CN114150350A - Preparation method of corrosion-resistant and hydrophobic micro-nano part - Google Patents

Preparation method of corrosion-resistant and hydrophobic micro-nano part Download PDF

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CN114150350A
CN114150350A CN202111323519.XA CN202111323519A CN114150350A CN 114150350 A CN114150350 A CN 114150350A CN 202111323519 A CN202111323519 A CN 202111323519A CN 114150350 A CN114150350 A CN 114150350A
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micro
nano
nano part
polishing
corrosion
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CN114150350B (en
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王毅
索文华
刘壮壮
王善飞
梁翔宇
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Beijing University of Technology
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Beijing University of Technology
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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
    • C25D1/00—Electroforming
    • C25D1/003—3D structures, e.g. superposed patterned layers
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
    • C21D1/74—Methods of treatment in inert gas, controlled atmosphere, vacuum or pulverulent material
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D1/00—Electroforming
    • C25D1/006—Nanostructures, e.g. using aluminium anodic oxidation templates [AAO]
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D15/00—Electrolytic or electrophoretic production of coatings containing embedded materials, e.g. particles, whiskers, wires
    • 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
    • C25F—PROCESSES FOR THE ELECTROLYTIC REMOVAL OF MATERIALS FROM OBJECTS; APPARATUS THEREFOR
    • C25F3/00—Electrolytic etching or polishing
    • C25F3/16—Polishing

Abstract

A preparation method of a corrosion-resistant and hydrophobic micro-nano part belongs to the field of micro-forming manufacturing. In the early stage, an electroforming technology is adopted to prepare the graphene-nickel micro-nano part, and then an electrochemical polishing technology is utilized to remove burrs on the surface of the micro-nano part, so that the precision of the micro-nano part is greatly improved; and finally, eliminating internal force of the micro-nano part by adopting a heat treatment technology to obtain the corrosion-resistant and hydrophobic graphene-nickel micro-nano part. The part can effectively prevent the corrosion of acid, alkali and salt, solve the problem of continuous use in harsh environments such as high temperature, high pressure, corrosion and the like, and solve the problems of poor uniformity of a cast layer, light weight and the like.

Description

Preparation method of corrosion-resistant and hydrophobic micro-nano part
Technical Field
The invention belongs to the field of micro-forming manufacturing, and particularly relates to a preparation method of a corrosion-resistant and hydrophobic micro-nano part.
Background
Electroformed nickel has been the dominant material for making metal microfeatures since the advent of UV-LIGA technology. However, nickel parts have not been able to meet the demands of various fields in terms of mechanical properties, corrosion resistance, and the like. Recent research on nano-material composite coatings shows that the mechanical property, the corrosion resistance and the like of the material can be improved by adding well-dispersed nano inert ions into a metal matrix, and therefore, a plurality of potential applications of the composite material in a micro-electro-mechanical system are opened. However, the micro electroforming technology has the problems of poor thickness uniformity of a casting layer, long manufacturing period, large residual internal stress, defects in the casting layer, poor performance and the like, and the application and the development of the electroforming technology are seriously restricted. Therefore, it is necessary to research a metal-based nanocomposite micro-nano part having high performance and good uniformity of a cast layer.
Disclosure of Invention
Aiming at the defects, the invention provides a preparation method of a corrosion-resistant and hydrophobic micro-nano part, which solves the problems of poor thickness uniformity, large residual internal stress, poor performance and the like of the micro-nano part. The preparation method can obtain the hydrophobic graphene-nickel micro-nano part with the contact angle with water of 137-152 degrees, and meanwhile, the part has the characteristics of strong corrosion resistance, light weight and the like.
In order to achieve the purpose, the experimental scheme of the invention is as follows:
the disclosure provides a preparation method of a corrosion-resistant and hydrophobic micro-nano part. In the early stage, an electroforming technology is adopted to prepare the graphene-nickel micro-nano part, and then an electrochemical polishing technology is utilized to remove burrs on the surface of the micro-nano part, so that the precision of the micro-nano part is greatly improved; and finally, eliminating internal force of the micro-nano part by adopting a heat treatment technology to obtain the corrosion-resistant and hydrophobic graphene-nickel micro-nano part.
