CN113549991B - Super-hydrophobic nano-structure high-entropy alloy and preparation method thereof - Google Patents
Super-hydrophobic nano-structure high-entropy alloy and preparation method thereof Download PDFInfo
- Publication number
- CN113549991B CN113549991B CN202110959707.5A CN202110959707A CN113549991B CN 113549991 B CN113549991 B CN 113549991B CN 202110959707 A CN202110959707 A CN 202110959707A CN 113549991 B CN113549991 B CN 113549991B
- Authority
- CN
- China
- Prior art keywords
- entropy alloy
- metal sheet
- solution
- alloy metal
- alcocrfeni
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- 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
- C25F3/02—Etching
Abstract
The invention relates to a super-hydrophobic nano-structure high-entropy alloy and a preparation method thereof. The lotus leaf nanostructure prepared by the invention ensures that the water contact angle of the AlCoCrFeNi high-entropy alloy sample is more than 150 degrees, has simple operation and economic feasibility, can obviously improve the corrosion resistance, and can be widely applied to the special application fields of aviation, aerospace, national defense war industry and the like.
Description
Technical Field
The invention relates to a super-hydrophobic nano-structure high-entropy alloy and a preparation method thereof, in particular to a nano-structure capable of enabling the high-entropy alloy to have super-hydrophobic characteristics, and belongs to the field of nano-functional materials.
Background
In recent years, the high-entropy alloy is one of hot spots of research and application in the field of metal materials, breaks through the design concept of the traditional alloy, and consists of multiple elements in equal atomic ratio or near equal atomic ratio. Compared with the traditional alloy, the high-entropy alloy has extremely high specific strength, and simultaneously has the characteristics of better fracture resistance, tensile strength, corrosion resistance, oxidation resistance and the like, and is a novel metal structure material with extremely large development potential.
The AlCoCrFeNi high-entropy alloy has very large mixed entropy, and simultaneously keeps a single solid solution structure. The unique property ensures that the steel plate has the characteristics of high strength and high plasticity, and has better fracture toughness, fatigue resistance and creep resistance, so that the steel plate has wide attention in industrial application, particularly in the special application fields of aviation, aerospace, national defense, military industry and the like. However, metal materials used in these applications are often subjected to extreme application conditions such as high temperature, high humidity and acidic environments, thereby increasing the damage thereto from corrosion. Facing this challenge, researchers have made extensive work on improving the interaction between metals and aqueous solutions, where increasing the hydrophobicity of the metal surface is an effective approach. Therefore, the improvement of the hydrophobicity of the surface of the AlCoCrFeNi high-entropy alloy is the key for improving the corrosion resistance effect of the AlCoCrFeNi high-entropy alloy.
Disclosure of Invention
In order to effectively solve the problems, the invention provides a nano structure on the surface of the AlCoCrFeNi high-entropy alloy, and can effectively improve the hydrophobicity of the AlCoCrFeNi high-entropy alloy.
The invention adopts the following technical scheme:
a preparation method of a super-hydrophobic nano-structure high-entropy alloy is characterized in that an AlCoCrFeNi high-entropy alloy sample is soaked in a surfactant solution, cleaned and blown to be dry, then placed in an etching agent solution, and the nano-structure is prepared by an electrochemical dealloying method.
Specifically, the method comprises the following steps:
s1, dissolving a certain amount of surfactant in deionized water at room temperature to prepare AlCoCrFeNi high-entropy alloy surfactant solution.
The surfactant in the AlCoCrFeNi high-entropy alloy surfactant solution is one or a mixture of trinitrophenol, trinitrophenol sodium, m-nitrophenol, p-nitrophenol and 5-nitro-1, 2, 4-triazole-5-ketone in any proportion, and the mass ratio of the surfactant to deionized water is 1: 10 to 100.
