specifically comprises the following steps:
s1, fixing a metal material aluminum alloy, focusing and irradiating a double-beam femtosecond laser pulse with a pulse width of 40fs onto the surface of the aluminum alloy by adopting a plano-convex lens with a focal length of 200 mm, and performing grid scanning irradiation on the surface of a sample by controlling a three-dimensional moving platform through a computer, wherein the scanning speed is 1mm/S, and the interval between scanning lines, namely the scanning interval, is 50 mu m.
S2, setting pulse time delay between two light beams as 50ps, wherein the power of the front and rear laser beams is 300 mW and 500 mW (power ratio is 3:5) respectively; scanning and irradiating for 1-6 times to form a periodic micro-nano groove structure on the surface of the metal material.
And S3, finishing scanning irradiation, carrying out ultrasonic cleaning on the surface of the aluminum alloy sample by using deionized water for 20min, drying by using nitrogen, and then placing the aluminum alloy sample in a vacuum drying oven with the temperature of 200 ℃ for annealing for 3h to obtain the super-hydrophobic anti-corrosion double-layer structure of the metal surface.
After the annealing treatment was completed, the contact angle of the water drop on the surface of the sample was measured to be 150 ° and the rolling angle was measured to be 5 °, as shown in fig. 3 (e).
Subsequently, we performed electrochemical corrosion test on the aluminum alloy sample processed by the double beam femtosecond laser with the parameter, and can know that the corrosion current value is 1.4X10 from the polarization curve -10 A cm -2 Reduced by 3 orders of magnitude compared to the laser unprocessed sample and by 1 order of magnitude compared to the sample of comparative example 2, as shown in fig. 7.
Comparative example 1
Selecting 6061 aluminum alloy which is not polished and subjected to femtosecond laser processing as a metal material, wherein the surface of the metal material contains a porous loose thinner oxide layer; the surface of the aluminum alloy sample is ultrasonically cleaned for 20min by using deionized water, and is dried by nitrogen, and then is placed in a vacuum drying oven with the temperature of 200 ℃ for annealing for 3h. The untreated aluminum alloy sample surface was measured to have a contact angle of 82 ° to water drops, and no rolling phenomenon, intrinsic hydrophilicity, as shown in fig. 3 (a).
Subsequently, electrochemical corrosion is carried out on the untreated aluminum alloy sampleThe test shows that the corrosion current value is 4.8X10 from the polarization curve -7 A cm -2 As shown in fig. 7.
Comparative example 2
A single-beam femtosecond laser pulse with the pulse width of 40fs is focused and irradiated to the surface of the aluminum alloy by adopting a plano-convex lens with the focal length of 200 mm, and the laser power is set to be 800 mW. Under the condition of fixed sample position, the three-dimensional moving platform is controlled by a computer to carry out grid scanning irradiation on the surface of the sample, wherein the scanning speed is 1mm/s, the interval between scanning lines, namely the scanning interval is 50 μm, and finally, a periodic micro-nano groove structure with the depth of 58 μm and the width of 50 μm is formed on the surface of the material, and the atomic contents of oxygen and aluminum elements on the surface of the material are measured to be 52.07% and 47.93%, respectively, as shown in fig. 2 (a-b). Subsequently, the surface of the aluminum alloy sample was ultrasonically cleaned with deionized water for 20min, and dried with nitrogen, and then placed in a vacuum oven at 200 ℃ for annealing for 3h. After the annealing treatment was completed, the contact angle of the water drop on the surface of the sample was measured to be 149 °, and the rolling angle was measured to be 5 °, as shown in fig. 3 (b).
A slice of the sample was then cut at the ridge of the trench using focused ion beam techniques and its cross-sectional structure was observed using a transmission electron microscope, as shown in FIG. 4 (a). At this time, we can refer to the loose region of the structure as the upper layer and the dense region of the structure as the lower layer, and it can be seen from the oxygen content distribution chart that the partial region of the lower layer has a low oxidation degree and is uneven, and aluminum substances of micrometer scale exist, as shown by the dotted line in fig. 4 (b). Then, high-definition transmission electron test is performed, wherein the upper layer is formed by embedding nano-crystals and amorphous phases, and the lower layer is in a crystalline phase structure, as shown in fig. 5 (a-b). Further, by performing an X-ray diffraction test, it was found that the amorphous peak was not apparent, indicating that the degree of amorphization of the material was low, as shown in fig. 6.