The preparation method of the corrosion-resistant and hydrophobic micro-nano part comprises the following steps:
s1, electroforming: preparing a micro-nano part rubber mold cavity by adopting SU-8 etching, configuring electroforming liquid, and performing electrodeposition on the micro-nano part rubber mold cavity by adopting the electroforming liquid until the micro-nano part rubber mold is fully cast to obtain an electroformed micro-nano part;
s2, electrochemical polishing: preparing polishing solution according to a proportion, and polishing the electroforming micro-nano part according to polishing parameters;
s3, heat treatment: by usingAt Ar + 4% volH2Under the protection of mixed atmosphere, placing the micro-nano part sample polished by S2 in a tubular furnace with the preset temperature range of 150-300 ℃, preserving heat for 2h, and then cooling along with the furnace to obtain the corrosion-resistant and hydrophobic composite micro-nano part;
the electroforming solution in S1 has the following components: graphene dispersion liquid and nickel sulfamate solution.
The preparation method of the graphene dispersion liquid comprises the following steps: uniformly mixing 1 g/L-2 g/L sodium dodecyl sulfate, 0.1 g/L-0.2 g/L hexadecyl trimethyl ammonium bromide, 0.1g/L single-layer graphene oxide and the balance of deionized water to obtain an aqueous solution, adding ammonia water to adjust the pH to 9-10, adding 1mL hydrazine hydrate serving as a reducing agent into every 50mL of the aqueous solution, placing the aqueous solution in an ultrasonic machine for ultrasonic treatment for 3 hours until the graphene is uniformly dispersed, and finally performing hydrothermal treatment at 80 ℃ for 1 hour to obtain a graphene dispersion liquid;
the preparation method of the nickel sulfamate solution comprises the following steps: preparing 350 g/L-400 g/L nickel sulfamate, 10 g/L-15 g/L nickel chloride, 40 g/L-50 g/L boric acid, 0.1 g/L-0.2 g/L sodium dodecyl sulfate, 2 g/L-3 g/L citric acid monohydrate, 1 g/L-2 g/L saccharin and the balance of deionized water in sequence at the temperature of 70 ℃ while stirring, filtering the obtained nickel sulfamate solution after dissolution, and adjusting the pH value to 3.8-4.0;
and finally, mixing the graphene dispersion liquid and the nickel sulfamate solution in a ratio of 1: 5, mixing ultrasonic waves for 1h to obtain electroforming solution;
the thickness of the single-layer graphene oxide nanosheet is 0.8-1.2 nm, and the diameter of the nanosheet is 0.5-5 microns;
the electrodeposition forming conditions in S1 are: the temperature is 40-50 ℃, and the current density is 5-8A/dm2The distance between the two electrodes is 3-4 cm, the magnetic stirring speed is 200-800 r/min, and the electroforming time is 40-44 h;
in the electrodeposition process, the graphene oxide is subjected to a reduction reaction on the surface of a cathode to form hydrophobic graphene;
the preparation method of the polishing solution in S2 comprises the following steps: preparing a mixed acid solution from 98% concentrated sulfuric acid and 85% concentrated phosphoric acid, mixing glycerol, thiourea, ammonium citrate, citric acid monohydrate and deionized water, and adding the mixture into the mixed acid solution, wherein the 98% concentrated sulfuric acid, the 85% concentrated phosphoric acid, the glycerol, the thiourea, the ammonium citrate, the citric acid monohydrate and the deionized water are respectively 24.68 wt.%, 67.49 wt.%, 3.24 wt.%, 1.00 wt.%, 0.1 wt.%, 1.49 wt.% and 2 wt.% according to the mass percentage, stirring for 5 hours at 60-70 ℃, then closing the heating, stirring and cooling to room temperature;
the electrochemical polishing parameters are as follows: polishing voltage is 16-18V, polishing temperature is 30-50 ℃, polishing polar distance is 2-4 cm, and polishing time is 2-4 min;
s3 heat treatment in Ar + 4% volH2Under the protection of mixed atmosphere, placing the polished micro-nano part sample in a tubular furnace with the preset temperature of 150-300 ℃, heating, preserving heat for 2 hours after reaching the preset temperature, cooling to room temperature along with the furnace, and removing the internal stress of the micro-nano part.
And analyzing the corrosion resistance of the micro-nano part before and after heat treatment by adopting a solution of 3.5 wt.% NaCl seawater.