S2, cutting the AlCoCrFeNi high-entropy alloy cast ingot into high-entropy alloy metal sheets with uniform size by using a linear cutting technology, and embedding the high-entropy alloy metal sheets of the connecting wires into epoxy resin by using a cold embedding technology; and sequentially grinding and polishing the surface of the high-entropy alloy metal sheet by using 100-2000 # abrasive paper, and sequentially ultrasonically cleaning the surface of the high-entropy alloy metal sheet in acetone, absolute ethyl alcohol and deionized water.
And S3, soaking the high-entropy alloy metal sheet obtained in the step S2 in the surfactant solution obtained in the step S1 for a certain time at a certain temperature. And then taking out, washing with ethanol and drying.
The temperature is 5-30 ℃, and the soaking time is 1-5 hours.
S4, preparing an etchant solution as an electrolyte and a reactant, and connecting the following three materials as electrodes on an electrochemical workstation: the high-entropy alloy metal sheet is used as a working electrode, the platinum wire is used as an auxiliary electrode, and the silver/silver chloride is used as a reference electrode.
The etching agent is one of sulfuric acid solution, nitric acid and sulfuric acid mixed solution or a mixture of the sulfuric acid solution and the nitric acid and sulfuric acid mixed solution in any proportion, and the mass fraction of the etching agent solution is 3% -15%.
And S5, cooling the electrolyte solution in an ice bath mode, and controlling the temperature of the electrolyte solution to be kept at a certain temperature. And applying a constant voltage for a period of time to the high-entropy alloy metal sheet by using an electrochemical workstation. And then taking out the high-entropy alloy metal sheet, sequentially cleaning the surface with ethanol and deionized water, and drying to obtain the AlCoCrFeNi high-entropy alloy with the surface having the nano structure.
The temperature is-5-15 ℃, the applied voltage is-4.0V, and the applied time is 0.5-8 hours.
The invention has the beneficial effects that:
1. the AlCoCrFeNi high-entropy alloy surfactant solution comprises one or more specified surfactants, and can selectively attack Fe elements in the AlCoCrFeNi high-entropy alloy after dissociation in an aqueous solution, so that pretreatment before electrochemical dealloying is realized, and the formation of a surface pore structure of the high-entropy alloy is facilitated.
2. Under a certain voltage, Al and Ni elements in the alloy components are selectively dissolved by an electrochemical dealloying method, and the formation of the lotus leaf nano structure on the surface of the high-entropy alloy is successfully realized by the synergistic effect of the Al and Ni elements and the beneficial effect 1. Meanwhile, the low-temperature control process in the electrochemical dealloying process ensures the distribution uniformity and pore-forming efficiency of the surface pores of the high-entropy alloy, and fully improves the hydrophobicity of the alloy. The lotus leaf nano structure obtained by the invention enables the AlCoCrFeNi high-entropy alloy to have a contact angle with water larger than 150 degrees, remarkably improves the hydrophobic property of the alloy and is expected to greatly and extremely improve the corrosion resistance effect of the alloy.
3. The preparation method has the advantages of simple preparation process, simple and convenient operation, mild experimental conditions, low production cost and easy realization of large-scale production.
Drawings
FIG. 1(a) is a microscopic lotus leaf nanostructure view of the surface of the high-entropy alloy in example 1 of the present invention;
FIG. 1(b) is a high entropy alloy surface microstructure without treatment according to the invention;
FIG. 2(a) is the contact angle of AlCoCrFeNi high entropy alloy with lotus leaf nano structure prepared by the invention to water;
FIG. 2(b) is the contact angle of a high entropy alloy that has not been subjected to the treatment of the present invention.
Detailed Description
The specific technical scheme of the invention is described by combining the embodiment.