Subsequently, we performed electrochemical corrosion test on the single beam femtosecond laser processed aluminum alloy sample, and from its polarization curve, we know that its corrosion current value is 1.8X10 -9 A cm -2 4.8X10 compared to the laser unprocessed sample -7 A cm -2 Reduced by 2 amountsStage, as shown in fig. 7.
The result shows that in the preparation method of the metal surface super-hydrophobic anti-corrosion double-layer protection structure, the upper layer substance is formed by embedding low-energy-state nanocrystals and amorphous phases, and has intrinsic super-hydrophobic performance; the lower layer substance is composed of uniform and compact amorphous phase, has the characteristic of intrinsic high corrosion resistance, and the double-layer structure has strong and uniform passivation behavior, so that more effective corrosion protection performance can be provided for the metal surface together.
The invention utilizes the strong thermodynamic correlation of the pulse time delay adjustable femtosecond laser and the substance in the action process to promote the high-efficiency absorption and the energy space local distribution of the material surface to the delayed light beam, thereby enhancing the high-temperature passivation and the amorphous phase generation effect of the material and realizing the double-layer anti-corrosion protection structure. Wherein the upper layer substance is formed by embedding nanocrystalline and amorphous phase, and endows the surface with superhydrophobic performance; the lower layer material is composed of uniform and compact amorphous phase, has the characteristic of intrinsic high corrosion resistance, and has strong and uniform passivation behavior in double-layer structure. The experiment shows that the corrosion current of the aluminum alloy sample after femtosecond laser processing can be reduced to 1.1X10 -10 A cm -2 The corrosion resistance of the material is obviously improved.
It should be appreciated that various forms of the flows shown above may be used to reorder, add, or delete steps. For example, the steps described in the present disclosure may be performed in parallel, sequentially, or in a different order, provided that the desired results of the technical solutions of the present disclosure are achieved, and are not limited herein.
The above embodiments do not limit the scope of the present invention. It will be apparent to those skilled in the art that various modifications, combinations, sub-combinations and alternatives are possible, depending on design requirements and other factors. Any modifications, equivalent substitutions and improvements made within the spirit and principles of the present invention should be included in the scope of the present invention.
Claims (10)
1. The preparation method of the super-hydrophobic anti-corrosion double-layer structure of the metal surface is characterized by comprising the following steps of:
s1, fixing a metal material, and focusing femtosecond laser pulses to the surface of the metal material by adopting a focusing element to perform grid scanning irradiation; the femtosecond laser pulse is a double-beam femtosecond laser pulse or a multi-beam femtosecond laser pulse; the scanning irradiation conditions are as follows: the scanning interval is 30-100 mu m, and the scanning speed is 0.1-3mm/s;
s2, setting pulse delay time and power ratio parameters between femtosecond laser beams, scanning and irradiating for 1-6 times, and forming a periodic micro-nano groove structure on the surface of the metal material;
and S3, finishing scanning irradiation, and performing ultrasonic cleaning and annealing treatment on the metal material to obtain the super-hydrophobic anti-corrosion double-layer structure of the metal surface.
2. The method for preparing the metal surface super-hydrophobic anti-corrosion double-layer structure according to claim 1, which is characterized in that: the femtosecond laser pulse is a double-beam femtosecond laser pulse.
3. The method for preparing the metal surface super-hydrophobic anti-corrosion double-layer structure according to claim 2, which is characterized in that: the femtosecond laser pulse conditions are as follows: the laser pulse width is 0.03-1 ps, and the frequency is 1-50kHz; the pulse time delay adjustment range between the two light beams is 5-100ps, the laser power range is 100-1000mW, and the power ratio range of the two light beams is 1:1.1-5.
4. The method for preparing the metal surface super-hydrophobic anti-corrosion double-layer structure according to claim 3, which is characterized in that: the pulse time delay between the two light beams is 10-50 ps, and the power ratio range of the two laser beams is 3: 5-9.
5. The method for preparing a super-hydrophobic anticorrosive double-layer structure on a metal surface according to claim 4, wherein the step S3 further comprises: blowing with nitrogen before annealing treatment; the annealing treatment conditions are as follows: the annealing temperature is 180-220 ℃, and the annealing time is 3-8 h.
6. The method for preparing the super-hydrophobic anticorrosive double-layer structure of the metal surface according to any one of claims 1 to 5, which is characterized by comprising the following steps: the metal material is aluminum alloy, titanium alloy or stainless steel.
7. The method for preparing the metal surface super-hydrophobic anti-corrosion double-layer structure according to claim 6, which is characterized in that: the focusing element is a plano-convex lens.
8. The preparation method of the metal surface super-hydrophobic anti-corrosion double-layer structure is characterized by comprising the following steps: the upper layer of the double-layer structure is a periodic micro-nano groove structure, and the depth of the groove structure is 30-70 um, and the width of the groove structure is 30-100 um, and the groove structure is formed by embedding nanocrystalline and amorphous phase; the lower layer substance of the double-layer structure is composed of uniform and compact amorphous phase.
9. The metallic surface super-hydrophobic corrosion protection double layer structure according to claim 8, wherein: the average size of the nanocrystals was 5.5nm, which was encapsulated by the amorphous phase and no grain boundaries were present.
10. The metallic surface superhydrophobic corrosion-resistant bilayer structure according to claim 9, wherein: the metal material is aluminum alloy; in the super-hydrophobic anti-corrosion double-layer structure of the metal surface, the nanocrystalline is gamma-Al 2 O 3 A substance having an amorphous phase of Al 2 O 3 A substance.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311748683.4A CN117431495B (en) | 2023-12-19 | 2023-12-19 | Super-hydrophobic anti-corrosion double-layer structure of metal surface and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311748683.4A CN117431495B (en) | 2023-12-19 | 2023-12-19 | Super-hydrophobic anti-corrosion double-layer structure of metal surface and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN117431495A true CN117431495A (en) | 2024-01-23 |
| CN117431495B CN117431495B (en) | 2024-02-13 |
Family
ID=89546505
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202311748683.4A Active CN117431495B (en) | 2023-12-19 | 2023-12-19 | Super-hydrophobic anti-corrosion double-layer structure of metal surface and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117431495B (en) |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102418082A (en) * | 2011-11-21 | 2012-04-18 | 中国矿业大学 | Method and device for preparing film coating micronano texture |
| CN102909477A (en) * | 2012-10-31 | 2013-02-06 | 北京工业大学 | Method and device for preparing large area of micro gratings on surface of target material by utilizing ultra-fast laser |
| WO2013141747A1 (en) * | 2012-03-19 | 2013-09-26 | Maximovsky Sergei Nikolaevich | Method for producing a multi-layered nano-structure |
| WO2021256994A1 (en) * | 2020-06-19 | 2021-12-23 | National University Of Singapore | Apparatus and method for patterning a nanostructure in a target material |
| US20220339725A1 (en) * | 2020-11-17 | 2022-10-27 | Soochow University | A method for preparing a cross-size micro-nano structure array |
| CN115786652A (en) * | 2023-01-09 | 2023-03-14 | 中国科学院长春光学精密机械与物理研究所 | Intrinsic super-hydrophobic material, preparation method and application thereof |
| CN116833578A (en) * | 2023-08-31 | 2023-10-03 | 中国科学院长春光学精密机械与物理研究所 | Laser processing method for metal surface electrolytic oxide layer super-hydrophobic corrosion prevention |
-
2023