The invention has the beneficial effects that:
(1) the hydrophobic angle of the electroformed micro-nano part is increased from 96-99 ℃ before electrochemical polishing to 105-107 ℃ after electrochemical polishing, further increased to 137-152 ℃ after heat treatment, and is soaked in acetone and absolute ethyl alcohol for a long time (more than 96 hours), and after drying, the hydrophobicity is still maintained;
(2) according to the invention, by skillfully utilizing the characteristics of large specific surface area, good hydrophobicity, good hardness and wear resistance of graphene and the nano structure formed in the composite electrodeposition process, the graphene can be uniformly distributed on the electrodeposition surface in a flaky structure, and most of the graphene is basically distributed at the crystal boundary of nickel crystal grains, so that the invasion of corrosive ions is successfully hindered. The hydrophobicity can be realized without subsequent modification and hydrophobization treatment;
(3) by applying an electrochemical polishing and heat treatment method, the surface uniformity and the corrosion resistance of the micro-nano part are improved, and the corrosion resistance is improved from 38.4% to 53.2%;
(4) the preparation method of the micro-nano part provided by the invention has the advantages of simple process, low production cost, no pollution, uniform formed surface, light weight, good performance, suitability for large-scale production and good practical prospect.
Drawings
Fig. 1 is an SEM image of a hydrophobic graphene-nickel micro-nano part prepared according to an embodiment of the present invention before and after polishing;
FIG. 2 is a contact angle diagram of a water drop before and after polishing of a hydrophobic graphene-nickel micro-nano part prepared by the embodiment of the invention;
FIG. 3 is a polarization curve diagram of the hydrophobic graphene-nickel micro-nano part prepared in the embodiment of the invention in a 3.5 wt.% NaCl solution before and after electrochemical polishing;
fig. 4 is a contact angle of the hydrophobic graphene-nickel micro-nano part prepared in the embodiment of the invention before and after heat treatment;
fig. 5 is a polarization curve diagram of the hydrophobic graphene-nickel micro-nano part prepared in the embodiment of the invention in a 3.5 wt.% NaCl solution before and after heat treatment.
Detailed Description
It is to be understood that the following detailed description is exemplary and is intended to provide further explanation of the invention as claimed. All technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
The surface of an electroforming layer is made of graphene and a nickel-based composite material, nickel is used as a main material, graphene nanosheets are distributed in an electrodeposited nickel matrix in a lamellar mode, and most of the graphene in a lamellar mode are basically distributed among nickel crystal grains. Due to the structural characteristics and the low surface energy of the graphene, the obtained micro-nano part has hydrophobicity.
Example 1
The embodiment provides a preparation method of an anti-corrosion and hydrophobic micro-nano part, which comprises the steps of adopting an electroforming technology to fully cast a rubber mold cavity with the thickness of 400-600 mu m prepared by UV-LIGA to obtain an electroformed graphene-nickel micro-nano part, then utilizing an electrochemical polishing technology to remove burrs on the surface of the micro-nano part, and greatly improving the surface precision of the micro-nano part; and finally, eliminating internal force of the micro-nano part by adopting a heat treatment technology to obtain the corrosion-resistant and hydrophobic graphene-nickel micro-nano part.
The embodiment provides a rubber mold, which is characterized in that a photoresist SU-8 is adopted to etch and prepare a rubber mold with a microstructure adhered to a conductive electroplated gold silicon sheet and used as an electroformed micro part, wherein the thickness of the rubber mold is 400-600 mu m;
the preparation method of the corrosion-resistant and hydrophobic micro-nano part provided by the embodiment comprises the following steps:
s1, electroforming: preparing electroforming liquid according to a proportion, and performing electrodeposition on a rubber mold prepared by SU-8 etching by using the electroforming liquid until a rubber mold cavity is full of the electroforming liquid, so as to obtain an electroformed micro-nano part;
s2, electrochemical polishing: preparing polishing solution according to a proportion, and polishing the electroforming micro-nano part according to polishing parameters;
s3, heat treatment: adopts the method that the volume H is Ar +4 percent2And under the protection of mixed atmosphere, placing the polished micro-nano part sample in a tubular furnace with the preset temperature of 150 ℃, preserving heat for 2h, and then cooling to room temperature along with the furnace to obtain the composite micro-nano part.
S4, adopting a 3.5 wt.% NaCl seawater solution to analyze the corrosion resistance of the micro-nano part before and after heat treatment.
The graphene-nickel composite casting solution for electroforming comprises the following components: 350g/L of nickel sulfamate, 10g/L of nickel chloride, 40g/L of boric acid, 0.1g/L of sodium dodecyl sulfate, 2g/L of citric acid monohydrate, 1g/L of saccharin, 0.1g/L of graphene oxide and a graphene dispersing agent, wherein the dispersing agent comprises 1g/L of sodium dodecyl sulfate and 0.1g/L of hexadecyl trimethyl ammonium bromide;
the preparation method provided by the embodiment further comprises the following steps of carrying out electrochemical polishing post-treatment on the surface of the micro-nano part: the polishing solution is 500mL, 98% concentrated sulfuric acid and 85% concentrated phosphoric acid are prepared into a mixed acid solution, then glycerin, thiourea, ammonium citrate, citric acid monohydrate and deionized water are mixed and added into the mixed acid solution, the mass percentages are 24.68 wt.%, 67.49 wt.%, 3.24 wt.%, 1.00 wt.%, 0.1 wt.%, 1.49 wt.% and 2 wt.% respectively, the mixture is stirred for 5 hours at the temperature of 60-70 ℃, then the heating is closed, and the mixture is stirred and cooled to the room temperature;
in this example, the electroforming was carried out using a SU-8 etched plastic mold as a cathode and a pure nickel plate as an anodeThe area ratio of the cathode to the anode is 1: 3, setting the electroforming temperature to be 50 ℃ and the current density to be 7A/dm2The distance between the two electrodes is 3cm, the magnetic stirring speed is 200r/min, and the electroforming time is 40-44 h. In the process, the electrodeposition liquid is kept stirring all the time, after the mold cavity is full, the rubber mold is taken down, cleaned by acetone and absolute ethyl alcohol for 30min and then put into an oven for drying and stripping;
in the embodiment, the electrochemical polishing is performed by taking a graphene-nickel micro-nano part as an anode and a pure lead plate as a cathode, wherein the area ratio of the anode to the cathode is 8: 1, setting a polishing voltage of 16V, a polishing temperature of 40 ℃, a polishing polar distance of 4cm and a polishing time of 3min for electrochemical polishing. The graphene-nickel micro-nano part with a smooth surface and a smooth mirror surface is obtained through the embodiment, the surface roughness of the graphene-nickel micro-nano part is reduced to 0.088 mu m from 3.589 mu m, the amplitude reduction ratio reaches 97.5%, and the use requirement of the micro-nano part Ra is less than 0.8 mu m is met;
the heat treatment process is carried out in N2+4％volH2Under the protection of mixed atmosphere, placing the polished micro-nano part sample in a tube furnace, and filling N into the tube furnace2+4％volH2And preventing the oxidation of the parts, heating the parts in a tube furnace at a heating rate of 5 ℃/min, keeping the temperature for 2h when the parts are heated to 150 ℃, and then cooling the parts to room temperature along with the furnace at a cooling rate of 5 ℃/min to eliminate the internal stress of the micro-nano parts.
Example 2
The embodiment provides a preparation method of an anti-corrosion and hydrophobic micro-nano part, which comprises the steps of adopting an electroforming technology to fully cast a rubber mold cavity with the thickness of 400-600 mu m prepared by UV-LIGA to obtain an electroformed graphene-nickel micro-nano part, then utilizing an electrochemical polishing technology to remove burrs on the surface of the micro-nano part, and greatly improving the surface precision of the micro-nano part; and finally, eliminating internal force of the micro-nano part by adopting a heat treatment technology to obtain the corrosion-resistant and hydrophobic graphene-nickel micro-nano part.
The embodiment provides a rubber mold, which is characterized in that a photoresist SU-8 is adopted to etch and prepare a rubber mold with a microstructure adhered to a conductive electroplated gold silicon sheet and used as an electroformed micro part, wherein the thickness of the rubber mold is 400-600 mu m;
the preparation method of the corrosion-resistant and hydrophobic micro-nano part provided by the embodiment comprises the following steps:
s1, electroforming: preparing electroforming liquid according to a proportion, and performing electrodeposition on a rubber mold prepared by SU-8 etching by using the electroforming liquid until a rubber mold cavity is full of the electroforming liquid, so as to obtain an electroformed micro-nano part;
s2, electrochemical polishing: preparing polishing solution according to a proportion, and polishing the electroforming micro-nano part according to polishing parameters;
s3, heat treatment: adopts the method that the volume H is Ar +4 percent2And under the protection of mixed atmosphere, placing the polished micro-nano part sample in a tubular furnace with the preset temperature of 200 ℃, preserving heat for 2h, and then cooling to room temperature along with the furnace to obtain the composite micro-nano part.
S4, adopting a 3.5 wt.% NaCl seawater solution to analyze the corrosion resistance of the micro-nano part before and after heat treatment.
The graphene-nickel composite casting solution for electroforming comprises the following components: 350g/L of nickel sulfamate, 10g/L of nickel chloride, 40g/L of boric acid, 0.1g/L of sodium dodecyl sulfate, 2g/L of citric acid monohydrate, 1g/L of saccharin, 0.1g/L of graphene oxide and a graphene dispersing agent, wherein the dispersing agent comprises 1g/L of sodium dodecyl sulfate and 0.1g/L of hexadecyl trimethyl ammonium bromide;
the preparation method provided by the embodiment further comprises the following steps of carrying out electrochemical polishing post-treatment on the surface of the micro-nano part: the polishing solution is 500mL, 98% concentrated sulfuric acid and 85% concentrated phosphoric acid are prepared into a mixed acid solution, then glycerin, thiourea, ammonium citrate, citric acid monohydrate and deionized water are mixed and added into the mixed acid solution, the mass percentages are 24.68 wt.%, 67.49 wt.%, 3.24 wt.%, 1.00 wt.%, 0.1 wt.%, 1.49 wt.% and 2 wt.% respectively, the mixture is stirred for 5 hours at the temperature of 60-70 ℃, then the heating is closed, and the mixture is stirred and cooled to the room temperature;
in the electroforming process of the embodiment, an SU-8 etched rubber mold is used as a cathode, a pure nickel plate is used as an anode, and the area ratio of the cathode to the anode is 1: 3, setting the electroforming temperature to be 50 ℃ and the current density to be 7A/dm2The distance between the two electrodes is 3cm, the magnetic stirring speed is 200r/min, and the electroforming time is 40-44 h. In the process, the electrodeposition solution is kept stirring all the time, after the mold cavity is full, the rubber mold is taken down, cleaned by acetone and absolute ethyl alcohol for 30min and then placedDrying and stripping in a drying oven;
in the embodiment, the electrochemical polishing is performed by taking a graphene-nickel micro-nano part as an anode and a pure lead plate as a cathode, wherein the area ratio of the anode to the cathode is 8: 1, setting a polishing voltage of 16V, a polishing temperature of 40 ℃, a polishing polar distance of 4cm and a polishing time of 3min for electrochemical polishing. The graphene-nickel micro-nano part with a smooth surface and a smooth mirror surface is obtained through the embodiment, the surface roughness of the graphene-nickel micro-nano part is reduced to 0.088 mu m from 3.589 mu m, the amplitude reduction ratio reaches 97.5%, and the use requirement of the micro-nano part Ra is less than 0.8 mu m is met;
the heat treatment process is carried out in N2+4％volH2Under the protection of mixed atmosphere, placing the polished micro-nano part sample in a tube furnace, and filling N into the tube furnace2+4％volH2And preventing the oxidation of the parts, heating the parts in a tube furnace at a heating rate of 5 ℃/min, keeping the temperature for 2h when the parts are heated to 200 ℃, and then cooling the parts to room temperature along with the furnace at a cooling rate of 5 ℃/min to eliminate the internal stress of the micro-nano parts.
Example 3
The embodiment provides a preparation method of an anti-corrosion and hydrophobic micro-nano part, which comprises the steps of adopting an electroforming technology to fully cast a rubber mold cavity with the thickness of 400-600 mu m prepared by UV-LIGA to obtain an electroformed graphene-nickel micro-nano part, then utilizing an electrochemical polishing technology to remove burrs on the surface of the micro-nano part, and greatly improving the surface precision of the micro-nano part; and finally, eliminating internal force of the micro-nano part by adopting a heat treatment technology to obtain the corrosion-resistant and hydrophobic graphene-nickel micro-nano part.
The embodiment provides a rubber mold, which is characterized in that a photoresist SU-8 is adopted to etch and prepare a rubber mold with a microstructure adhered to a conductive electroplated gold silicon sheet and used as an electroformed micro part, wherein the thickness of the rubber mold is 400-600 mu m;
the preparation method of the corrosion-resistant and hydrophobic micro-nano part provided by the embodiment comprises the following steps:
s1, electroforming: preparing electroforming liquid according to a proportion, and performing electrodeposition on a rubber mold prepared by SU-8 etching by using the electroforming liquid until a rubber mold cavity is full of the electroforming liquid, so as to obtain an electroformed micro-nano part;
s2, electrochemical polishing: preparing polishing solution according to a proportion, and polishing the electroforming micro-nano part according to polishing parameters;
s3, heat treatment: adopts the method that the volume H is Ar +4 percent2And under the protection of mixed atmosphere, placing the polished micro-nano part sample in a tubular furnace with the preset temperature of 250 ℃, preserving heat for 2h, and then cooling to room temperature along with the furnace to obtain the composite micro-nano part.
S4, adopting a 3.5 wt.% NaCl seawater solution to analyze the corrosion resistance of the micro-nano part before and after heat treatment.
The graphene-nickel composite casting solution for electroforming comprises the following components: 350g/L of nickel sulfamate, 10g/L of nickel chloride, 40g/L of boric acid, 0.1g/L of sodium dodecyl sulfate, 2g/L of citric acid monohydrate, 1g/L of saccharin, 0.1g/L of graphene oxide and a graphene dispersing agent, wherein the dispersing agent comprises 1g/L of sodium dodecyl sulfate and 0.1g/L of hexadecyl trimethyl ammonium bromide;
the preparation method provided by the embodiment further comprises the following steps of carrying out electrochemical polishing post-treatment on the surface of the micro-nano part: the polishing solution is 500mL, 98% concentrated sulfuric acid and 85% concentrated phosphoric acid are prepared into a mixed acid solution, then glycerin, thiourea, ammonium citrate, citric acid monohydrate and deionized water are mixed and added into the mixed acid solution, the mass percentages are 24.68 wt.%, 67.49 wt.%, 3.24 wt.%, 1.00 wt.%, 0.1 wt.%, 1.49 wt.% and 2 wt.% respectively, the mixture is stirred for 5 hours at the temperature of 60-70 ℃, then the heating is closed, and the mixture is stirred and cooled to the room temperature;
in the electroforming process of the embodiment, an SU-8 etched rubber mold is used as a cathode, a pure nickel plate is used as an anode, and the area ratio of the cathode to the anode is 1: 3, setting the electroforming temperature to be 50 ℃ and the current density to be 7A/dm2The distance between the two electrodes is 3cm, the magnetic stirring speed is 200r/min, and the electroforming time is 40-44 h. In the process, the electrodeposition liquid is kept stirring all the time, after the mold cavity is full, the rubber mold is taken down, cleaned by acetone and absolute ethyl alcohol for 30min and then put into an oven for drying and stripping;
in the embodiment, the electrochemical polishing is performed by taking a graphene-nickel micro-nano part as an anode and a pure lead plate as a cathode, wherein the area ratio of the anode to the cathode is 8: 1, setting a polishing voltage of 16V, a polishing temperature of 40 ℃, a polishing polar distance of 4cm and a polishing time of 3min for electrochemical polishing. The graphene-nickel micro-nano part with a smooth surface and a smooth mirror surface is obtained through the embodiment, the surface roughness of the graphene-nickel micro-nano part is reduced to 0.088 mu m from 3.589 mu m, the amplitude reduction ratio reaches 97.5%, and the use requirement of the micro-nano part Ra is less than 0.8 mu m is met;
the heat treatment process is carried out in N2+4％volH2Under the protection of mixed atmosphere, placing the polished micro-nano part sample in a tube furnace, and filling N into the tube furnace2+4％volH2And preventing the oxidation of the parts, heating the parts in a tube furnace at a heating rate of 5 ℃/min, keeping the temperature for 2h when the parts are heated to 250 ℃, and then cooling the parts to room temperature along with the furnace at a cooling rate of 5 ℃/min to eliminate the internal stress of the micro-nano parts.
Example 4
The embodiment provides a preparation method of an anti-corrosion and hydrophobic micro-nano part, which comprises the steps of adopting an electroforming technology to fully cast a rubber mold cavity with the thickness of 400-600 mu m prepared by UV-LIGA to obtain an electroformed graphene-nickel micro-nano part, then utilizing an electrochemical polishing technology to remove burrs on the surface of the micro-nano part, and greatly improving the surface precision of the micro-nano part; and finally, eliminating internal force of the micro-nano part by adopting a heat treatment technology to obtain the corrosion-resistant and hydrophobic graphene-nickel micro-nano part.
The embodiment provides a rubber mold, which is characterized in that a photoresist SU-8 is adopted to etch and prepare a rubber mold with a microstructure adhered to a conductive electroplated gold silicon sheet and used as an electroformed micro part, wherein the thickness of the rubber mold is 400-600 mu m;
the preparation method of the corrosion-resistant and hydrophobic micro-nano part provided by the embodiment comprises the following steps:
s1, electroforming: preparing electroforming liquid according to a proportion, and performing electrodeposition on a rubber mold prepared by SU-8 etching by using the electroforming liquid until a rubber mold cavity is full of the electroforming liquid, so as to obtain an electroformed micro-nano part;
s2, electrochemical polishing: preparing polishing solution according to a proportion, and polishing the electroforming micro-nano part according to polishing parameters;
s3, heat treatment: adopts the method that the volume H is Ar +4 percent2And under the protection of mixed atmosphere, placing the polished micro-nano part sample in a tubular furnace with the preset temperature of 300 ℃, preserving heat for 2h, and then cooling to room temperature along with the furnace to obtain the composite micro-nano part.
S4, adopting a 3.5 wt.% NaCl seawater solution to analyze the corrosion resistance of the micro-nano part before and after heat treatment.
The graphene-nickel composite casting solution for electroforming comprises the following components: 350g/L of nickel sulfamate, 10g/L of nickel chloride, 40g/L of boric acid, 0.1g/L of sodium dodecyl sulfate, 2g/L of citric acid monohydrate, 1g/L of saccharin, 0.1g/L of graphene oxide and 0.0004M of graphene dispersing agent, wherein the dispersing agent comprises 1g/L of sodium dodecyl sulfate and 0.1g/L of hexadecyl trimethyl ammonium bromide;
the preparation method provided by the embodiment further comprises the following steps of carrying out electrochemical polishing post-treatment on the surface of the micro-nano part: the polishing solution is 500mL, 98% concentrated sulfuric acid and 85% concentrated phosphoric acid are prepared into a mixed acid solution, then glycerin, thiourea, ammonium citrate, citric acid monohydrate and deionized water are mixed and added into the mixed acid solution, the mass percentages are 24.68 wt.%, 67.49 wt.%, 3.24 wt.%, 1.00 wt.%, 0.1 wt.%, 1.49 wt.% and 2 wt.% respectively, the mixture is stirred for 5 hours at the temperature of 60-70 ℃, then the heating is closed, and the mixture is stirred and cooled to the room temperature;
in the electroforming process of the embodiment, an SU-8 etched rubber mold is used as a cathode, a pure nickel plate is used as an anode, and the area ratio of the cathode to the anode is 1: 3, setting the electroforming temperature to be 50 ℃ and the current density to be 7A/dm2The distance between the two electrodes is 3cm, the magnetic stirring speed is 200r/min, and the electroforming time is 40-44 h. In the process, the electrodeposition liquid is kept stirring all the time, after the mold cavity is full, the rubber mold is taken down, cleaned by acetone and absolute ethyl alcohol for 30min and then put into an oven for drying and stripping;
in the embodiment, the electrochemical polishing is performed by taking a graphene-nickel micro-nano part as an anode and a pure lead plate as a cathode, wherein the area ratio of the anode to the cathode is 8: 1, setting a polishing voltage of 16V, a polishing temperature of 40 ℃, a polishing polar distance of 4cm and a polishing time of 3min for electrochemical polishing. The graphene-nickel micro-nano part with a smooth surface and a smooth mirror surface is obtained through the embodiment, the surface roughness of the graphene-nickel micro-nano part is reduced to 0.088 mu m from 3.589 mu m, the amplitude reduction ratio reaches 97.5%, and the use requirement of the micro-nano part Ra is less than 0.8 mu m is met;
the heat treatment process is carried out in N2+4％volH2Placing the polished micro-nano part sample in a tube type under the protection of mixed atmosphereIn-furnace, tube furnace is filled with N2+4％volH2And preventing the oxidation of the parts, heating the parts in a tube furnace at a heating rate of 5 ℃/min, keeping the temperature for 2h when the parts are heated to 300 ℃, and then cooling the parts to room temperature along with the furnace at a cooling rate of 5 ℃/min to eliminate the internal stress of the micro-nano parts.
According to the invention, nickel is used as a main material of the electrodeposition layer, the flaky graphene nanosheets are uniformly distributed in the electrodeposition nickel matrix, the size of nickel crystal grains is reduced due to the addition of the graphene nanosheets, the dissociation of corrosive ions is hindered due to the addition of the graphene, the corrosion process is reduced, and the corrosion of the composite micro-nano part is avoided on the basis of improving the mechanical property. Through detection, the graphene content before and after the electrochemical polishing and heat treatment process is respectively 3.12 wt.% and 3.10 wt.%, and the graphene content is not changed.
The surface roughness and the surface compactness uniformity of the micro-nano part before and after electrochemical polishing can be seen from figure 1. Comparing and analyzing the hydrophobicity and the corrosion resistance of the graphene-nickel micro-nano part before and after polishing through a graph 2 and a graph 3; fig. 4 and 5 respectively analyze the hydrophobicity and the corrosion resistance of the graphene-nickel micro-nano part before and after heat treatment. The corrosion resistance of the micro-nano part before and after heat treatment is analyzed by adopting a solution of 3.5 wt.% NaCl seawater, a constant potential rectifier CHI60E of Shanghai Chenghua instruments company is adopted in electrochemical test, a working electrode is a micro-nano part to be detected, an auxiliary electrode is a Pt foil, and a reference electrode is an Ag/AgCl electrode. The corrosion resistance polarization curve is tested for 120min at normal temperature.

Claims (6)

1. A preparation method of a corrosion-resistant and hydrophobic micro-nano part is characterized by comprising the following steps:
s1, electroforming: preparing a micro-nano part rubber mold cavity by adopting SU-8 etching, configuring electroforming liquid, and performing electrodeposition on the micro-nano part rubber mold cavity by adopting the electroforming liquid until the micro-nano part rubber mold is fully cast to obtain an electroformed micro-nano part;
s2, electrochemical polishing: preparing polishing solution according to a proportion, and polishing the electroforming micro-nano part according to polishing parameters;
s3, heat treatment: adopts the method that the volume H is Ar +4 percent2Throwing S2 under the protection of mixed atmospherePlacing the polished micro-nano part sample in a tubular furnace with the preset temperature range of 150-;
the electroforming solution in S1 has the following components: graphene dispersion liquid and nickel sulfamate solution.
2. The preparation method of the corrosion-resistant and hydrophobic micro-nano part according to claim 1, wherein the graphene dispersion liquid is prepared by a method comprising the following steps: uniformly mixing 1 g/L-2 g/L sodium dodecyl sulfate, 0.1 g/L-0.2 g/L hexadecyl trimethyl ammonium bromide, 0.1g/L single-layer graphene oxide and the balance of deionized water to obtain an aqueous solution, adding ammonia water to adjust the pH to 9-10, adding 1mL hydrazine hydrate serving as a reducing agent into every 50mL of the aqueous solution, placing the aqueous solution in an ultrasonic machine for ultrasonic treatment for 3 hours until the graphene is uniformly dispersed, and finally performing hydrothermal treatment at 80 ℃ for 1 hour to obtain a graphene dispersion liquid;
the preparation method of the nickel sulfamate solution comprises the following steps: preparing 350 g/L-400 g/L nickel sulfamate, 10 g/L-15 g/L nickel chloride, 40 g/L-50 g/L boric acid, 0.1 g/L-0.2 g/L sodium dodecyl sulfate, 2 g/L-3 g/L citric acid monohydrate, 1 g/L-2 g/L saccharin and the balance of deionized water in sequence at the temperature of 70 ℃ while stirring, filtering the obtained nickel sulfamate solution after dissolution, and adjusting the pH value to 3.8-4.0;
and finally, mixing the graphene dispersion liquid and the nickel sulfamate solution in a ratio of 1: 5, mixing ultrasonic waves for 1h to obtain electroforming solution;
the thickness of the single-layer graphene oxide nanosheet is 0.8-1.2 nm, and the diameter of the nanosheet is 0.5-5 microns;
3. the preparation method of the corrosion-resistant and hydrophobic micro-nano part according to claim 1, wherein the electrodeposition forming conditions in S1 are as follows: the temperature is 40-50 ℃, and the current density is 5-8A/dm2The distance between the two electrodes is 3-4 cm, the magnetic stirring speed is 200-800 r/min, and the electroforming time is 40-44 h;
and in the electrodeposition process, the graphene oxide is subjected to a reduction reaction on the surface of the cathode to form hydrophobic graphene.
4. The preparation method of the corrosion-resistant and hydrophobic micro-nano part according to claim 1, wherein the preparation method of the polishing solution in S2 comprises the following steps: preparing a mixed acid solution from 98% concentrated sulfuric acid and 85% concentrated phosphoric acid, mixing glycerol, thiourea, ammonium citrate, citric acid monohydrate and deionized water, and adding the mixture into the mixed acid solution, wherein the 98% concentrated sulfuric acid, the 85% concentrated phosphoric acid, the glycerol, the thiourea, the ammonium citrate, the citric acid monohydrate and the deionized water are respectively 24.68 wt.%, 67.49 wt.%, 3.24 wt.%, 1.00 wt.%, 0.1 wt.%, 1.49 wt.% and 2 wt.% according to the mass percentage, stirring for 5 hours at 60-70 ℃, then closing and heating, stirring and cooling to room temperature.
5. The preparation method of the corrosion-resistant and hydrophobic micro-nano part according to claim 1, wherein the electrochemical polishing parameters are as follows: the polishing voltage is 16-18V, the polishing temperature is 30-50 ℃, the polishing polar distance is 2-4 cm, and the polishing time is 2-4 min.
6. The method for preparing a corrosion-resistant hydrophobic micro-nano part according to claim 1, wherein the heat treatment in S3 is performed in Ar + 4% volH2Under the protection of mixed atmosphere, placing the polished micro-nano part sample in a tubular furnace with the preset temperature of 150-300 ℃, heating, preserving heat for 2 hours after reaching the preset temperature, cooling to room temperature along with the furnace, and removing the internal stress of the micro-nano part.
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