CN116833578B - Laser processing method for metal surface electrolytic oxide layer super-hydrophobic corrosion prevention - Google Patents

Laser processing method for metal surface electrolytic oxide layer super-hydrophobic corrosion prevention Download PDF

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CN116833578B
CN116833578B CN202311114035.3A CN202311114035A CN116833578B CN 116833578 B CN116833578 B CN 116833578B CN 202311114035 A CN202311114035 A CN 202311114035A CN 116833578 B CN116833578 B CN 116833578B
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oxide layer
laser processing
metal
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CN116833578A (en
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杨建军
胡龙金
邹婷婷
闫丹丹
许家沛
李林
张睿智
于伟利
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Changchun Institute of Optics Fine Mechanics and Physics of CAS
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B23MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23KSOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K26/00Working by laser beam, e.g. welding, cutting or boring
    • B23K26/36Removing material
    • B23K26/362Laser etching
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B23MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23KSOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K26/00Working by laser beam, e.g. welding, cutting or boring
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    • B23K26/702Auxiliary equipment

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Abstract

The invention relates to the technical field of laser processing, in particular to a super-hydrophobic anti-corrosion laser processing method for an electrolytic oxide layer on a metal surface. The invention combines femtosecond laser processing and micro-arc oxidation, utilizes femtosecond laser pulse to perform focusing irradiation treatment on the metal surface subjected to micro-arc oxidation treatment, eliminates pores and cracks on the surface and the section of an oxide layer by preparing a micro-nano structure on the metal surface, realizes further oxidation on the material surface, maintains the amorphous phase state of an electrolytic oxide layer, realizes the reduction of the surface energy of the material by low-temperature annealing treatment, and obtains the metal surface with superhydrophobic and high corrosion resistance.

Description

Laser processing method for metal surface electrolytic oxide layer super-hydrophobic corrosion prevention
Technical Field
The invention relates to the technical field of laser processing, in particular to a laser processing method for super-hydrophobic corrosion prevention of an electrolytic oxide layer on a metal surface.
Background
The aluminum alloy material has wide and important application in the fields of aerospace, aviation, construction and the like due to the excellent physical properties. However, because aluminum is an active metal, phenomena such as corrosion, cracking and deformation are very easy to occur in air humidity and water environment, the service life of related equipment is severely limited, and a great deal of waste of resources and energy sources is caused, and even life safety is endangered. Therefore, it is important to improve the corrosion resistance of the surface of the aluminum alloy material.
The existing common aluminum alloy corrosion prevention method has anodic oxidation and micro-arc oxidation treatment technologies, and a layer of oxide film is formed on the surface of the aluminum alloy by a chemical electrolysis mode, so that the material corrosion prevention effect is improved. The invention discloses an aluminum alloy surface treatment process, which mainly comprises the steps of firstly carrying out micro-arc oxidation treatment on the surface of an aluminum material, then directionally corroding gamma-alumina by an etching solution, and finally coating acrylic paint on the surface of the material. Compared with a blank aluminum alloy, the corrosion resistance of the material measured after the whole treatment process is finished is improved by two orders of magnitude. The paper 7075 high-strength aluminum alloy anodic oxidation treatment and abrasion and corrosion resistance research reports that the optimal anodic oxidation parameters aiming at aluminum alloy materials are explored by changing factors such as components, voltage, duration, current density and the like of chemical electrolyte, and a hole sealing technology is optimized, so that the corrosion current of the aluminum alloy material is reduced by 20 times compared with that of a blank aluminum alloy.
In addition to the method, the improvement of the anti-corrosion performance of the material surface by utilizing the super-hydrophobic effect in recent years is gradually attracting attention. The method mainly aims at preventing penetration and contact of corrosive medium into the material by preparing the super-hydrophobic surface, so that the anti-corrosion effect is achieved. The invention discloses a super-hydrophobic layer with long service life and high corrosion resistance and wear resistance and a preparation method thereof, and the method carries out multi-step coating treatment for obtaining the super-hydrophobic surface: firstly, silanization is carried out on the surface of the aluminum alloy, then Polydimethylsiloxane (PDMS) is adopted to reduce the surface energy of the material, and spray particles are utilized to prepare a micro-nano structure, so that the super-hydrophobic surface is finally obtained. In this case, the measured surface corrosion protection effect of the material is improved by about two orders of magnitude compared with that of the blank aluminum alloy.
In fact, at present, the oxide layer on the surface of the material prepared by adopting micro-arc oxidation or anodic oxidation technology inevitably has more tiny pores and cracks, so that corrosive medium easily permeates into the material, and finally, the substrate is corroded in a large area, and the methods have great limitation on slowing down the corrosion rate of the material.
Disclosure of Invention
The invention aims to overcome the defects of the prior art, and provides a super-hydrophobic anti-corrosion laser processing method for an electrolytic oxide layer on a metal surface, which can obtain the metal surface with super-hydrophobic and efficient anti-corrosion characteristics.
In order to achieve the above purpose, the present invention adopts the following specific technical scheme:
the invention provides a laser processing method for super-hydrophobic corrosion prevention of an electrolytic oxide layer on a metal surface, which comprises the following steps:
s1, preparing a metal sample, performing electrolytic oxidation pretreatment on the surface of the metal sample, and forming an electrolytic oxidation layer on the surface of the metal sample;
s2, carrying out single focusing scanning irradiation on the metal sample prepared in the step S1 by using ultra-fast laser, ablating to form a micro-nano groove structure on the surface of the metal sample, and densifying the electrolytic oxide layer, so that the oxide layer and the substrate are integrated and are not layered any more, and meanwhile, the amorphous phase state of the electrolytic oxide layer is maintained;
s3, changing the energy density of the ultrafast laser, carrying out at least one-time focusing scanning irradiation on the metal sample prepared in the step S2, carrying out further oxidation on the surface of the metal sample, and simultaneously, retaining the amorphous phase state of the electrolytic oxide layer again;
and S4, performing ultrasonic cleaning on the metal sample processed in the step S3, and performing annealing treatment on the metal sample subjected to ultrasonic cleaning to obtain the metal sample with superhydrophobicity and corrosion resistance.
Preferably, the metal sample is an aluminum alloy, a magnesium alloy or stainless steel.
Preferably, the electrolytic oxidation pretreatment employs a micro-arc oxidation treatment or an anodic oxidation treatment.
Preferably, the thickness of the electrolytic oxide layer is 10 μm to 30 μm.
Preferably, the pulse width of the ultrafast laser is 30 fs-300 ps, and the focusing laser flux is 0.1J/cm 2 ~20J/cm 2 The laser scanning interval is 30-100 μm, the scanning speed is 0.1-5 mm/s, and the groove structure period is 40-80 μm.