- 2023-12-19 CN CN202311748683.4A patent/CN117431495B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102418082A (en) * | 2011-11-21 | 2012-04-18 | 中国矿业大学 | Method and device for preparing film coating micronano texture |
| WO2013141747A1 (en) * | 2012-03-19 | 2013-09-26 | Maximovsky Sergei Nikolaevich | Method for producing a multi-layered nano-structure |
| CN102909477A (en) * | 2012-10-31 | 2013-02-06 | 北京工业大学 | Method and device for preparing large area of micro gratings on surface of target material by utilizing ultra-fast laser |
| WO2021256994A1 (en) * | 2020-06-19 | 2021-12-23 | National University Of Singapore | Apparatus and method for patterning a nanostructure in a target material |
| US20220339725A1 (en) * | 2020-11-17 | 2022-10-27 | Soochow University | A method for preparing a cross-size micro-nano structure array |
| CN115786652A (en) * | 2023-01-09 | 2023-03-14 | 中国科学院长春光学精密机械与物理研究所 | Intrinsic super-hydrophobic material, preparation method and application thereof |
| CN116833578A (en) * | 2023-08-31 | 2023-10-03 | 中国科学院长春光学精密机械与物理研究所 | Laser processing method for metal surface electrolytic oxide layer super-hydrophobic corrosion prevention |
Also Published As
| Publication number | Publication date |
|---|---|
| CN117431495B (en) | 2024-02-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Raciukaitis et al. | Use of high repetition rate and high power lasers in microfabrication: How to keep the efficiency high? | |
| US5473138A (en) | Method for increasing the surface area of ceramics, metals and composites | |
| US20140314995A1 (en) | Pulsed laser processing method for producing superhydrophobic surfaces | |
| Gecys et al. | Ripple formation by femtosecond laser pulses for enhanced absorptance of stainless steel | |
| WO2016207659A1 (en) | Method of, and apparatus for, laser blackening of a surface, wherein the laser has a specific power density and/or a specific pulse duration | |
| CN101198433A (en) | Method for finely polishing/structuring thermosensitive dielectric materials by a laser beam | |
| CN115786652B (en) | Intrinsic super-hydrophobic material, preparation method and application thereof | |
| JP2020146725A (en) | Control method for wettability of metallic surface | |
| CN117431495B (en) | Super-hydrophobic anti-corrosion double-layer structure of metal surface and preparation method thereof | |
| Vestentoft et al. | Formation of an extended nanostructured metal surface by ultra-short laser pulses: single-pulse ablation in the high-fluence limit | |
| Landström et al. | Single-step patterning and the fabrication of contact masks by laser-induced forward transfer | |
| CN116727868A (en) | Method for preparing controllable wettability of aviation aluminum alloy surface by infrared nanosecond laser | |
| Kam et al. | Formation mechanism of micro-spikes on AISI 4340 steel with femtosecond laser pulses at near-threshold fluence | |
| Yang et al. | Sub-wavelength surface structuring of NiTi alloy by femtosecond laser pulses | |
| CN115717231A (en) | Paracrystalline metal material, preparation method and application thereof | |
| CN116814908A (en) | Laser micro-texture-based iron-based amorphous alloy coating with superhydrophobicity and corrosion resistance and preparation method thereof | |
| CN116174893A (en) | Method for improving superhydrophobicity of nickel-titanium alloy by laser composite processing | |
| Zimmer et al. | Using IR laser radiation for backside etching of fused silica | |
| CN114799528A (en) | Method for remotely and rapidly preparing corrosion-resistant structure on irregular metal surface in large area | |
| CN107225329A (en) | A kind of method for improving glass copper facing bonding strength | |
| Stolz et al. | Engineering meter-scale laser resistant coatings for the near IR | |
| Vidhya et al. | Influence of Laser Beam Profile on Nd^ sup 3+^: YAG Laser Assisted Formation of Polycrystalline-Si Films in Underwater Conditions | |
| US4087695A (en) | Method for producing optical baffling material using pulsed electron beams | |
| KR100913151B1 (en) | Method and apparatus of descaling metal using pulse laser-induced shock wave | |
| Ronoh et al. | Analysis of processing efficiency, surface, and bulk chemistry, and nanomechanical properties of the Monel® alloy 400 after ultrashort pulsed laser ablation |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |