CN112207010A - Self-cleaning metal surface and preparation method and preparation device thereof - Google Patents
Self-cleaning metal surface and preparation method and preparation device thereof Download PDFInfo
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- CN112207010A CN112207010A CN202011083620.8A CN202011083620A CN112207010A CN 112207010 A CN112207010 A CN 112207010A CN 202011083620 A CN202011083620 A CN 202011083620A CN 112207010 A CN112207010 A CN 112207010A
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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
- B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
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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
- 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
- B05D3/04—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 exposure to gases
- B05D3/0406—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 exposure to gases the gas being air
- B05D3/0413—Heating with air
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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
- 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
- B05D3/06—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 exposure to radiation
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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
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- 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
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- 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
- B23K26/36—Removing material
- B23K26/362—Laser etching
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Abstract
The invention discloses a self-cleaning metal surface and a preparation method and a preparation device thereof, wherein the measurement method comprises the following steps: s1, cleaning and drying the surface of the metal; s2, irradiating the surface of the metal by using pulse laser to etch particles with nano-scale or micro-scale sizes, and adsorbing organic matters on the surface of the metal after laser etching, wherein the organic matters have functional groups for reducing surface energy; and S3, performing heating treatment on the metal surface etched with the particles. The invention can prepare the self-cleaning metal surface with super lyophobic property or lyophobic property only by adopting pulse laser and heating treatment, does not need chemical process treatment, and has simple process, high efficiency, environmental protection and lasting performance.
Description
Technical Field
The invention relates to the technical field of laser processing, in particular to a self-cleaning metal surface and a preparation method and a preparation device thereof.
Background
The wetting characteristics of a solid surface are defined by measuring the contact angle of a drop of water when it comes into contact with the solid surface. When the contact angle is in the range of 90-150 degrees, the solid surface is defined to have hydrophobicity; when the contact angle is greater than 150 °, the solid surface is defined to have superhydrophobicity. Superhydrophobic surfaces have low surface energy molecules. However, the use of low surface energy molecules alone is not enough to form a superhydrophobic surface, and a micro-nano composite structure needs to be added on the solid surface. On the other hand, super-hydrophobic surfaces exist in nature, such as lotus leaves, butterfly wings, fish scales, sharkskin and the like, and have unique waterproof and self-cleaning functions. In the technical field of engineering, many researchers are inspired by the above natural phenomena, and a super-hydrophobic metal interface is prepared by using laser and applied to waterproof and anticorrosion aspects. The traditional preparation process of the super-hydrophobic metal surface comprises two steps: firstly, femtosecond, picosecond or nanosecond laser is used for processing and preparing a micron, nanometer or even micro-nano multilayer structure on the surface of a material, such as a net, a point, a recess, a column, a laser-induced periodic stripe structure, a groove and the like; secondly, the metal surface is changed from hydrophilicity to hydrophobicity or super hydrophobicity by increasing the polymer coating with low surface energy and carrying out aging treatment for a long time in the later period.
However, the existing post-processing method has many limitations. For example: hydrophobic polymer coatings are relatively complex to manufacture, expensive in chemical coating equipment or use toxic chemicals. Moreover, the duration of the chemical coating and the applicable temperature range are narrow; the post-aging treatment takes weeks or even months to achieve the superhydrophobic property. For example, laser ablation of aluminum takes 30-40 days to achieve superhydrophobic properties, laser ablation of stainless steel takes 14-60 days, and laser ablation of other metallic materials such as copper, brass, and titanium takes 11-30 days. This post-processing process takes too long and the technique does not meet the goals of the manufacturing industry.
Disclosure of Invention
The invention aims to solve the technical problems and provides a self-cleaning metal surface, a preparation method and a preparation device thereof, so as to solve the problems that the existing post-treatment mode is too long in time consumption and not environment-friendly.
In order to achieve the purpose, the invention adopts the following specific technical scheme:
the invention provides a self-cleaning metal surface, wherein particles for realizing super-lyophobic property or lyophobic property are etched on the metal surface by laser, the size of the particles is nano-scale or micro-scale, organic matters are adsorbed on the surfaces of the particles, and the organic matters have functional groups for reducing surface energy.
Preferably, the contact angle of the surface of the metal is greater than 150 ° or between 90 ° and 150 °, and the sliding angle of the surface of the metal is less than 10 °.
Preferably, the functional group is a methyl group, a methylene group or a carbon-carbon double bond.