Preferably, in step S3, the number of focus scanning irradiation times is 1 to 6.
Preferably, in step S4, the annealing temperature is 150-250 ℃ and the annealing time is 3-8 h.
The invention can obtain the following technical effects:
the method combines micro-arc oxidation and femtosecond laser processing, firstly carries out micro-arc oxidation treatment on the metal surface to obtain an oxide layer with a certain thickness, then carries out focusing irradiation treatment by using femtosecond laser pulse, not only prepares and forms a micro-nano structure on the oxide layer, but also realizes further oxidation treatment on the material surface, and finally realizes the reduction of the material surface energy by low-temperature annealing treatment, thereby obtaining the metal surface with superhydrophobic and high-efficiency corrosion resistance.
Drawings
Fig. 1 is a flow chart of a laser processing method for super-hydrophobic corrosion prevention of an electrolytic oxide layer on a metal surface, which is provided by an embodiment of the invention.
Fig. 2 is a microscopic image of spatially periodically distributed micro-nano structures formed on the surface of a micro-arc alumina alloy, and an oxygen content profile according to the different laser parameters and processing times provided in comparative example 1 and examples 1-2 of the present invention.
Fig. 3 is a schematic diagram of contact angle and rolling angle measured when superhydrophobic effect is obtained on the surface of micro-arc alumina alloy according to different laser parameters and processing times provided in comparative example 1 and examples 1-2 of the present invention.
FIG. 4 is a schematic illustration of polarization curves of metal samples obtained by performing electrochemical corrosion tests according to the different laser parameters and processing times provided in comparative example 1 and examples 1-2 of the present invention.
Fig. 5 is an X-ray diffraction pattern of comparative example 1 and examples 1 to 2 according to the present invention.
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 embodiment of the invention provides a laser processing method for super-hydrophobic corrosion prevention of an electrolytic oxide layer on a metal surface, wherein fig. 1 shows the flow of the laser processing method, and as shown in fig. 1, the method comprises the following steps:
preparing a metal sample, performing electrolytic oxidation pretreatment on the surface of the metal sample, and forming an electrolytic oxidation layer on the surface of the metal sample.
The metal sample can be aluminum alloy, magnesium alloy or stainless steel, the electrolytic oxidation pretreatment adopts micro-arc oxidation treatment or anodic oxidation treatment, and the thickness of the electrolytic oxidation layer is 10-30 mu m.
S2, carrying out single focusing scanning irradiation on the metal sample prepared in the step S1 by using ultra-fast laser, ablating to form a micro-nano groove structure on the surface of the metal sample, and densifying the electrolytic oxide layer, so that the oxide layer and the substrate are fused into a whole and are not layered, and meanwhile, the amorphous phase state of the electrolytic oxide layer is reserved.
The pulse width of the ultrafast laser is 30 fs-300 ps, and the flux of the focused laser is 0.1J/cm 2 ~20J/cm 2 The laser scanning interval is 30-100 μm, the scanning speed is 0.1-5 mm/s, and the groove structure period is 40-80 μm.
S3, changing the energy density of the ultrafast laser, carrying out at least one focusing scanning irradiation on the metal sample prepared in the step S2, carrying out further oxidation on the surface of the metal sample, and simultaneously, retaining the amorphous phase state of the electrolytic oxide layer again. Wherein the focusing scanning irradiation times are 1-6 times.
And S4, performing ultrasonic cleaning on the metal sample subjected to the ultrafast laser processing, and performing annealing treatment on the metal sample subjected to the ultrasonic cleaning to obtain the metal sample with superhydrophobicity and corrosion resistance. The annealing temperature is 150-250 ℃, and the annealing time is 3-8 h.
The metal material obtained through the processing can be applied to the fields of corrosion resistance, superhydrophobicity, self-cleaning, biofouling prevention, icing resistance and water resistance reduction, amorphous components of the processed sample are reserved, and large-area crystallization does not occur.
The laser processing method for the super-hydrophobic corrosion prevention of the electrolytic oxide layer on the metal surface provided by the invention is described below with reference to specific examples.
Fig. 2 is a microscopic image of spatially periodically distributed micro-nano structures formed on the surface of a micro-arc alumina alloy, and an oxygen content profile according to the different laser parameters and processing times provided in comparative example 1 and examples 1-2 of the present invention. Fig. 3 is a schematic diagram of contact angle and rolling angle measured when superhydrophobic effect is obtained on the surface of micro-arc alumina alloy according to different laser parameters and processing times provided in comparative example 1 and examples 1-2 of the present invention. FIG. 4 is a schematic illustration of polarization curves of metal samples obtained by performing electrochemical corrosion tests according to the different laser parameters and processing times provided in comparative example 1 and examples 1-2 of the present invention. Fig. 5 is an X-ray diffraction chart of comparative example 1 and examples 1 to 2.
Comparative example 1
FIG. 2 (a) shows the surface morphology of a micro-arc alumina alloy sample used before femtosecond laser processing, and the surface is smooth and has no obvious micro-nano groove structure, so that air cannot be stored for realizing super-hydrophobic performance, a large number of holes exist, and corrosive media are easy to permeate the sample; FIG. 2 (b) is a view showing a cross section of a micro-arc alumina alloy surface oxide layer in the depth direction before femtosecond laser processing, in which many gaps and cracks are clearly visible, the width of the gaps is 1 μm to 10 μm, and a distinct layered structure is formed between the surface electrolytic oxide and the base material; the bright portion in FIG. 2 (c) is an oxide layer (arrow mark region in the figure) having a thickness of 10 μm to 20 μm and an oxygen element content of 64% was measured.
After ultrasonic cleaning of the micro-arc aluminum oxide alloy surface with deionized water for 30min, the contact angle of the surface to water drops is 80 degrees, no rolling phenomenon exists, and the micro-arc aluminum oxide alloy surface is intrinsically hydrophilic, as shown in fig. 3 (a).
Subsequently, an electrochemical corrosion test was performed on the micro-arc oxidized aluminum alloy sample to determine a polarization curve, and the corrosion current value was 1.398×10 -11 A/cm 2 As shown in fig. 4; the sample had a large number of amorphous phases as shown in fig. 5.
Example 1
Focusing and irradiating femtosecond laser pulse with the pulse width of 40fs to the surface of the micro-arc aluminum oxide alloy by adopting a lens with the focal length of 200mm, and adjusting the laser flux to 7.96J/cm 2 Under the condition of fixed sample position, the three-dimensional moving platform is controlled by a computer to scan the sample in a grid mode, the scanning speed is 1mm/s, the scanning interval is 60 mu m, and finally, the periodic micro-nano groove structure with the depth of 50 mu m and the width of 60 mu m is formed on the surface of the material through ablation, and the periodic micro-nano groove structure is shown in fig. 2 (d). From the depth cross section microscopic image, the original micron-sized gap and crack structure of the oxide layer can be obviously disappeared,
and no obvious layering phenomenon exists between the surface oxide substance and the substrate, as shown in fig. 2 (e). The oxide layer (arrow mark region in the figure) becomes thin after processing, and the oxygen element content thereof is measured to be 53%, as shown in fig. 2 (f).
After ultrasonic cleaning is carried out on the surface of an aluminum alloy sample by using deionized water for 30min, the sample is placed in a vacuum drying oven with the temperature of 200 ℃ for annealing for 3h, the surface of the sample is taken out to obtain superhydrophobicity, the contact angle of water drops is 160 degrees, the rolling angle is 5 degrees, and the sample has superhydrophobicity, as shown in fig. 3 (b).
Subsequently, an electrochemical corrosion test was performed on the aluminum alloy sample, and a polarization curve thereof was measured, and the result is shown in fig. 4. The aluminum alloy sample obtained in this exampleThe corrosion current value is 6.00 multiplied by 10 -13 A/cm 2 1.398×10 compared with comparative example 1 -11 A/cm 2 At least 1.5 orders of magnitude lower, and no significant crystallization of the amorphous phase of this example occurred, as shown in fig. 5.
Example 2
Focusing and irradiating femtosecond laser pulse with the pulse width of 40fs to the surface of the micro-arc aluminum oxide alloy by adopting a lens with the focal length of 200mm, and adjusting the laser flux to 7.96J/cm 2 Under the condition of fixed sample position, the three-dimensional moving platform is controlled by a computer to perform grid scanning on the sample, the scanning speed is 1mm/s, the scanning interval is 60 mu m, and finally, the periodic micro-nano groove structure with the depth of 40 mu m and the width of 60 mu m is formed by ablating on the surface of the material. Then, the incident laser flux was reduced to 0.12J/cm 2 Scanning irradiation was again performed, and at this time, a micro-nano trench structure having a depth of 57 μm and a width of 60 μm was formed on the surface of the material, as shown in fig. 2 (g). The corresponding deep cross-sectional microscopic image shows that the micron-sized pores and cracks disappear, and no obvious layering phenomenon exists between the surface oxide and the substrate, as shown in fig. 2 (h). After the re-processing, the thickness of the oxide layer (the arrow mark region in the figure) increased to about 10 μm, and the oxygen element content was measured to be 66%, as shown in FIG. 2 (i).
After the aluminum alloy surface is ultrasonically cleaned for 30min by using deionized water, the aluminum alloy surface is placed in a vacuum drying oven with the temperature of 200 ℃ for annealing for 3h, the surface is subjected to super-hydrophobic phenomenon after being taken out, the contact angle of water drops is 161 degrees, the rolling angle is 4 degrees, and the aluminum alloy surface has super-hydrophobic property, as shown in fig. 3 (c).
Subsequently, an electrochemical corrosion test was performed on the aluminum alloy sample, and a polarization curve thereof was measured, and the result is shown in FIG. 4, in which the aluminum alloy sample obtained in this example had a corrosion current value of 9.675X 10 -14 A/cm 2 Compared with the micro-arc alumina alloy sample 1.398×10 in comparative example 1 -11 A/cm 2 At least 2 orders of magnitude lower, the amorphous phase of which is not significantly crystallized, as shown in fig. 5.
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 are not necessarily directed 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, the different embodiments or examples described in this specification and the features of the different embodiments or examples may be combined and combined by those skilled in the art without contradiction.
While 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 to the above embodiments by one of ordinary skill in the art within the scope of the invention.
The above embodiments of the present invention do not limit the scope of the present invention. Any of various other corresponding changes and modifications made according to the technical idea of the present invention should be included in the scope of the claims of the present invention.

Claims (7)

1. The super-hydrophobic anti-corrosion laser processing method for the electrolytic oxide layer on the metal surface is characterized by comprising the following steps of:
s1, preparing a metal sample, carrying out electrolytic oxidation pretreatment on the surface of the metal sample, and forming an electrolytic oxidation layer on the surface of the metal sample;
s2, carrying out single focusing scanning irradiation on the metal sample prepared in the step S1 by using ultrafast laser, ablating the surface of the metal sample to form a micro-nano groove structure, densifying the electrolytic oxide layer, integrating the oxide layer and the substrate, preventing layering, and keeping the amorphous state of the electrolytic oxide layer;
s3, changing the energy density of the ultrafast laser, carrying out at least one-time focusing scanning irradiation on the metal sample prepared in the step S2, carrying out further oxidation on the surface of the metal sample, and simultaneously, retaining the amorphous phase state of the electrolytic oxide layer again;
and S4, performing ultrasonic cleaning on the metal sample processed in the step S3, and performing annealing treatment on the metal sample subjected to ultrasonic cleaning to obtain the metal sample with superhydrophobicity and corrosion resistance.
2. The laser processing method of metal surface electrolytic oxide layer super-hydrophobic corrosion protection according to claim 1, wherein the metal sample is aluminum alloy, magnesium alloy or stainless steel.
3. The laser processing method for super-hydrophobic anticorrosion of an electrolytic oxide layer on a metal surface according to claim 1, wherein the electrolytic oxidation pretreatment adopts micro-arc oxidation treatment or anodic oxidation treatment.
4. The laser processing method for super-hydrophobic corrosion protection of an electrolytic oxide layer on a metal surface according to claim 1, wherein the thickness of the electrolytic oxide layer is 10 μm to 30 μm.
5. The laser processing method for the super-hydrophobic corrosion protection of the electrolytic oxide layer on the metal surface according to claim 1, wherein the pulse width of the ultrafast laser is 30 fs-300 ps, and the focused laser flux is 0.1J/cm 2 ~20J/cm 2 The laser scanning interval is 30-100 μm, the scanning speed is 0.1-5 mm/s, and the groove structure period is 40-80 μm.
6. The laser processing method for the super-hydrophobic corrosion protection of the electrolytic oxide layer on the metal surface according to claim 1, wherein in the step S3, the number of times of focusing scanning irradiation is 1 to 6.
7. The laser processing method for the super-hydrophobic corrosion protection of the electrolytic oxide layer on the metal surface according to claim 1, wherein in the step S4, the annealing temperature is 150-250 ℃, and the annealing time is 3-8 h.
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CN117431495B (en) * 2023-12-19 2024-02-13 中国科学院长春光学精密机械与物理研究所 Super-hydrophobic anti-corrosion double-layer structure of metal surface and preparation method thereof

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