CN114178795A - Preparation method of anisotropic super-hydrophobic surface of metal material - Google Patents

Preparation method of anisotropic super-hydrophobic surface of metal material Download PDF

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CN114178795A
CN114178795A CN202111543614.0A CN202111543614A CN114178795A CN 114178795 A CN114178795 A CN 114178795A CN 202111543614 A CN202111543614 A CN 202111543614A CN 114178795 A CN114178795 A CN 114178795A
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metal material
anisotropic
array structure
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CN114178795B (en
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胡静
杨晓红
叶霞
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Changzhou University
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23P—METAL-WORKING NOT OTHERWISE PROVIDED FOR; COMBINED OPERATIONS; UNIVERSAL MACHINE TOOLS
    • B23P15/00—Making specific metal objects by operations not covered by a single other subclass or a group in this subclass
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B08—CLEANING
    • B08B—CLEANING IN GENERAL; PREVENTION OF FOULING IN GENERAL
    • B08B3/00—Cleaning by methods involving the use or presence of liquid or steam
    • B08B3/04—Cleaning involving contact with liquid
    • B08B3/10—Cleaning involving contact with liquid with additional treatment of the liquid or of the object being cleaned, e.g. by heat, by electricity or by vibration
    • B08B3/12—Cleaning involving contact with liquid with additional treatment of the liquid or of the object being cleaned, e.g. by heat, by electricity or by vibration by sonic or ultrasonic vibrations
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23H—WORKING OF METAL BY THE ACTION OF A HIGH CONCENTRATION OF ELECTRIC CURRENT ON A WORKPIECE USING AN ELECTRODE WHICH TAKES THE PLACE OF A TOOL; SUCH WORKING COMBINED WITH OTHER FORMS OF WORKING OF METAL
    • B23H11/00—Auxiliary apparatus or details, not otherwise provided for
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23H—WORKING OF METAL BY THE ACTION OF A HIGH CONCENTRATION OF ELECTRIC CURRENT ON A WORKPIECE USING AN ELECTRODE WHICH TAKES THE PLACE OF A TOOL; SUCH WORKING COMBINED WITH OTHER FORMS OF WORKING OF METAL
    • B23H7/00—Processes or apparatus applicable to both electrical discharge machining and electrochemical machining
    • B23H7/02—Wire-cutting
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23H—WORKING OF METAL BY THE ACTION OF A HIGH CONCENTRATION OF ELECTRIC CURRENT ON A WORKPIECE USING AN ELECTRODE WHICH TAKES THE PLACE OF A TOOL; SUCH WORKING COMBINED WITH OTHER FORMS OF WORKING OF METAL
    • B23H7/00—Processes or apparatus applicable to both electrical discharge machining and electrochemical machining
    • B23H7/22—Electrodes specially adapted therefor or their manufacture
    • B23H7/24—Electrode material
    • 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
    • B23K26/08—Devices involving relative movement between laser beam and workpiece
    • B23K26/082—Scanning systems, i.e. devices involving movement of the laser beam relative to the laser head
    • 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
    • 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
    • B23K26/70—Auxiliary operations or equipment
    • B23K26/702—Auxiliary equipment

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Plasma & Fusion (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • ing And Chemical Polishing (AREA)
  • Electrical Discharge Machining, Electrochemical Machining, And Combined Machining (AREA)

Abstract

The invention belongs to the technical field of surface modification, and particularly relates to a preparation method of an anisotropic super-hydrophobic surface of a metal material. The method comprises the steps of firstly adopting linear cutting equipment to pretreat a metal surface, then adopting a laser marking machine to prepare a periodic array structure on the metal surface, and then carrying out chemical modification in a stearic acid solution to obtain an anisotropic super-hydrophobic surface, wherein a contact angle is larger than 150 degrees. The surface has wide application prospect in microfluid equipment.

Description

Preparation method of anisotropic super-hydrophobic surface of metal material
Technical Field
The invention belongs to the technical field of surface modification, and particularly relates to a preparation method of an anisotropic super-hydrophobic surface of a metal material.
Background
Under the inspiration of nature, more and more bionic surfaces are prepared, and the preparation method has important application in the fields of self-cleaning, micro-fluidic, oil-water separation and the like. The bionic surface with anisotropy becomes a research hotspot in the bionic field because of the advantages of the bionic surface in the aspects of water collection, medicine supply and the like. The biological surface has an anisotropic structure, so that the biological surface is endowed with special performance and is beneficial to the adaptation of organisms to the environment. The biological surface generally has a micro-nano structure and an anisotropic structure, so that the fluid has special infiltration, movement and transmission performances on the biological surface. Many grass surfaces have an anisotropic, thorn-like structure. When the liquid drops are condensed on the blade, the liquid drops are not easy to separate from the blade due to the function of the thorn structure. The anisotropic micro-nano structure and its properties can be applied to practical production life, such as self-cleaning coatings, directional transport of liquid droplets, directional microfluidic devices, and the like.
Currently, various researchers have proposed studies for preparing anisotropic superhydrophobic surfaces. Chinese patent 'an anisotropic super-hydrophobic surface of aluminum material and a preparation method thereof', proposes that hard rough materials are used for carrying out directional coarse grinding and fine grinding on the aluminum material, then the aluminum material is soaked in weakly alkaline boiling water, and finally, low surface energy substances are used for modifying, so that the anisotropic super-hydrophobic surface is obtained. The preparation method needs a plurality of working procedures before low surface energy modification, is relatively complex, and meanwhile, the directional coarse grinding or fine grinding can not be parameterized, so that the obtained directional structure is not easy to control.
The anisotropic microstructure has a special wettability. Therefore, the development of a simple, efficient, controllable and low-cost preparation method of the super-hydrophobic surface of the metal material with the wetting anisotropy is imperative.
Disclosure of Invention
The invention provides an anisotropic super-hydrophobic surface of a metal material and a preparation method thereof. The preparation method of the anisotropic super-hydrophobic surface of the metal material comprises the following steps:
(1) wire cutting pretreatment: performing surface cutting on the metal material on a linear cutting device;
the processing parameters of the wire cutting pretreatment are as follows: the voltage is 1-2V, the current is 0-3A, the cutting frequency is 30-45 Hz, the pulse width of the pulse power supply is 32 mu S, and the pulse interval is 8 mu S.
The wire cutting pretreatment adopts a molybdenum wire with the diameter of 0.18mm, the discharge gap is 0.1mm, and the compensation is 0.19 mm.
(2) Ultrasonic cleaning;
the ultrasonic cleaning solution is an alcohol solution, and the ultrasonic time is 30 minutes.
(3) Preparing a rectangular groove periodic array structure by using a laser marking machine;
and constructing a rectangular groove periodic structure on the surface of the metal material by using an infrared nanosecond laser. The partial periodic structure is divided into A and A⊥The rectangular groove structure A is a groove array structure obtained by a laser scanning line by line under the control of a CAD program; rectangular groove structure A⊥Is an array structure obtained by the way that the laser scans column by column, theoretically, a rectangular groove structure A and A⊥The rectangular structures are perpendicular to each other.
Adopting an electrochemical workstation to compare blank samples and groove array structures A and A⊥The corrosion resistance of the rectangular structure shows that the groove array structures A and A⊥The corrosion voltage of the rectangular structure is shifted to the left, the corrosion performance is obviously improved, but the corrosion performance of the A ^ rectangular structure is superior to that of the groove array structure A, and the A ^ rectangular structure has higher corrosion resistance than that of the groove array structure A⊥The wetting property of the rectangular structure is superior to that of the groove array structure A, gradient change of the wetting property is realized, and application of the microfluidic device can be realized.
(4) A stearic acid solution is used for low surface energy modification.
The concentration of stearic acid is 2 wt%, the water bath temperature during modification is 70 ℃, and the soaking time is 2 h.
The metal material anisotropic super-hydrophobic surface prepared by the method has super-hydrophobicity along the direction of the groove array structure A, and the contact angle is 148.2-150.1 degrees. Along the trench array structure A⊥And the contact angle is 155.4-158.9 degrees.
Advantageous effects
(1) The method comprises the steps of utilizing pulse power supply parameters of a regulating and controlling linear cutting device to pretreat the surface of a metal material to obtain a surface microstructure, then obtaining a submicron structure through infrared laser etching, and modifying with low surface energy to obtain the super-hydrophobic surface structure with anisotropy.
(2) The rough structure is obtained by linear cutting pretreatment, and the laser etching shape is controllable.
Drawings
FIG. 1 is a flow chart of an experiment;
FIG. 2 is a schematic view of the flow of water droplets;
FIG. 3 is a photograph of example 1 after a wire cutting pretreatment;
FIG. 4 is a SEM picture and contact angle of the laser-etched substrate of example 1;
FIG. 5 is a graph showing the corrosion-resistant electric polarization of example 1 and a blank.
Detailed Description
The preparation method of the anisotropic super-hydrophobic surface of the metal material comprises the following processing steps:
wire cutting pretreatment: carrying out cutting pretreatment on the metal surface by using linear cutting equipment to process a rough surface structure;
ultrasonic cleaning: soaking the sample in an alcohol solution for ultrasonic cleaning;
preparing a periodic array structure: etching the periodic array on the online cutting surface by using an infrared nanosecond laser etching method to process a surface microstructure;
low surface energy modification: and the surface free energy of the material is reduced by using stearic acid solution for modification.
Example 1
Taking TC4 as an example, the implementation process of the preparation method of the anisotropic superhydrophobic surface of the metal material is described, and the preparation method comprises the following steps:
wire cutting pretreatment: the TC4 material is fixed on a linear cutting device, a molybdenum wire with phi of 0.18mm is adopted to cut along the surface of the material, the cutting path is controlled by a pre-drawn CAD graph, the cutting path is a straight line, the discharge gap Z is 0.1mm, the compensation is 0.19mm, the pulse is a rectangular pulse, the voltage is 1V, the current is 3A, and the frequency is 30 Hz. And after the processing is finished, carrying out ultrasonic cleaning for 30 min.
Preparing a periodic array structure: and (2) preparing a rectangular groove array structure on the surface of TC4 by using an infrared laser etching method, and processing a surface microstructure, wherein the scanning power is 24W, the scanning interval is 100 mu m, and the scanning speed is 50 mm/s.
Low surface energy modification: the processed sample was immersed in a 2 wt% stearic acid solution at a bath temperature of 70 ℃ for 2 hours.
Example 2
Wire cutting pretreatment: the TC4 material is fixed on a linear cutting device, a molybdenum wire with phi of 0.18mm is adopted to cut along the surface of the material, the cutting path is controlled by a pre-drawn CAD graph, the cutting path is a straight line, the discharge gap Z is 0.1mm, the compensation is 0.19mm, the pulse is a rectangular pulse, the voltage is 2V, the current is 2A, and the frequency is 40 Hz. And after the processing is finished, carrying out ultrasonic cleaning for 30 min.
Preparing a periodic array structure: and (2) preparing a rectangular groove array structure on the surface of TC4 by using an infrared laser etching method, and processing a surface microstructure, wherein the scanning power is 24W, the scanning interval is 100 mu m, and the scanning speed is 50 mm/s.
Low surface energy modification: the processed sample was immersed in a 2 wt% stearic acid solution at a bath temperature of 70 ℃ for 2 hours.
Example 3
Wire cutting pretreatment: the TC4 material is fixed on a linear cutting device, a molybdenum wire with phi of 0.18mm is adopted to cut along the surface of the material, the cutting path is controlled by a pre-drawn CAD graph, the cutting path is a straight line, the discharge gap Z is 0.1mm, the compensation is 0.19mm, the pulse is a rectangular pulse, the voltage is 1V, the current is 3A, and the frequency is 45 Hz. And after the processing is finished, carrying out ultrasonic cleaning for 30 min.
Preparing a periodic array structure: and (2) preparing a rectangular groove array structure on the surface of TC4 by using an infrared laser etching method, and processing a surface microstructure, wherein the scanning power is 24W, the scanning interval is 100 mu m, and the scanning speed is 50 mm/s.
Low surface energy modification: the processed sample was immersed in a 2 wt% stearic acid solution at a bath temperature of 70 ℃ for 2 hours.
Comparative example
Taking the TC4 as an example,
ultrasonic cleaning: carrying out ultrasonic cleaning on the sample for 30 min;
preparing a periodic array structure: and (2) preparing a rectangular groove array structure on the surface of TC4 by using an infrared laser etching method, and processing a surface microstructure, wherein the scanning power is 24W, the scanning interval is 100 mu m, and the scanning speed is 50 mm/s.
Low surface energy modification: the processed sample was immersed in a 2 wt% stearic acid solution at a bath temperature of 70 ℃ for 2 hours.
The superhydrophobic surfaces prepared in examples 1-3 and the superhydrophobic surface prepared in the comparative example were subjected to contact angle measurement, and the results are shown in table 1, except that the superhydrophobic surface was blank.
Figure BDA0003415141780000051

Claims (6)

1. A preparation method of a metal material anisotropic super-hydrophobic surface is characterized by comprising the following steps:
(1) wire cutting pretreatment: performing surface cutting on a metal material on a linear cutting device, and roughening the metal surface to prepare a texture structure;
(2) ultrasonic cleaning;
(3) an infrared nanosecond laser is adopted to construct a groove periodic structure on the surface of a metal material, the groove structure is controlled by a CAD program to firstly carry out line-by-line scanning to obtain a parallel groove array structure A, and secondly, the program control is carried out to carry out line-by-line scanning to obtain the groove array structure A which is vertical to the groove array structure A⊥To obtain A⊥Structure;
(4) a stearic acid solution is used for low surface energy modification.
2. The method for preparing the anisotropic superhydrophobic surface of the metal material according to claim 1, wherein the processing parameters of the wire-cutting pretreatment in the step (1) are as follows: the voltage is 1-2V, the current is 0-3A, the cutting frequency is 30-45 Hz, the pulse width of the pulse power supply is 32 mu S, and the pulse interval is 8 mu S.
3. The method for preparing the anisotropic superhydrophobic surface of the metal material as claimed in claim 1, wherein the wire-cutting pretreatment in step (1) is a molybdenum wire with a diameter of 0.18mm, a discharge gap of 0.1mm, and a compensation of 0.19 mm.
4. The method for preparing the anisotropic superhydrophobic surface of the metal material according to claim 1, wherein the ultrasonic cleaning in step (2) is performed in an alcohol solution for 30 minutes.
5. The method for preparing the anisotropic superhydrophobic surface of the metal material according to claim 1, wherein the concentration of stearic acid in the step (4) is 2 wt%, the temperature of the water bath is 70 ℃, and the soaking time is 2 h.
6. The anisotropic superhydrophobic surface of any one of claims 1-5, wherein the contact angle along the trench array structure A is 148.2-150.1 °. Along the trench array structure A⊥And the contact angle is 155.4-158.9 degrees.
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Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102586771A (en) * 2012-02-14 2012-07-18 中南林业科技大学 Metallic aluminum bionic super-hydrophobic surface preparation method
KR20130142740A (en) * 2012-06-20 2013-12-30 포항공과대학교 산학협력단 Surface fabricating method of metal substrate and metal substrate with the surface fabricated by the method
CN103590023A (en) * 2013-10-25 2014-02-19 湖南工业大学 Preparation method of lotus-leaf-like surface structure superhydrophobic copper sheet
CN106733555A (en) * 2017-01-06 2017-05-31 南京航空航天大学 A kind of controllable super hydrophobic surface and its construction method for clashing into drop bounce-back direction
CN106757224A (en) * 2016-12-01 2017-05-31 吉林大学 A kind of preparation method with the anisotropic fine copper super hydrophobic surface of wetting
CN107262916A (en) * 2017-06-20 2017-10-20 长春理工大学 The nanosecond laser rescan preparation method of aluminum alloy surface superhydrophobic microstructure
CN109021826A (en) * 2018-05-15 2018-12-18 天津大学 A kind of method for preparing super-hydrophobic surface based on metal material
CN109047958A (en) * 2018-08-31 2018-12-21 厦门大学 A kind of method that Wire EDM prepares super-hydrophobic metal surface
CN109127331A (en) * 2018-09-28 2019-01-04 江苏理工学院 A kind of method that infrared laser prepares super-hydrophobic zinc alloy surface
CN110653493A (en) * 2019-10-31 2020-01-07 山东大学 Nanosecond laser ablation and chemical thermal decomposition composite preparation method of stainless steel surface super-hydrophobic micro-nano structure
CN110900687A (en) * 2019-12-20 2020-03-24 湖北理工学院 Preparation method of bionic rice leaf surface lattice anisotropic super-hydrophobic surface material
CN112376089A (en) * 2020-10-09 2021-02-19 江苏大学 Preparation method of stainless steel super-hydrophobic surface with infiltration anisotropy

Patent Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102586771A (en) * 2012-02-14 2012-07-18 中南林业科技大学 Metallic aluminum bionic super-hydrophobic surface preparation method
KR20130142740A (en) * 2012-06-20 2013-12-30 포항공과대학교 산학협력단 Surface fabricating method of metal substrate and metal substrate with the surface fabricated by the method
CN103590023A (en) * 2013-10-25 2014-02-19 湖南工业大学 Preparation method of lotus-leaf-like surface structure superhydrophobic copper sheet
CN106757224A (en) * 2016-12-01 2017-05-31 吉林大学 A kind of preparation method with the anisotropic fine copper super hydrophobic surface of wetting
CN106733555A (en) * 2017-01-06 2017-05-31 南京航空航天大学 A kind of controllable super hydrophobic surface and its construction method for clashing into drop bounce-back direction
CN107262916A (en) * 2017-06-20 2017-10-20 长春理工大学 The nanosecond laser rescan preparation method of aluminum alloy surface superhydrophobic microstructure
CN109021826A (en) * 2018-05-15 2018-12-18 天津大学 A kind of method for preparing super-hydrophobic surface based on metal material
CN109047958A (en) * 2018-08-31 2018-12-21 厦门大学 A kind of method that Wire EDM prepares super-hydrophobic metal surface
CN109127331A (en) * 2018-09-28 2019-01-04 江苏理工学院 A kind of method that infrared laser prepares super-hydrophobic zinc alloy surface
CN110653493A (en) * 2019-10-31 2020-01-07 山东大学 Nanosecond laser ablation and chemical thermal decomposition composite preparation method of stainless steel surface super-hydrophobic micro-nano structure
CN110900687A (en) * 2019-12-20 2020-03-24 湖北理工学院 Preparation method of bionic rice leaf surface lattice anisotropic super-hydrophobic surface material
CN112376089A (en) * 2020-10-09 2021-02-19 江苏大学 Preparation method of stainless steel super-hydrophobic surface with infiltration anisotropy

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