CN114737230B - Method and device for preparing functional film with trans-scale micro-nano structure by laser enhanced electrochemical deposition - Google Patents
Method and device for preparing functional film with trans-scale micro-nano structure by laser enhanced electrochemical deposition Download PDFInfo
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- 238000004070 electrodeposition Methods 0.000 title claims abstract description 74
- 239000002086 nanomaterial Substances 0.000 title claims abstract description 46
- 238000000034 method Methods 0.000 title claims abstract description 35
- 238000000151 deposition Methods 0.000 claims abstract description 19
- 239000011248 coating agent Substances 0.000 claims abstract description 17
- 238000000576 coating method Methods 0.000 claims abstract description 17
- 230000000694 effects Effects 0.000 claims abstract description 12
- 239000000758 substrate Substances 0.000 claims abstract description 12
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 30
- 239000007788 liquid Substances 0.000 claims description 20
- 230000008021 deposition Effects 0.000 claims description 14
- 229910052802 copper Inorganic materials 0.000 claims description 13
- 239000010949 copper Substances 0.000 claims description 13
- UGKDIUIOSMUOAW-UHFFFAOYSA-N iron nickel Chemical compound [Fe].[Ni] UGKDIUIOSMUOAW-UHFFFAOYSA-N 0.000 claims description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- 239000000243 solution Substances 0.000 claims description 8
- 239000011259 mixed solution Substances 0.000 claims description 7
- 238000012545 processing Methods 0.000 claims description 7
- CVHZOJJKTDOEJC-UHFFFAOYSA-N saccharin Chemical compound C1=CC=C2C(=O)NS(=O)(=O)C2=C1 CVHZOJJKTDOEJC-UHFFFAOYSA-N 0.000 claims description 7
- 229940081974 saccharin Drugs 0.000 claims description 7
- 235000019204 saccharin Nutrition 0.000 claims description 7
- 239000000901 saccharin and its Na,K and Ca salt Substances 0.000 claims description 7
- 241000080590 Niso Species 0.000 claims description 6
- 230000005684 electric field Effects 0.000 claims description 4
- 239000003792 electrolyte Substances 0.000 claims description 4
- 238000010336 energy treatment Methods 0.000 claims description 4
- 238000005282 brightening Methods 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 230000007246 mechanism Effects 0.000 claims description 3
- 239000003381 stabilizer Substances 0.000 claims description 3
- 239000000080 wetting agent Substances 0.000 claims description 3
- 239000002131 composite material Substances 0.000 abstract description 3
- 238000002360 preparation method Methods 0.000 abstract description 3
- 230000009467 reduction Effects 0.000 abstract description 3
- 238000012423 maintenance Methods 0.000 abstract description 2
- 238000005530 etching Methods 0.000 abstract 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 10
- 239000000463 material Substances 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 4
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 238000010586 diagram Methods 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
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- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 238000007747 plating Methods 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 239000010963 304 stainless steel Substances 0.000 description 1
- 244000020998 Acacia farnesiana Species 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 235000010643 Leucaena leucocephala Nutrition 0.000 description 1
- 229910000589 SAE 304 stainless steel Inorganic materials 0.000 description 1
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- 238000000137 annealing Methods 0.000 description 1
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- 238000005265 energy consumption Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 238000010329 laser etching Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 210000001595 mastoid Anatomy 0.000 description 1
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- 229910052751 metal Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000001259 photo etching Methods 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/011—Electroplating using electromagnetic wave irradiation
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D21/00—Processes for servicing or operating cells for electrolytic coating
- C25D21/12—Process control or regulation
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/12—Electroplating: Baths therefor from solutions of nickel or cobalt
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/20—Electroplating: Baths therefor from solutions of iron
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/34—Pretreatment of metallic surfaces to be electroplated
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
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- Automation & Control Theory (AREA)
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Abstract
The invention discloses a method and a device for preparing a functional film with a trans-scale micro-nano structure by laser enhanced electrochemical deposition, and belongs to the field of laser composite electrochemical preparation. The method utilizes the thermal effect and the photoelectric effect of laser irradiation to enhance the electrodeposition rate and quality of an irradiation area, selects and induces a trans-scale micro-nano structure while depositing a coating, simplifies the preparation process of a functional surface and can improve the precision and uniformity of the micro-nano structure. And the laser enhanced electrochemical deposition method is adopted, so that the substrate damage caused by etching is avoided. Compared with the prior art, the functional film prepared by the invention can be taken down from the substrate and adhered on the working surface, improves the working performance, the stability and the service life on the premise of not damaging parts, and has the advantages of convenient replacement and reduction of the subsequent maintenance cost.
Description
Technical Field
The invention relates to the field of laser enhanced electrochemical deposition, in particular to a method and a device for preparing a functional film with a trans-scale micro-nano structure.
Background
With the deep development of modern industry, higher and higher requirements are put on the product performance, and the product with qualified macroscopic appearance and size cannot meet the requirements of the actual working environment. The functional surface has the specific performances of antifriction, drag reduction, self cleaning, corrosion resistance and the like, can be applied to the industries of aerospace, medical equipment, pipeline transportation and the like, can improve the service length of a workpiece, reduce the overhaul cost, improve the working efficiency and reduce the energy consumption. Therefore, the functional characteristics of the material are combined with the surface technology, so that the surface plating layer with the functional properties is obtained, and the method has important significance for developing a novel manufacturing technology, reducing material consumption and improving the surface performance of engineering parts.
Many natural organisms have excellent surface functional characteristics, the surfaces often grow different micro-nano structures, the characteristic sizes of the micro-nano structures are different from hundreds of micrometers to tens of nanometers, and the micro-nano structures have various shapes and complex structures.
For the preparation of the trans-scale micro-nano structure, the method can be divided into electrochemical deposition method, vapor deposition, laser ablation, photoetching-electrochemical deposition, laser-electrochemical deposition and the like. The ultra-hydrophobic surface with the micro-nano mastoid structure is efficiently prepared by electrochemical deposition on a stainless steel mesh by Longgang Wang and the like, but the micro-nano structure obtained by the electrochemical deposition is uneven and the quality of a coating is poor; the carbon nanotube array is deposited on the surface of 304 stainless steel by chemical vapor deposition, the contact angle of water on the surface of a stainless steel sample is 154.6 degrees, the rolling angle is less than 5 degrees, but the physical/chemical vapor deposition processing efficiency is lower, and the flexibility is poor; an He et al uses nanosecond laser to ablate first, then ethanol is used for assisting low-temperature annealing, and a superhydrophobic surface is obtained on the copper surface, but the laser ablation method can cause damages such as chipping, fracture and the like on the surface microstructure. Shirttliffe and the like firstly process a short cylinder with a diameter on the surface of a copper substrate by a mask photoetching technology, then deposit copper grains on the surface of the short cylinder and gaps by electrochemical deposition to obtain micro-nano particles, but the method has the defects of complex process, low binding force of a nano structure, difficult repair after functional loss and the like; gu Qinming and the like propose a method for preparing a metal super-hydrophobic surface without modification by laser-electrochemical deposition, wherein micron-submicron-nanometer trans-scale hierarchical structures and 3D reentrant corner structures are prepared on a copper surface by combining laser ablation of micron protrusions and electrochemical deposition of nanometer pyramids, but the process is complicated, and damage is caused to a surface microstructure by laser ablation.
Disclosure of Invention
Aiming at the defects existing in the prior art, the invention provides a method for preparing a functional film with a cross-scale micro-nano structure by laser enhanced electrochemical deposition. The laser enhanced electrochemical deposition method avoids substrate damage caused by laser etching, has higher quality of the obtained functional surface and better effect, and can be used for improving the working performance and durability of products.
The present invention achieves the above technical object by the following means.
A method for preparing a functional film with a trans-scale micro-nano structure by laser enhanced electrochemical deposition utilizes the thermal effect and the photoelectric effect of laser irradiation to enhance the electro-deposition rate and quality of an irradiation area, and utilizes laser irradiation to induce a trans-scale micro-nano array structure on the surface of a coating while depositing the coating, wherein the laser irradiation path is controlled by a program.
In the scheme, the array structure is a strip array, when the strip array is processed, the laser single pulse energy is 15-18 mu J, the defocusing amount is 0.5-1 mm, the scanning interval is 120-180 mu m, the scanning speed is 3500-4000 mm/s, the frequency is 0.5-1.5 MHz, the electrolyte thickness is 5-7 mm, the cathode copper plate thickness is 1.5mm, the pulse power supply frequency is 1kHz, the duty ratio is 50%, and the current density is 40-60 mA/cm 2 。
In the scheme, electrolyte is arranged in the rectangular electrolytic tank, so that the influence of an electric field on array stray deposition is reduced.