Preferably, the metal is aluminum, titanium, zinc, aluminum alloy, copper titanium alloy, iron, or stainless steel.
Preferably, the object of the ultralyophobic property or the lyophobic property is water, coffee, milk, an acid-base solution, a neutral solution, a copper phthalocyanine solution, or a rhodamine6G solution.
The second aspect of the invention provides a preparation method of a self-cleaning metal surface, which comprises the following steps:
s1, cleaning and drying the metal surface;
s2, irradiating the metal surface with pulsed laser to etch particles with nanometer or micron size, and adsorbing organic matter on the surface of the particles, wherein the organic matter has functional groups for reducing surface energy.
Preferably, after step S2, the method further includes the following steps:
and S3, performing heating treatment on the metal surface etched with the particles.
Preferably, the functional group is a methyl group, a methylene group or a carbon-carbon double bond.
Preferably, step S3 specifically includes the following steps:
s31, introducing air into the heating equipment;
s32, starting heating equipment, and putting the metal into the heating equipment for heating; wherein the heating temperature is more than 100 ℃, and the heating time is more than 10 minutes.
The third aspect of the invention provides a preparation device for a self-cleaning metal surface, which comprises a pulse laser, a controller, a focusing lens, a reflecting mirror and a three-dimensional moving platform, wherein the reflecting mirror is arranged in the emergent direction of the pulse laser, the focusing lens is arranged in the reflecting direction of the reflecting mirror, the three-dimensional moving platform is arranged on the focal plane of the focusing lens, and metal is placed on the three-dimensional moving platform; the controller controls the pulse laser to emit pulse laser, the pulse laser is reflected to the focusing lens through the reflector, and then the pulse laser is converged to the metal surface of the three-dimensional moving platform through the focusing lens, so that particles with nanoscale or micron-sized dimensions are etched, and organic matters are adsorbed on the surfaces of the particles, wherein the organic matters have functional groups for reducing the surface energy.
The invention can obtain the following technical effects:
1. the self-cleaning metal surface with the super-lyophobic property or the lyophobic property can be prepared by adopting the pulse laser and the heating treatment, the chemical process treatment is not needed, the process is simple, the efficiency is high, and the environment is protected.
2. The self-cleaning metal surface prepared by the pulse laser etching has super lyophobic property or lyophobic property, and the performance is durable.
Drawings
Fig. 1 is a schematic structural diagram of a self-cleaning metal surface provided by an embodiment of the invention.
FIG. 2 is a schematic structural diagram of an apparatus for preparing a self-cleaning metal surface according to an embodiment of the present invention.
Fig. 3 is a schematic flow chart of a method for preparing a self-cleaning metal surface according to an embodiment of the present invention.
Fig. 4 is a graph of the ultraphobic results of the treated aluminum surface of water, coffee, milk, hydrochloric acid solution at ph 1, sodium hydroxide solution at ph 14, copper phthalocyanine solution, and rhodamine6G solution provided in one embodiment of the present invention.
FIG. 5 shows an aluminum surface having 3% CuCl concentration before and after laser treatment according to one embodiment of the present invention2Comparative graph of corrosion results.
Fig. 6 is a graph showing the measurement result of the contact angle of the surface of aluminum, titanium, zinc, aluminum alloy, copper-titanium alloy, iron, stainless steel after laser treatment according to one embodiment of the present invention.
FIG. 7 is a microstructure diagram of an aluminum surface after laser treatment according to one embodiment of the present invention.
FIG. 8 is a Fourier transform infrared spectrum of an aluminum surface before and after treatment according to one embodiment of the present invention.
Fig. 9 is a graph of the results of contact angle and roll angle on the treated aluminum surface for different laser scanning pitches provided by one embodiment of the present invention.
FIG. 10 is a graph of the results of wetting characteristics of contact angle and roll angle for an aluminum surface provided by one embodiment of the present invention.
Wherein the reference numerals include: the device comprises metal 1, particles 2, organic matters 3, a pulse laser 4, a controller 5, a reflector 6, a focusing lens 7 and a three-dimensional moving platform 8.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in further detail below with reference to the accompanying drawings and specific embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not to be construed as limiting the invention.
Noun interpretation
Super-hydrophobic characteristics: the method refers to that when a water drop is in contact with a solid surface and the contact angle is larger than 150 degrees, the solid surface is defined to have super-hydrophobic characteristics.
Hydrophobic property: the method is characterized in that when a water drop is in contact with the solid surface and the contact angle is in the range of 90-150 degrees, the solid surface is defined to have hydrophobic characteristics.
Super lyophobic property: refers to the contact angle of water drops and other liquids (such as milk, coffee and the like) with the solid surface, and the contact angle is more than 150 degrees, and the solid surface is defined to have super lyophobic property. The ultralyophobic property is a generic concept of the ultrahydrophobic property.
Lyophobic property: refers to the condition that water drops and other liquids (such as milk, coffee and the like) are contacted with the solid surface, and the contact angle is in the range of 90-150 degrees, and the solid surface is defined to have lyophobic property. Lyophobic properties are a generic concept of hydrophobic properties.
Because the self-cleaning metal surface provided by the invention not only shows the super-hydrophobic property to water, but also shows the super-hydrophobic property to other liquids, for convenience of expression, the self-cleaning metal surface is collectively called as super-lyophobic property or lyophobic property, and does not show that the metal surface does not have the super-hydrophobic property or hydrophobic property.
The self-cleaning metal surface provided by the embodiment of the invention, and the preparation method and the preparation device thereof will be described in detail below.
Fig. 1 shows a structure of a self-cleaning metal surface provided by an embodiment of the present invention.
As shown in fig. 1, particles 2 which are different in size and are randomly distributed are etched on the surface of a metal 1 through pulse laser, the size of the particles 2 is nano-scale or micron-scale, the particles 2 are important components forming a micro-nano structure on the surface of the metal 1, and the micro-nano structure is used as one of conditions for forming an ultra-lyophobic property or a lyophobic property on the surface of the metal 1.
Another condition for the metal 1 surface to form the super lyophobic property or the lyophobic property is that the contact angle and the rolling angle of the metal 1 surface satisfy the following requirements:
contact angle is larger than 150 degrees;
the contact angle is more than or equal to 90 degrees and less than or equal to 150 degrees;
and the rolling angle is less than 10 degrees.
The magnitude of the contact angle determines whether the surface of the metal 1 has super-liquid repellency or liquid repellency. When the contact angle is larger than 150 degrees, the surface of the metal 1 has super lyophobic property, and when the contact angle is larger than or equal to 90 degrees and smaller than or equal to 150 degrees, the surface of the metal 1 has lyophobic property.
The size of the roll angle determines whether the metal 1 surface has a lotus effect or a rose effect. The rolling angle is less than 10 degrees, and the lotus leaf effect is shown; conversely, if the roll angle is greater than 10 ° or there is no roll angle, a rose effect is shown.
It should be noted that the contact angle is affected by changing the surface energy and roughness of the surface of the metal 1, and the performance of the ultralyophobic property of the surface of the metal 1 is better when the contact angle is larger and the rolling angle is smaller.
After the surface of the metal 1 is treated by the pulse laser, the surface of the metal 1 can be adsorbed with an organic matter 3 with the super-hydrophobic effect, the organic matter 3 comprises a functional group, and the functional group with the super-hydrophobic effect is actually a functional group which is a methyl (-CH)3) Methylene group (-CH)2-) or a carbon-carbon double bond (C ═ C). The functional group has the super-hydrophobic property, can reduce the surface energy of the surface of the metal 1, improves the lyophobicity of the surface of the metal 1, promotes the contact angle to be more than 150 degrees, and changes the surface roughness by combining the micro-nano structure of the surface of the metal 1, so that the surface of the metal 1 achieves the super-hydrophobic property.
In some embodiments of the present invention, the metal 1 may be aluminum, titanium, zinc, aluminum alloy, copper-titanium alloy, iron, stainless steel, or the like.
In some examples of the invention, the ultralyophobic properties of the metal 1 surface refer to ultralyophobic properties to water, coffee, milk, acid-base solutions, neutral solutions, copper phthalocyanine solutions, and rhodamine6G solutions. That is, the self-cleaning metal surface provided by the invention not only can be super-hydrophobic, but also can be super-hydrophobic in coffee, milk, acid-base solution, neutral solution, copper phthalocyanine solution and Rhodamine6G (Rhodamine6G) solution. The contact angles of water, coffee, milk, acid-base solution, neutral solution, copper phthalocyanine solution and rhodamine6G solution with the surface of the metal 1 are all larger than 90 degrees. The acid-base solution in the present invention refers to an acidic solution and a basic solution.
The foregoing describes in detail the self-cleaning metal surface provided by the embodiment of the present invention, and the present invention further provides a device for manufacturing a self-cleaning metal surface, corresponding to the self-cleaning metal surface.
Fig. 2 shows the structure of the device for preparing the self-cleaning metal surface provided by the embodiment of the invention.
As shown in fig. 2, the apparatus for preparing a self-cleaning metal surface according to an embodiment of the present invention includes: the device comprises a pulse laser 4, a controller 5, a reflector 6, a focusing lens 7 and a three-dimensional moving platform 8, wherein the pulse laser 4 is used for emitting pulse laser which can be femtosecond pulse laser, picosecond pulse laser or nanosecond pulse laser. The controller 5 is used to control the operating parameters of the pulsed laser 4, such as: controlling the wavelength, frequency, pulse width, power, etc. of the laser. The number of the reflecting mirrors 6 is at least one, and is provided in the emission direction of the pulse laser 4 for guiding the laser light to the focusing lens 7.
The focusing lens 7 is arranged in the reflection direction of the reflector 6 and used for focusing laser to the three-dimensional moving platform 8, the three-dimensional moving platform 8 is arranged on the focal plane of the focusing lens 7, the metal 1 is placed on the three-dimensional moving platform 8, and the three-dimensional moving platform 8 is used for driving the metal 1 to move along three directions. The three-dimensional moving platform 8 is a common moving platform in the market, and the specific structure thereof is not described in detail in the present invention.
The controller 5 controls the pulse laser 4 to emit pulse laser, the pulse laser is reflected to the focusing lens 7 through the reflector 6, and then the pulse laser is converged on the surface of the metal 1 placed on the three-dimensional moving platform 8 through the focusing lens 7, the metal 1 is moved through the three-dimensional moving platform 8, grooves, meshes and other micron-scale and nanometer-scale etching structures are formed on the surface of the metal 1, and the etching structures are patterns formed by particles with micron-scale and nanometer-scale sizes.
In one example of the present invention, the pulsed laser 4 is a solid state laser diode pumped Yb-doped dielectric laser whose pump source is a single frequency diode.
The device for preparing the self-cleaning metal surface can also comprise heating equipment, wherein the heating equipment can be a drying box or the like and is used for heating the surface of the metal 1 after laser treatment so as to accelerate the speed of adsorbing organic matters on the surface of the metal 1 and increase the adsorption quantity of the organic matters.
In a specific example of the present invention, the operating parameters of the pulsed laser 4 are: the laser wavelength is 800nm, the pulse width is 40fs, the repetition frequency is 1k-1MHz, and the laser power is 50 mW-20W.
In some preferred embodiments of the present invention, the femtosecond pulse laser preferably has a repetition frequency of 1kHz and a laser power of 200mW, and the contact angles of the prepared metal 1 surface wetting characteristics are all more than 155 °, and the metal 1 surface wetting characteristics are expressed as ultralyophobic characteristics.
The above-mentioned details describe the apparatus for preparing a self-cleaning metal surface according to the embodiment of the present invention, and the present invention further provides a method for preparing a self-cleaning metal surface corresponding to the apparatus for preparing a self-cleaning metal surface.
Fig. 3 shows a flow of a method for preparing a self-cleaning metal surface according to an embodiment of the present invention.
As shown in fig. 3, the method for preparing a self-cleaning metal surface according to an embodiment of the present invention includes the following steps:
and S1, cleaning and drying the metal surface.
The cleaning of the metal surface may be, but is not limited to, the following: the metal is firstly put into acetone for ultrasonic cleaning, and then put into deionized water for ultrasonic cleaning.
The drying treatment mode of the cleaned metal can be a cold air blow drying or drying mode and the like.
And S2, irradiating the metal surface by using pulse laser to etch particles with nano-scale or micron-scale sizes.
The pulsed laser may be a femtosecond, picosecond, or nanosecond pulsed laser.
After the metal surface is treated by laser, the self-cleaning metal surface can be obtained. According to some embodiments of the present invention, the metal is mainly aluminum, titanium, copper-titanium alloy, aluminum alloy, zinc, iron, stainless steel, etc., and the self-cleaning function is mainly embodied by the super-hydrophobic property of the surface of aluminum, titanium, copper-titanium alloy, aluminum alloy, zinc, iron, stainless steel, coffee, milk, acid-base solution, neutral solution, copper phthalocyanine solution and rhodamine6G solution.
When the metal surface is processed by laser, the metal reacts with oxygen and water vapor in the air at high temperature to generate oxides and hydroxides with adsorbability on the metal surface, and the oxides and hydroxides absorb organic matters (mostly existing in methyl, methylene and carbon-carbon double bonds) in the air to react with the organic matters, so that functional groups for reducing the surface energy are generated on the metal surface.
The reaction formula of the hydroxide reacting with the organic matter in the air to generate the functional group is as follows:
the reaction formula of the oxide and the organic matter in the air to generate the functional group is as follows:
in the above two reaction formulae, 2 represents an organic substance present in the air.
The oxides and hydroxides generated on the metal surface adsorb organic matters in the air to react to generate functional groups with reduced surface energy, so that the lyophobicity of the metal surface is improved.
Preferably, after step S2, the method further includes the following steps:
and S3, performing heating treatment on the metal surface etched with the particles.
The heating treatment can accelerate the adsorption speed of the metal surface, shorten the adsorption time and enable the metal surface to adsorb organic matters with low enough surface energy in a short time.
In some examples of the present invention, step S3 specifically includes the following steps:
and S31, introducing air into the heating device.
And S32, starting the heating equipment, and putting the metal into the heating equipment for heating.
The heating temperature is more than 100 ℃, and the heating time is more than 10 minutes.
According to the preparation method provided by the invention, the self-cleaning metal surface can be prepared only by carrying out heat treatment on the metal surface after the metal surface is processed by the femtosecond pulse laser, aging treatment is not needed, the metal surface has super lyophobic property or lyophobic property in a short time, chemical coating modification treatment is not needed, the process is simple, the efficiency is high, toxic chemicals are not needed, and the preparation method is green and environment-friendly.
The self-cleaning metal surface prepared by the preparation method has lasting self-cleaning performance and liquid repellency, and can be super-hydrophobic, super-hydrophobic coffee, milk, acid-base solution, neutral solution, copper phthalocyanine solution and rhodamine6G solution.
The invention carries out laser etching and heating treatment on the metal surface to enable the metal surface to have the super-hydrophobic characteristic, and the nonmetal material with low surface energy is easier to process to realize the super-hydrophobic characteristic.
The metal was tested with aluminum as an example. As shown in fig. 4, the contact angles of water, coffee, milk, hydrochloric acid solution of ph 1, sodium hydroxide solution of ph 14, copper phthalocyanine solution, and rhodamine6G solution with the aluminum surface which was not laser-treated were less than 90 °, and after laser irradiation and heat treatment on the aluminum surface, these solutions exhibited a spherical shape on the aluminum surface after processing, and a contact angle with the aluminum surface after laser treatment was more than 150 °, exhibiting ultraphobic properties. The contact angles of the aluminum with these solutions were measured again after leaving the aluminum in air for 3 months, and were unable to adhere to the aluminum surface, and the rolling angle was less than 10 °. These results indicate that the ultralyophobic properties of the aluminum surface can be maintained for more than three months. Therefore, the experimental result shows that the aluminum surface after laser treatment has liquid repellency.
In addition, the self-cleaning metal surface prepared by the preparation method has good corrosion resistance, and CuCl with the concentration of 3% is put into the untreated and treated aluminum surface2In the solution, after soaking for 3 minutes, the change of the aluminum surface morphology is observed comparatively, as shown in fig. 5, the area of the aluminum surface after laser treatment is soaked in the solution, no obvious change occurs, no copper is precipitated on the surface, the area of the aluminum surface without laser treatment has a large amount of copper reaction precipitation, after rinsing with clean water, the area of the aluminum surface without laser treatment is found to have obvious corrosion, and the area of the aluminum surface after laser treatment is nearly unchanged, so the result shows that the area of the aluminum surface after laser treatment is obtainedThe domains have good corrosion resistance.
The advantageous effects of the present invention are verified below in several embodiments.
Example 1
Placing the cleaned aluminum on a three-dimensional moving platform, and adjusting working parameters of a pulse laser light source: the wavelength is 800nm, the pulse width is 40fs, the power is 200mw, the grid scanning interval is 100 microns, the three-dimensional moving platform moves at the speed of 1mm/s, laser irradiates the surface of the aluminum, the surface of the aluminum is heated after scanning a grid structure with the interval of 100 microns, and then the heating treatment is carried out for 30 minutes at the temperature of 200 ℃. Titanium, iron, copper, zinc, 1:1 copper-titanium alloy, 304 stainless steel were subjected to the same treatment. The measurement results are shown in fig. 6, and it can be seen that aluminum, titanium, iron, copper, zinc, 1:1 copper-titanium alloy, and 304 stainless steel all have a contact angle of about 150 °, and except for zinc, all have a rolling angle of about 10 °, and are in a hydrophobic/superhydrophobic state.
Microstructure observation, Fourier infrared spectrum test and wetting performance test are respectively carried out on the aluminum surface, and the test results are respectively shown in fig. 7, fig. 8, fig. 9 and fig. 10.
The method for testing the wetting performance comprises the following steps: the contact angle of the surface wettability of the sample was measured at room temperature using a commercial contact angle measuring instrument (PowereachJC2000D3) supplied by the digital technology equipment ltd. The droplet size was 10 microliters and the contact angle and the roll angle were measured.
Microstructure observation method: the microscopic image of the surface of the sample was measured at room temperature in a vacuum environment using a commercial electron scanning microscope (ProX800-07334) supplied by phenomwold corporation at a voltage of 15 KV.
The Fourier infrared spectrum test method comprises the following steps: the surface IR spectrum of the sample was measured at room temperature using a commercial Fourier Infrared Spectroscopy (Cary630FTIR) available from Agilent technologies, Inc.
Fig. 7 shows the microstructure of the aluminum surface after laser treatment, and it can be seen that after laser irradiation, a large amount of micro-nano structured particles are generated on the aluminum surface, which greatly increases the roughness of the aluminum surface.
FIG. 8 shows Fourier transform infrared spectra of aluminum surfaces before and after treatment, from which FIG. 8 it can be seen that after femtosecond laser irradiation and heat treatment, the aluminum surface has significant-CH3、-CH2The absorption peaks of-and-C ═ C, the result proves that the processed aluminum surface has obvious organic adsorption, and the processed aluminum surface has obvious organic adsorption due to-CH 3, -CH2The presence of-and C ═ C reduces the surface energy of the aluminum surface.
Fig. 9 shows the results of contact angle, roll angle on the treated aluminum surface for different laser scanning pitches. In fig. 9, the surface treated in a grid pattern with a laser irradiation pitch of 100 μm was in a superhydrophobic state with a contact angle of more than 150 ° and a rolling angle of about 5 °.
Fig. 10 shows the results of wetting characteristics of the contact angle and the rolling angle of the aluminum surface after repeating the treatment 10 times. As shown in fig. 10, the aluminum surface obtained by irradiating the aluminum surface with the wavelength of 800nm, the pulse width of 40fs, the power of 200mw, the grid scanning interval of 100 μm and the scanning speed of 1mm/s was repeatedly used 10 times, followed by heating at 200 ℃ for 30 minutes, and the contact angle and the rolling angle of the aluminum surface were measured, and it was found that the contact angle of the aluminum surface treated by the method was about 160 °, and the rolling angle was about 5 °, which was repeatable and stable.
It is emphasized that methylene (-CH) was detected on the surface of the laser-treated aluminum as shown in FIG. 72-) methyl (-CH3) Or carbon-carbon double bond (C ═ C), which is not detected on the surface of the aluminum that has not been treated by laser, and which has hydrophobic property, so that it can be concluded that the increase of carbon atom content on the surface of the aluminum comes from the absorption of organic matters in the air environment during the action of the surface of the metal sample and the femtosecond laser.
Example 2
Placing the cleaned aluminum on a three-dimensional moving platform, and adjusting working parameters of a femtosecond pulse laser light source: the wavelength is 800nm, the pulse width is 40fs, the power is 200mw, the grid-shaped scanning interval is 300 microns, the scanning speed is 1mm/s, the aluminum surface is irradiated with light, then the aluminum surface is heated at 200 ℃ for 30 minutes to obtain a processed sample with the super-hydrophobic surface, and the contact angle and the rolling angle of the processed sample are respectively tested, and the result is shown in figure 9, which shows that the contact angle is larger than 150 degrees, the rolling angle is about 10 degrees, and the sample shows the super-hydrophobic characteristic.
Example 3
Placing the cleaned aluminum on a three-dimensional moving platform, and adjusting working parameters of a femtosecond pulse laser light source: the wavelength is 800nm, the pulse width is 40fs, the power is 200mw, the grid-shaped scanning interval is 500 microns, the scanning speed is 1mm/s, the aluminum surface is irradiated, then the heating treatment is carried out at 200 ℃ for 30 minutes, and the contact angle and the rolling angle of the aluminum surface are respectively tested, and the result is shown in figure 9, which shows that the contact angle is more than 150 degrees, the rolling angle is about 20 degrees, and the super-hydrophobic characteristic is represented.
Example 4
Placing the cleaned aluminum on a three-dimensional moving platform, and adjusting working parameters of a femtosecond pulse laser light source: the wavelength is 800nm, the pulse width is 40fs, the power is 200mw, linear scanning in a single dimensional direction is carried out, the interval is 100 microns, the scanning speed is 1mm/s, the aluminum surface is irradiated, and then heating treatment is carried out at 200 ℃ for 30 minutes, so that the aluminum surface is still in a super-hydrophobic state.
In the description herein, references to the description of the term "one embodiment," "some embodiments," "an example," "a specific example," or "some examples," etc., mean 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 invention. In this specification, the schematic representations of the terms used above are not necessarily intended to refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, various embodiments or examples and features of different embodiments or examples described in this specification can be combined and combined by one skilled in the art without contradiction.
Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention, and that variations, modifications, substitutions and alterations can be made to the above embodiments by those of ordinary skill in the art within the scope of the present invention.
The above embodiments of the present invention should not be construed as limiting the scope of the present invention. Any other corresponding changes and modifications made according to the technical idea of the present invention should be included in the protection scope of the claims of the present invention.
Claims (10)
1. A self-cleaning metal surface is characterized in that particles for realizing super-lyophobic property or lyophobic property are etched on the metal surface by laser, the size of the particles is nano-scale or micro-scale, and organic matters are adsorbed on the surfaces of the particles and have functional groups for reducing the surface energy.
2. Self-cleaning metal surface according to claim 1, wherein the contact angle of the metal surface is more than 150 ° or between 90 ° and 150 °, and the sliding angle of the metal surface is less than 10 °.
3. The self-cleaning metal surface of claim 1 wherein said functional group is a methyl group, a methylene group, or a carbon-carbon double bond.
4. The self-cleaning metal surface according to claim 1 or 2, wherein the metal is aluminum, titanium, zinc, aluminum alloy, copper-titanium alloy, iron or stainless steel.
5. Self-cleaning metal surface according to claim 4, wherein the object of ultralyophobic properties or lyophobic properties is water, coffee, milk, acid-base solutions, neutral solutions, copper phthalocyanine solutions or rhodamine6G solutions.
6. A preparation method of a self-cleaning metal surface is characterized by comprising the following steps:
s1, cleaning and drying the metal surface;
and S2, irradiating the metal surface by using pulsed laser to etch particles with nanometer or micron size, and adsorbing organic matters on the surfaces of the particles, wherein the organic matters have functional groups for reducing the surface energy.
7. The method for preparing a self-cleaning metal surface according to claim 6, further comprising the following steps after step S2:
and S3, performing heating treatment on the metal surface etched with the particles.
8. Method for producing a self-cleaning metal surface according to claim 6 or 7, characterised in that the functional group is a methyl, methylene or carbon-carbon double bond.
9. The method for preparing a self-cleaning metal surface according to claim 7, wherein step S3 specifically comprises the steps of:
s31, introducing air into the heating equipment;
s32, starting the heating equipment, and putting metal into the heating equipment for heating; wherein the heating temperature is more than 100 ℃, and the heating time is more than 10 minutes.
10. A preparation device for self-cleaning metal surfaces is characterized by comprising a pulse laser, a controller, a focusing lens, a reflecting mirror and a three-dimensional moving platform, wherein the reflecting mirror is arranged in the emergent direction of the pulse laser, the focusing lens is arranged in the reflecting direction of the reflecting mirror, the three-dimensional moving platform is arranged on the focal plane of the focusing lens, and metal is placed on the three-dimensional moving platform; the controller controls the pulse laser to emit pulse laser, the pulse laser is reflected to the focusing lens through the reflector and then is converged on the metal surface through the focusing lens, particles with nanoscale or micron-sized dimensions are etched, and organic matters are adsorbed on the surfaces of the particles, wherein the organic matters have functional groups for reducing surface energy.
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