Example 1
At room temperature, 1.0g of trinitrophenol is dissolved in 20mL of deionized water to prepare AlCoCrFeNi high-entropy alloy surfactant solution. Cutting the AlCoCrFeNi high-entropy alloy cast ingot into high-entropy alloy metal sheets with uniform sizes by using a linear cutting technology, and embedding the high-entropy alloy metal sheets connected with the leads into epoxy resin by using a cold embedding technology; and sequentially grinding and polishing the surface of the high-entropy alloy metal sheet by using 100-2000 # abrasive paper, and sequentially ultrasonically cleaning the surface of the high-entropy alloy metal sheet in acetone, absolute ethyl alcohol and deionized water. And (3) soaking the obtained high-entropy alloy metal sheet in a surfactant solution for 1 hour at the temperature of 30 ℃, then taking out, washing with ethanol, and drying.
Concentrated sulfuric acid was added to 30mL of deionized water to prepare a sulfuric acid solution having a mass fraction of 4% as an electrolyte solution. Inserting a high-entropy alloy metal sheet, a platinum wire and silver/silver chloride into an electrolyte solution, and connecting the following three materials as electrodes on an electrochemical workstation: the high-entropy alloy metal sheet is used as a working electrode, the platinum wire is used as an auxiliary electrode, and the silver/silver chloride is used as a reference electrode.
And (3) cooling the electrolyte solution by using an ice bath mode, and controlling the temperature of the electrolyte solution to be kept at 5 ℃. And applying a constant voltage of-0.2V to the high-entropy alloy metal sheet for 8 hours by using an electrochemical workstation. And then taking out the high-entropy alloy metal sheet, sequentially cleaning the surface with ethanol and deionized water, and drying to obtain the AlCoCrFeNi high-entropy alloy with the lotus leaf nano-structure on the surface.
When the lotus leaf-shaped nanostructure surface of the AlCoCrFeNi high-entropy alloy is observed by using a scanning electron microscope, as shown in FIG. 1(a), the lotus leaf-shaped nanostructure is indeed presented on the surface. For comparison, the surface structure of the AlCoCrFeNi high-entropy alloy which is not treated by the method of the present invention is observed under the same conditions, as shown in FIG. 1 (b).
Example 2
At room temperature, 1.5g of m-nitrophenol and p-nitrophenol are respectively dissolved in 50mL of deionized water to prepare AlCoCrFeNi high-entropy alloy surfactant solution. Cutting the AlCoCrFeNi high-entropy alloy cast ingot into high-entropy alloy metal sheets with uniform sizes by using a linear cutting technology, and embedding the high-entropy alloy metal sheets connected with the leads into epoxy resin by using a cold embedding technology; the surface of the high-entropy alloy metal sheet is sequentially polished by using 100-2000 # abrasive paper and is sequentially subjected to ultrasonic cleaning in acetone, absolute ethyl alcohol and deionized water. And (3) soaking the obtained high-entropy alloy metal sheet in a surfactant solution for 4 hours at 10 ℃, taking out, washing with ethanol, and drying.
Concentrated sulfuric acid was added to 30mL of deionized water to prepare a sulfuric acid solution having a mass fraction of 1% as an electrolyte solution. Inserting a high-entropy alloy metal sheet, a platinum wire and silver/silver chloride into an electrolyte solution, and connecting the following three materials as electrodes on an electrochemical workstation: the high-entropy alloy metal sheet is used as a working electrode, the platinum wire is used as an auxiliary electrode, and the silver/silver chloride is used as a reference electrode.
And (3) cooling the electrolyte solution by using an ice bath mode, and controlling the temperature of the electrolyte solution to be kept at 5 ℃. And applying a constant voltage of-0.4V to the high-entropy alloy metal sheet for 5 hours by using an electrochemical workstation. And then taking out the high-entropy alloy metal sheet, sequentially cleaning the surface with ethanol and deionized water, and drying to obtain the AlCoCrFeNi high-entropy alloy with the lotus leaf nano-structure on the surface.
Example 3
At room temperature, respectively dissolving 2g of 5-nitro-1, 2, 4-triazole-5-ketone in 40mL of deionized water to prepare AlCoCrFeNi high-entropy alloy surfactant solution. Cutting the AlCoCrFeNi high-entropy alloy cast ingot into high-entropy alloy metal sheets with uniform sizes by using a linear cutting technology, and embedding the high-entropy alloy metal sheets connected with the leads into epoxy resin by using a cold embedding technology; and sequentially grinding and polishing the surface of the high-entropy alloy metal sheet by using 100-2000 # abrasive paper, and sequentially ultrasonically cleaning the surface of the high-entropy alloy metal sheet in acetone, absolute ethyl alcohol and deionized water. And (3) soaking the obtained high-entropy alloy metal sheet in a surfactant solution for 2 hours at 15 ℃, then taking out, washing with ethanol, and drying.
Concentrated sulfuric acid is added into 30mL of deionized water, and a sulfuric acid solution with a fixed mass fraction of 6% is prepared to serve as an electrolyte solution. Inserting a high-entropy alloy metal sheet, a platinum wire and silver/silver chloride into an electrolyte solution, and connecting the following three materials as electrodes on an electrochemical workstation: the high-entropy alloy metal sheet is used as a working electrode, the platinum wire is used as an auxiliary electrode, and the silver/silver chloride is used as a reference electrode.
And (3) cooling the electrolyte solution by using an ice bath mode, and controlling the temperature of the electrolyte solution to be kept at-5 ℃. And applying a constant voltage of 0.2V to the high-entropy alloy metal sheet for 1 hour by using an electrochemical workstation. And then taking out the high-entropy alloy metal sheet, sequentially cleaning the surface with ethanol and deionized water, and drying to obtain the AlCoCrFeNi high-entropy alloy with the lotus leaf nano-structure on the surface.
Example 4
At room temperature, 1g of trinitrophenol, trinitrophenol sodium, m-nitrophenol, p-nitrophenol and 5-nitro-1, 2, 4-triazole-5-ketone are respectively dissolved in 60mL of deionized water to prepare AlCoCrFeNi high-entropy alloy surfactant solution. Cutting the AlCoCrFeNi high-entropy alloy cast ingot into high-entropy alloy metal sheets with uniform sizes by using a linear cutting technology, and embedding the high-entropy alloy metal sheets connected with the leads into epoxy resin by using a cold embedding technology; and sequentially grinding and polishing the surface of the high-entropy alloy metal sheet by using 100-2000 # abrasive paper, and sequentially ultrasonically cleaning the surface of the high-entropy alloy metal sheet in acetone, absolute ethyl alcohol and deionized water. And (3) soaking the obtained high-entropy alloy metal sheet in a surfactant solution for 5 hours at 10 ℃, then taking out, washing with ethanol, and drying.
Concentrated sulfuric acid is added into 30mL of deionized water, and a sulfuric acid solution with a fixed mass fraction of 10% is prepared to serve as an electrolyte solution. Inserting a high-entropy alloy metal sheet, a platinum wire and silver/silver chloride into an electrolyte solution, and connecting the following three materials as electrodes on an electrochemical workstation: the high-entropy alloy metal sheet is used as a working electrode, the platinum wire is used as an auxiliary electrode, and the silver/silver chloride is used as a reference electrode.
And (3) cooling the electrolyte solution by using an ice bath mode, and controlling the temperature of the electrolyte solution to be kept at 0 ℃. A constant voltage of 0.4V is applied to the high-entropy alloy metal sheet for 1 hour by using an electrochemical workstation. And then taking out the high-entropy alloy metal sheet, sequentially cleaning the surface with ethanol and deionized water, and drying to obtain the AlCoCrFeNi high-entropy alloy with the lotus leaf nano-structure on the surface.
To prove the hydrophobic effect of the lotus leaf nanostructure, the contact angle of water of the sample obtained in example 4 was measured, and the result is shown in fig. 2(a), wherein the contact angle is 156 °, and the sample belongs to super-hydrophobic effect. In addition, for comparison, the AlCoCrFeNi high entropy alloy sample which is not treated by the method of the present invention was subjected to the water contact angle test under the same conditions, and the result is shown in fig. 2(b), in which the contact angle is 96 °. Therefore, the hydrophobicity of the AlCoCrFeNi high-entropy alloy sample with the lotus leaf nano structure prepared by the method is greatly improved.