In the scheme, the iron-nickel combination is used as an anode, the copper plate is used as a cathode, and the electrodeposition time is 25-35 min; the electrodeposition liquid is NiSO 4 ·6H 2 O、FeSO 4 ·7H 2 O、NiCl 2 ·6H 2 O、Na 3 C 6 H 5 O 7 ·2H 2 O、H 3 BO 3 Saccharin and C1 2 H 25 SO 4 Na (Na); wherein, niSO 4 ·6H 2 O and FeSO 4 ·7H 2 O is used as Ni 2+ 、Fe 2+ An ion source; niCl 2 ·6H 2 O may provide part of Ni 2+ And Cl to promote anodic dissolution - ；H 3 BO 3 The pH value of the deposition solution is 2.5-3; na (Na) 3 C 6 H 5 O 7 ·2H 2 O is used as a stabilizer to effectively inhibit Fe 2+ Is oxidized by (a); saccharin is used as a brightening agent to improve the brightness of a coating; C1C 1 2 H 25 SO 4 Na is used as a wetting agent to effectively wet the surface of the cathode and reduce the adhesion of bubbles on the surface of the copper plate.
In the scheme, after the laser enhanced electrodeposition is performed for 25-35 min, the laser is turned off, and the electrodeposition is continued for about 50s.
In the scheme, the interval laser scanning is adopted, the even-numbered strip-shaped structures are scanned firstly, and then the odd-numbered strip-shaped structures are scanned, so that stray deposition can be reduced, and the uniform micro-nano array structure with high depth-to-diameter ratio is obtained.
The scheme comprises the following steps:
step one: setting up a processing system for laser enhanced electrochemical deposition;
step two: the method comprises the steps of utilizing a laser thermal effect to enhance an electrodeposition mechanism, adopting laser to irradiate a solid-liquid interface to induce a cross-scale micro-nano structure in an irradiation area while depositing a coating on a substrate, and obtaining the coating with the cross-scale micro-nano structure;
and step three, performing low surface energy treatment in a mixed solution of 1H, 2H-perfluoro decyl triethoxysilane and alcohol.
In the above scheme, in the third step, the sample after laser enhanced deposition is placed in a mixed solution of 1% of 1H, 2H-perfluorodecyl triethoxysilane and alcohol, heated for 12 hours at 65 ℃, and then dried for 12 hours.
The device for preparing the functional film with the trans-scale micro-nano structure by the laser enhanced electrochemical deposition comprises a laser irradiation system, an electrodeposition system and a motion control system; the laser irradiation system comprises a laser, a reflecting mirror and a focusing lens; laser emitted by the laser is irradiated to the interface of the cathode copper plate and the electrodeposit liquid through the laser beam of which the optical path is changed by the reflector and focused by the focusing lens;
the electrodeposition system comprises a pulse power supply, a cathode copper block, an iron-nickel combined anode, an electrodeposition liquid, an electrolytic tank and a pump; the inside of the electrolytic tank is provided with a loop-shaped structure, an iron-nickel combined anode is arranged at one end of the electrolytic tank, a cathode copper plate is arranged inside the loop-shaped structure of the electrolytic tank, and a baffle is arranged between the iron-nickel combined anode and the cathode copper plate to separate;
the motion control system comprises a computer, a motion controller and an x-y-z three-coordinate moving platform, wherein the computer controls a laser and a pulse power supply; the motion controller controls the x-y-z three-coordinate moving platform; and an electrolytic tank is arranged on the x-y-z three-coordinate moving platform.
In the above scheme, the laser may be a nanosecond laser or a picosecond laser.
The beneficial effects are that:
(1) The invention adopts a laser-assisted electro-deposition composite processing method, can conveniently and rapidly grow a coating of the cross-scale micro-nano structure on the substrate material, does not damage the substrate material, and provides a new thought for preparing the cross-scale micro-nano structure of the functional surface.
(2) The functional film prepared by the invention can be taken down from the substrate and adhered on the working surface, improves the working performance, stability and service life on the premise of not damaging parts, and has the advantages of convenient replacement and reduction of subsequent maintenance cost.
(3) The micro-nano array structures with different densities are swept out through different laser parameters, so that the film is in a gradient structure, and the self-transportation function of liquid drops can be realized.
Drawings
FIG. 1 is a schematic diagram of a processing system for preparing a functional film with a trans-scale micro-nano structure by laser enhanced electrochemical deposition according to an embodiment of the present invention;
FIG. 2 is a schematic diagram of a loop-shaped electrolytic cell according to an embodiment of the invention;
FIG. 3 is a graph of the surface topography of a functional film with a trans-scale micro-nano structure prepared by laser enhanced electrochemical deposition according to example 1 of the present invention;
wherein, (a) is a strip array surface topography map with the magnification of 200 times, (b) is a single strip array surface topography map with the magnification of 500 times, and (c) is a single strip array region 1 position magnification 20000 times topography map;
FIG. 4 in example 1, the result of observation of bouncing and contact angle test of liquid drops on the surface of a functional copper film with a trans-scale micro-nano structure is prepared by laser enhanced electrodeposition at a scanning interval of 150 μm+30 min;
wherein, (a) is a droplet bounce observation result, and (b) is a surface contact angle test result.
FIG. 5 in example 1, after laser enhanced electrodeposition with a scan plane spacing of 150 μm+30min, 50s of laser-free electrodeposition was added to prepare a droplet bounce observation result for a functional copper film surface with a trans-scale micro-nano structure.
Reference numerals:
1-computer, 2-picosecond laser, 3-reflector, 4-focusing lens, 5-laser beam, 6-pump, 7-cathode copper plate, 8-iron-nickel combined anode, 9-electrodeposition liquid, 10-electrolytic tank, 11-pulse power supply, 12-motion controller and 13-x-y-z workbench.
Detailed Description
Embodiments of the present invention are described in detail below, examples of which are illustrated in the accompanying drawings, wherein like or similar reference numerals refer to like or similar elements or elements having like or similar functions throughout. The embodiments described below by referring to the drawings are illustrative and intended to explain the present invention and should not be construed as limiting the invention.
In the description of the present invention, it should be understood that the terms "center," "longitudinal," "transverse," "length," "width," "thickness," "upper," "lower," "axial," "radial," "vertical," "horizontal," "inner," "outer," and the like indicate orientations or positional relationships based on the orientation or positional relationships shown in the drawings, merely to facilitate describing the present invention and simplify the description, and do not indicate or imply that the devices or elements referred to must have a specific orientation, be configured and operated in a specific orientation, and therefore should not be construed as limiting the present invention. Furthermore, the terms "first," "second," and the like, are used for descriptive purposes only and are not to be construed as indicating or implying a relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defining "a first" or "a second" may explicitly or implicitly include one or more such feature. In the description of the present invention, the meaning of "a plurality" is two or more, unless explicitly defined otherwise.
In the present invention, unless explicitly specified and limited otherwise, the terms "mounted," "connected," "secured," and the like are to be construed broadly and may be, for example, fixedly connected, detachably connected, or integrally connected; can be mechanically or electrically connected; can be directly connected or indirectly connected through an intermediate medium, and can be communication between two elements. The specific meaning of the above terms in the present invention can be understood by those of ordinary skill in the art according to the specific circumstances.
A method for preparing a functional film with a trans-scale micro-nano structure by laser enhanced electrochemical deposition, wherein the thermal effect and the photoelectric effect of laser irradiation enhance the rate and the quality of electrodeposition in an irradiation area, and the trans-scale micro-nano structure is selectively induced while a coating is deposited. The method comprises the following steps:
step one: setting up a processing system for laser enhanced electrochemical deposition;
step two: the method comprises the steps of utilizing a laser thermal effect to enhance an electrodeposition mechanism, adopting laser to irradiate a solid-liquid interface to induce a cross-scale micro-nano structure in an irradiation area while depositing a coating on a substrate, and obtaining the coating with the cross-scale micro-nano structure;
and step three, performing low surface energy treatment in a mixed solution of 1H, 2H-perfluoro decyl triethoxysilane and alcohol.
In the above scheme, in the first step, a loop-shaped electrolytic tank is adopted to reduce the influence of the electric field on array stray deposition.
In the above scheme, in the second step, while the plating layer grows, a cross-scale micro-nano array structure is induced on the surface by laser irradiation, and the laser irradiation path is controlled by a program.
In the above scheme, the array structure is a strip array.
In the scheme, when the strip array is processed, the laser single pulse energy is 15-18 mu J, the defocusing amount is 0.5-1 mm, the scanning interval is 120-180 mu m, the scanning speed is 3500-4000 mm/s, the frequency is 0.5-1.5 MHz, the thickness of the solution of the electrolytic tank 10 is 5-7 mm, the thickness of the cathode copper plate is 1.5mm, the pulse power supply frequency is 1KHz, the duty ratio is 50%, and the current density is 40-60 mA/cm 2 。
In the scheme, the electrochemical deposition takes the combination of iron and nickel 8 as an anode, the copper plate 7 as a cathode, and the electrodeposition time is 25-35 min. The electrodeposition liquid is NiSO 4 ·6H 2 O、FeSO 4 ·7H 2 O、NiCl 2 ·6H 2 O、Na 3 C 6 H 5 O 7 ·2H 2 O、H 3 BO 3 Saccharin and C1 2 H 25 SO 4 Na. Wherein NiSO 4 ·6H 2 O and FeSO 4 ·7H 2 O is used as Ni 2+ 、Fe 2+ An ion source; niCl 2 ·6H 2 O may provide part of Ni 2+ And Cl to promote anodic dissolution - ；H 3 BO 3 The pH value of the deposition solution is 2.5-3; na (Na) 3 C 6 H 5 O 7 ·2H 2 O is used as a stabilizer to effectively inhibit Fe 2+ Is oxidized by (a); saccharin is used as a brightening agent to improve the brightness of a coating; C1C 1 2 H 25 SO 4 Na is used as a wetting agent to effectively wet the surface of the cathode and reduce the adhesion of bubbles on the surface of the cathode copper plate 7.
In the scheme, the sample after laser enhanced deposition is placed in a mixed solution of 1% of 1H, 2H-perfluoro decyl triethoxysilane and alcohol, and is heated for 12 hours at 65 ℃ and then dried for 12 hours.
The device for preparing the functional film with the trans-scale micro-nano structure by laser enhanced electrochemical deposition comprises a picosecond laser irradiation system, an electrodeposition system and a motion control system. The laser irradiation system comprises a picosecond laser 2, a reflecting mirror 3 and a focusing lens 4; the laser beam 5 which is emitted by the laser 2 and is focused by the focusing lens 4 after the light path of the laser is changed by the reflecting mirror 3 is irradiated to the interface between the cathode copper plate 7 and the electrodeposition liquid 9; the electrodeposition system comprises a pulse power supply 11, a cathode copper block 7, an iron-nickel combined anode 8, an electrodeposition liquid 9, an electrolytic tank 10 and a pump 6; the inside of the electrolytic tank is provided with a square structure, an iron-nickel combined anode 8 is arranged at one end of the electrolytic tank, a cathode copper plate 7 is arranged in the square structure, and a baffle is arranged between the iron-nickel combined anode 8 and the cathode copper plate 7; the motion control system comprises a computer 1, a motion controller 12 and an x-y-z three-coordinate moving platform 13, wherein the computer 1 controls the picosecond laser 2 and the pulse power supply 11; the motion controller 12 controls the x-y-z three-coordinate moving platform 13; the electrolytic tank 10 is arranged on the x-y-z three-coordinate moving platform 13.
In the scheme, after the laser enhanced electrodeposition is performed for 25-35 min, the picosecond laser is turned off, and the electrodeposition is continued for about 50s, so that more nanoscale structures can be obtained, and the nano-scale structure has better hydrophobic performance and the like.
In the scheme, the trans-scale micro-nano array structures with different densities are swept out through different laser parameters, so that the film is in a gradient structure, and the self-transportation function of liquid drops is realized.
In the scheme, interval laser scanning is adopted, for example, even-numbered strip structures are scanned firstly and odd-numbered strip structures are scanned secondly, stray deposition can be reduced, and a uniform microstructure unit with high depth-to-diameter ratio is obtained.
In the above-described embodiment, the laser 2 may be a nanosecond or picosecond laser.
Example 1
The implementation process of the method for preparing the functional film with the trans-scale micro-nano structure by using the laser enhanced electrochemical deposition is described below by taking a copper substrate as a cathode and combining iron and nickel as an anode, and comprises the following steps:
building a processing system of picosecond laser composite electrochemical enhanced electrodeposition shown in figure 1; wherein the laser irradiation system comprises a picosecond laser 2, a reflecting mirror 3 and a focusing lens 4; pulse laser with the wavelength of 1064nm and the pulse duration of 30min and the spot diameter of 20 mu m is generated by a picosecond laser 2, a scanning path is determined by a reflector 3, and then the laser is focused by a focusing lens 4, and the focused laser beam 5 is irradiated to the interface between a cathode copper plate 7 and an electrodeposition liquid 9; the electrochemical deposition part comprises a pulse power supply 11, a cathode copper block 7, an iron-nickel combined anode 8, an electrodeposition liquid 9, an electrolytic tank 10 and a pump 6; the cathode copper plate 7 is connected with the cathode of the pulse power supply 11, the iron-nickel combined anode 8 is connected with the anode of the pulse power supply 11, the liquid inlet of the pump 6 is connected with the bottom end of the electrolytic tank 10, and the liquid outlet is connected with the top end of the electrolytic tank 10; referring to fig. 2, the electrolytic tank 10 is internally provided with a square structure, the iron-nickel combined anode 8 is arranged at one end of the electrolytic tank 10, the cathode copper plate 7 is arranged in the square structure, the iron-nickel combined anode 8 is separated from the cathode copper plate 7 by a baffle, and the square electrolytic tank can reduce the influence of an electric field on array stray deposition; the motion control system comprises a computer 1, a motion controller 12 and an x-y-z three-coordinate moving platform 13, wherein the computer 1 controls the picosecond laser 2 and the pulse power supply 11, the motion controller 12 controls the x-y-z three-coordinate moving platform 13, and the electrolytic tank 10 is arranged on the x-y-z three-coordinate moving platform 13.
And determining anode and cathode parameters, laser parameters, electric parameters and solution proportion. The adopted cathode is a copper substrate with the thickness of 1.5mm, the combination of iron and nickel is an anode, and the current density is 50mA/cm 2 The method comprises the steps of carrying out a first treatment on the surface of the Adopting a unidirectional pulse power supply, wherein the pulse frequency is 1kHz, the duty ratio is 50%, the laser single pulse energy is 18 mu J, the defocusing amount is 0.5mm, the scanning speed is 3500mm/s, the laser pulse frequency is 1MHz, the scanning interval is 150 mu m, the thickness of the electrolytic bath solution is 6mm, and the electrodeposition is carried out for 30min; the electrodeposition solution used consisted essentially of 120g/LNiSO 4 ·6H 2 O、20g/LFeSO 4 ·7H 2 O、40g/LNiCl 2 ·6H 2 O、20g/L Na 3 C 6 H 5 O 7 ·2H 2 O、40g/L H 3 BO 3 3g/L Saccharin (Saccharin), 1g/L C1 2 H 25 SO 4 Na, wherein the pH value of the solution is 2.5-3.0, and the ambient temperature is 25 ℃; the sample after laser enhanced deposition is placed in 1% of a mixed solution of 1H, 2H-perfluoro decyl triethoxysilane and alcohol, and is heated for 12 hours at 65 ℃ and then dried for 12 hours.
With reference to fig. 3, under this parameter, the nanostructure is loose, coral-shaped, grows in the form of branches, and accumulates into a micron-sized wire structure with reference to fig. 3, diagrams (a), (b); meanwhile, gaps exist at the positions of the branched structures, and nano particle protrusions are arranged at the top of the branched structures and combined with the graph (c) in the figure 3, so that air cells are formed between the liquid drops and the micro-nano structures, the gas-liquid contact area is increased, and the water contact angle is increased.
With reference to fig. 4, after the laser enhanced electrochemical deposition is performed for 30min and the low surface energy treatment is performed, the droplet bouncing experiment shows that the droplet bounces 5 times, and the droplet is supported by a tiny air sac at the moment, so that the energy dissipation is low, which proves the importance of the micro-nano structure for obtaining the Cassie super-hydrophobic state; the contact angle of water of the prepared coral-shaped micro-nano structure is 155 degrees, so that the super-hydrophobic performance is achieved.
With the combination of figure 5, the laser is turned off after the electrochemical deposition is enhanced for 30min, and the electro-deposition is continued for about 50s, so that more nano structures are obtained, and when the droplet bounce observation test is carried out, the water droplets spontaneously move along a specific direction, thereby proving the capability of the technology for preparing the surface with the self-transportation function.
In the description of the present specification, a description referring to terms "one embodiment," "some embodiments," "examples," "specific examples," or "some examples," etc., means that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present invention. In this specification, schematic representations of the above terms do not necessarily refer to the same embodiments or examples. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
Although embodiments of the present invention have been shown and described above, it will be understood that the above embodiments are illustrative and not to be construed as limiting the invention, and that variations, modifications, alternatives, and variations may be made in the above embodiments by those skilled in the art without departing from the spirit and principles of the invention.
Claims (8)
1. A method for preparing a functional film with a trans-scale micro-nano structure by laser enhanced electrochemical deposition is characterized in that the thermal effect and the photoelectric effect of laser irradiation are utilized to enhance the electro-deposition rate and quality of an irradiation area, and a trans-scale micro-nano array structure is induced on the surface of a coating by laser irradiation while the coating is deposited, wherein the laser irradiation path is controlled by a program; the laser single pulse energy is 15-18 mu J, the scanning speed is 3500-4000 mm/s, and the frequency is 0.5-1.5 MHz.
2. The method for preparing the functional film with the trans-scale micro-nano structure by using the laser enhanced electrochemical deposition according to claim 1, wherein the array structure is a strip array; when processing the strip array, the defocusing amount is 0.5-1 mm, the scanning interval is 120-180 mu m, the thickness of the electrolyte is 5-7 mm, the thickness of the cathode copper plate is 1.5mm, the pulse power supply frequency is 1kHz, the duty ratio is 50%, and the current density is 40-60 mA/cm 2 。
3. The method for preparing the functional film with the trans-scale micro-nano structure by using the laser enhanced electrochemical deposition according to claim 2, wherein electrolyte is placed in a loop-shaped electrolytic tank, and the influence of an electric field on array stray deposition is reduced.
4. The method for preparing the functional film with the trans-scale micro-nano structure by using the laser enhanced electrochemical deposition according to claim 1, wherein the method is characterized in that iron-nickel combination is used as an anode, a copper plate is used as a cathode, and the electrodeposition time is 25-35 min; the electrodeposition liquid is NiSO 4 ·6H 2 O、FeSO 4 ·7H 2 O、NiCl 2 ·6H 2 O、Na 3 C 6 H 5 O 7 ·2H 2 O、H 3 BO 3 Saccharin and C 12 H 25 SO 4 Na (Na); wherein, niSO 4 ·6H 2 O and FeSO 4 ·7H 2 O is used as Ni 2+ 、Fe 2+ An ion source; niCl 2 ·6H 2 O may provide part of Ni 2+ And promoteCl dissolved in anode - ；H 3 BO 3 The pH value of the deposition solution is 2.5-3; na (Na) 3 C 6 H 5 O 7 ·2H 2 O is used as a stabilizer to effectively inhibit Fe 2+ Is oxidized by (a); saccharin is used as a brightening agent to improve the brightness of a coating; c (C) 12 H 25 SO 4 Na is used as a wetting agent to effectively wet the surface of the cathode and reduce the adhesion of bubbles on the surface of the copper plate.
5. The method for preparing the functional film with the trans-scale micro-nano structure by using the laser enhanced electrochemical deposition according to claim 1, wherein the laser is turned off after the laser enhanced electrochemical deposition is performed for 25-35 min, and the electrochemical deposition is continued for 50s.
6. The method for preparing the functional film with the cross-scale micro-nano structure by using the laser enhanced electrochemical deposition according to claim 1, wherein the method is characterized in that the interval laser scanning is adopted, the even-numbered strip structures are scanned firstly, and then the odd-numbered strip structures are scanned, so that the stray deposition can be reduced, and the uniform micro-nano array structure with the high depth-to-diameter ratio is obtained.
7. The method of preparing a functional film with a trans-scale micro-nano structure by laser enhanced electrochemical deposition according to claim 1, comprising the steps of:
step one: setting up a processing system for laser enhanced electrochemical deposition;
step two: the method comprises the steps of utilizing a laser thermal effect to enhance an electrodeposition mechanism, adopting laser to irradiate a solid-liquid interface to induce a cross-scale micro-nano structure in an irradiation area while depositing a coating on a substrate, and obtaining the coating with the cross-scale micro-nano structure;
and step three, performing low surface energy treatment in a mixed solution of 1H, 2H-perfluoro decyl triethoxysilane and alcohol.
8. The method for preparing a functional film with a trans-scale micro-nano structure by laser enhanced electrochemical deposition according to claim 7, wherein in the third step, the sample after laser enhanced deposition is placed in a 1% mixed solution of 1h,2 h-perfluorodecyl triethoxysilane and alcohol, heated for 12 hours at 65 ℃, and then dried for 12 hours.
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