The above detailed description is intended to illustrate the objects, aspects and advantages of the present invention, and it should be understood that the above detailed description is only exemplary of the present invention and is not intended to limit the scope of the present invention, and any modifications, equivalents, improvements and the like made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (3)
1. A preparation method of a super-hydrophobic nano-structure high-entropy alloy is characterized by comprising the following steps: soaking an AlCoCrFeNi high-entropy alloy sample in a surfactant solution, cleaning and drying, then putting the sample into an etchant solution, and preparing the nano structure by using an electrochemical dealloying method;
the method specifically comprises the following steps:
s1, dissolving a surfactant in deionized water to prepare AlCoCrFeNi high-entropy alloy surfactant solution;
the surfactant is one or a mixture of more of trinitrophenol, trinitrophenol sodium, m-nitrophenol, p-nitrophenol and 5-nitro-1, 2, 4-triazole-5-ketone, and the mass ratio of the surfactant to deionized water is 1: 10 to 100 parts;
s2, cutting the AlCoCrFeNi high-entropy alloy cast ingot into high-entropy alloy metal sheets with uniform size by using a linear cutting technology, and embedding the high-entropy alloy metal sheets of the connecting wires into epoxy resin by using a cold embedding technology; sequentially grinding and polishing the surface of the high-entropy alloy metal sheet by using No. 100-2000 abrasive paper, and sequentially ultrasonically cleaning the surface of the high-entropy alloy metal sheet in acetone, absolute ethyl alcohol and deionized water;
s3, soaking the high-entropy alloy metal sheet obtained in the step S2 in the surfactant solution obtained in the step S1 for a certain time; then taking out, washing with ethanol and drying;
s4, preparing an etchant solution as an electrolyte and a reactant, and connecting the following three materials as electrodes on an electrochemical workstation: the high-entropy alloy metal sheet is used as a working electrode, the platinum wire is used as an auxiliary electrode, and the silver/silver chloride is used as a reference electrode;
the etching agent is sulfuric acid solution or mixed solution of nitric acid and sulfuric acid; the mass fraction of the etchant solution is 3% -15%;
s5, cooling the electrolyte solution in an ice bath mode, and controlling the temperature of the electrolyte solution to be kept at a certain temperature; applying constant voltage to the high-entropy alloy metal sheet by using an electrochemical workstation; the conditions for applying constant voltage are as follows: the temperature is-5-15 ℃, the applied voltage is-4.0V, and the applied time is 0.5-8 hours; and then taking out the high-entropy alloy metal sheet, sequentially cleaning the surface by using ethanol and deionized water, and drying to obtain the AlCoCrFeNi high-entropy alloy with the surface having the nano structure.
2. The preparation method of the super-hydrophobic nano-structure high-entropy alloy according to claim 1, wherein in S3, the soaking temperature is 5-30 ℃ and the soaking time is 1-5 hours.
3. A preparation method of a super-hydrophobic nano-structure high-entropy alloy is characterized by being obtained according to the preparation method of claim 1 or 2.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110959707.5A CN113549991B (en) | 2021-08-20 | 2021-08-20 | Super-hydrophobic nano-structure high-entropy alloy and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110959707.5A CN113549991B (en) | 2021-08-20 | 2021-08-20 | Super-hydrophobic nano-structure high-entropy alloy and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113549991A CN113549991A (en) | 2021-10-26 |
| CN113549991B true CN113549991B (en) | 2022-07-19 |
Family
ID=78134086
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110959707.5A Active CN113549991B (en) | 2021-08-20 | 2021-08-20 | Super-hydrophobic nano-structure high-entropy alloy and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113549991B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113684526A (en) * | 2021-09-18 | 2021-11-23 | 北京理工大学 | High-entropy alloy material with super-hydrophobic surface structure and preparation method thereof |
| CN116837382B (en) * | 2023-07-25 | 2023-12-08 | 中国船舶集团有限公司第七一九研究所 | Eutectic high-entropy alloy with wear-resistant superhydrophobic surface and preparation method thereof |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105256342B (en) * | 2015-10-19 | 2017-10-20 | 华南理工大学 | A kind of super hydrophobic surface based on copper and preparation method thereof |
| WO2017206050A1 (en) * | 2016-05-31 | 2017-12-07 | City University Of Hong Kong | Method for treating a surface of a metallic structure |
| CN109161958A (en) * | 2018-10-26 | 2019-01-08 | 长春理工大学 | A kind of method and device preparing copper surface super hydrophobic structure |
| US11359266B2 (en) * | 2018-11-20 | 2022-06-14 | City University Of Hong Kong | High entropy alloy structure and a method of preparing the same |
| CN109468678B (en) * | 2019-01-16 | 2021-02-02 | 沈阳航空航天大学 | Electrolytic corrosion solution for high-melting-point and high-entropy alloy and use method thereof |
| CN111530126B (en) * | 2020-05-12 | 2021-12-21 | 太原理工大学 | Preparation method and application of super-hydrophobic foam iron |
-
2021
- 2021-08-20 CN CN202110959707.5A patent/CN113549991B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN113549991A (en) | 2021-10-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN113549991B (en) | Super-hydrophobic nano-structure high-entropy alloy and preparation method thereof | |
| CN102230210B (en) | Non-chromium electrolytic polishing solution for stainless steel and surface polishing process for stainless steel | |
| CN112609218A (en) | Preparation method of super-hydrophobic micro-arc oxidation composite membrane | |
| CN104404520A (en) | Metallographic structure etching solution of high-nitrogen stainless steel and metallographic etching method | |
| CN109457245B (en) | Machining-state wrought aluminum alloy grain boundary corrosive agent and preparation method and application thereof | |
| CN101634027A (en) | Method for preparing monocrystal silicon textured surface | |
| CN106702383A (en) | Metallographic-phase corrosion liquid of beta titanium alloy and corrosion method | |
| CN107855254B (en) | Preparation method of corrosion-resistant organic composite coating on surface of magnesium alloy | |
| CN110726743B (en) | Method for preparing pure titanium EBSD sample at room temperature | |
| CN104264196A (en) | Method for preparing super-hydrophobic membrane layer on surface of magnesium alloy through one-step method as well as alloy and application of uper-hydrophobic membrane layer | |
| CN105092580A (en) | Observation method for industrial pure zirconium microstructure | |
| CN110644026B (en) | Preparation method of super-hydrophobic aluminum alloy surface with self-repairing characteristic | |
| CN103305846A (en) | Corrosive liquid for 300M metallographic analysis and corrosion method | |
| CN106676619B (en) | A kind of preparation method of glassy metal nano-porous structure | |
| LI et al. | Corrosion action and passivation mechanism of magnesium alloy in fluoride solution | |
| CN110618153A (en) | Preparation method of electropolished titanium alloy large-size rod-shaped or plate-shaped sample | |
| CN110629266B (en) | Preparation method of super-hydrophobic stainless steel surface with self-repairing characteristic | |
| CN110165158B (en) | Preparation method of silicon-copper composite nanowire | |
| CN113684526A (en) | High-entropy alloy material with super-hydrophobic surface structure and preparation method thereof | |
| CN110552044A (en) | Steel anodic oxidation electrolyte and anodic oxidation method thereof | |
| CN108251871B (en) | Method for electrodepositing Al-Pt alloy in imidazole type ionic liquid | |
| CN111139481B (en) | Stainless steel corrosive agent for fuel cell bipolar plate and metallographic phase preparation method | |
| CN109628989B (en) | Preparation method of high-chromium alloy super-hydrophilic surface | |
| CN107931073B (en) | Treatment method for corrosion-resistant modification of aluminum alloy surface | |
| Yang et al. | Surface modification of nitinol by chemical and electrochemical etching |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |