CN114686865B - Metal covered with fatty acid salt coating - Google Patents
Metal covered with fatty acid salt coating Download PDFInfo
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- CN114686865B CN114686865B CN202210277853.4A CN202210277853A CN114686865B CN 114686865 B CN114686865 B CN 114686865B CN 202210277853 A CN202210277853 A CN 202210277853A CN 114686865 B CN114686865 B CN 114686865B
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- fatty acid
- metal
- acid salt
- coating
- aqueous solution
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- 229910052751 metal Inorganic materials 0.000 title claims abstract description 129
- 239000002184 metal Substances 0.000 title claims abstract description 129
- 235000014113 dietary fatty acids Nutrition 0.000 title claims abstract description 92
- 229930195729 fatty acid Natural products 0.000 title claims abstract description 92
- 239000000194 fatty acid Substances 0.000 title claims abstract description 92
- -1 fatty acid salt Chemical class 0.000 title claims abstract description 86
- 239000011248 coating agent Substances 0.000 title claims abstract description 72
- 238000000576 coating method Methods 0.000 title claims abstract description 72
- 230000003075 superhydrophobic effect Effects 0.000 claims abstract description 38
- 239000007864 aqueous solution Substances 0.000 claims abstract description 33
- 238000001035 drying Methods 0.000 claims abstract description 18
- 238000004140 cleaning Methods 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 8
- 238000005530 etching Methods 0.000 claims abstract description 5
- 239000010949 copper Substances 0.000 claims description 19
- BTURAGWYSMTVOW-UHFFFAOYSA-M sodium dodecanoate Chemical compound [Na+].CCCCCCCCCCCC([O-])=O BTURAGWYSMTVOW-UHFFFAOYSA-M 0.000 claims description 18
- 229940082004 sodium laurate Drugs 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 16
- 229910052802 copper Inorganic materials 0.000 claims description 16
- 150000004665 fatty acids Chemical class 0.000 claims description 12
- 238000002360 preparation method Methods 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 6
- 239000012266 salt solution Substances 0.000 claims description 2
- 238000005260 corrosion Methods 0.000 abstract description 12
- 230000007797 corrosion Effects 0.000 abstract description 11
- 239000008204 material by function Substances 0.000 abstract description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 29
- 238000002791 soaking Methods 0.000 description 14
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 11
- 239000000243 solution Substances 0.000 description 8
- 150000001768 cations Chemical class 0.000 description 7
- 235000019441 ethanol Nutrition 0.000 description 7
- 239000002253 acid Substances 0.000 description 5
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 5
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 4
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 239000005639 Lauric acid Substances 0.000 description 4
- 229910001431 copper ion Inorganic materials 0.000 description 4
- 239000011737 fluorine Substances 0.000 description 4
- 229910052731 fluorine Inorganic materials 0.000 description 4
- 229910044991 metal oxide Inorganic materials 0.000 description 4
- 150000004706 metal oxides Chemical class 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 238000002329 infrared spectrum Methods 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- KAKVFSYQVNHFBS-UHFFFAOYSA-N (5-hydroxycyclopenten-1-yl)-phenylmethanone Chemical compound OC1CCC=C1C(=O)C1=CC=CC=C1 KAKVFSYQVNHFBS-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 239000005751 Copper oxide Substances 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229910000431 copper oxide Inorganic materials 0.000 description 2
- JDPSPYBMORZJOD-UHFFFAOYSA-L copper;dodecanoate Chemical compound [Cu+2].CCCCCCCCCCCC([O-])=O.CCCCCCCCCCCC([O-])=O JDPSPYBMORZJOD-UHFFFAOYSA-L 0.000 description 2
- GHVNFZFCNZKVNT-UHFFFAOYSA-N decanoic acid Chemical compound CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 description 2
- 238000004108 freeze drying Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000001307 helium Substances 0.000 description 2
- 229910052734 helium Inorganic materials 0.000 description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 229940114930 potassium stearate Drugs 0.000 description 2
- QDIGBJJRWUZARS-UHFFFAOYSA-M potassium;decanoate Chemical compound [K+].CCCCCCCCCC([O-])=O QDIGBJJRWUZARS-UHFFFAOYSA-M 0.000 description 2
- MQOCIYICOGDBSG-UHFFFAOYSA-M potassium;hexadecanoate Chemical compound [K+].CCCCCCCCCCCCCCCC([O-])=O MQOCIYICOGDBSG-UHFFFAOYSA-M 0.000 description 2
- ANBFRLKBEIFNQU-UHFFFAOYSA-M potassium;octadecanoate Chemical compound [K+].CCCCCCCCCCCCCCCCCC([O-])=O ANBFRLKBEIFNQU-UHFFFAOYSA-M 0.000 description 2
- PYJBVGYZXWPIKK-UHFFFAOYSA-M potassium;tetradecanoate Chemical compound [K+].CCCCCCCCCCCCCC([O-])=O PYJBVGYZXWPIKK-UHFFFAOYSA-M 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 229940045845 sodium myristate Drugs 0.000 description 2
- RYYKJJJTJZKILX-UHFFFAOYSA-M sodium octadecanoate Chemical compound [Na+].CCCCCCCCCCCCCCCCCC([O-])=O RYYKJJJTJZKILX-UHFFFAOYSA-M 0.000 description 2
- 229940045870 sodium palmitate Drugs 0.000 description 2
- 229940080350 sodium stearate Drugs 0.000 description 2
- FIWQZURFGYXCEO-UHFFFAOYSA-M sodium;decanoate Chemical compound [Na+].CCCCCCCCCC([O-])=O FIWQZURFGYXCEO-UHFFFAOYSA-M 0.000 description 2
- GGXKEBACDBNFAF-UHFFFAOYSA-M sodium;hexadecanoate Chemical compound [Na+].CCCCCCCCCCCCCCCC([O-])=O GGXKEBACDBNFAF-UHFFFAOYSA-M 0.000 description 2
- JUQGWKYSEXPRGL-UHFFFAOYSA-M sodium;tetradecanoate Chemical compound [Na+].CCCCCCCCCCCCCC([O-])=O JUQGWKYSEXPRGL-UHFFFAOYSA-M 0.000 description 2
- 238000004506 ultrasonic cleaning Methods 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 239000005632 Capric acid (CAS 334-48-5) Substances 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 235000021314 Palmitic acid Nutrition 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 235000021588 free fatty acids Nutrition 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- TUNFSRHWOTWDNC-HKGQFRNVSA-N tetradecanoic acid Chemical compound CCCCCCCCCCCCC[14C](O)=O TUNFSRHWOTWDNC-HKGQFRNVSA-N 0.000 description 1
- 238000009941 weaving Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/48—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 not containing phosphates, hexavalent chromium compounds, fluorides or complex fluorides, molybdates, tungstates, vanadates or oxalates
Abstract
The invention belongs to the technical field of functional materials, and particularly relates to a metal covered with a fatty acid salt coating. A metal coated with a fatty acid salt coating comprising a metal and a fatty acid salt coating coated on a surface of the metal, the fatty acid salt coating formed by a method comprising: sequentially etching, cleaning and drying the metal; the dried metal is soaked in the aqueous solution of fatty acid salt, and the surface of the metal is covered with the fatty acid salt coating. The prepared super-hydrophobic metal surface coating has uniform thickness and good corrosion resistance.
Description
The invention is based on the application number 201811441638.3, the application date is number 2018, 11 month 29, and the application is the division application provided by the university of Rudong with the invention name of 'a super-hydrophobic metal surface coating and a preparation method thereof'.
Technical Field
The invention belongs to the technical field of functional materials, and particularly relates to a metal covered with a fatty acid salt coating.
Background
Metals play an indispensable role in daily life, however, corrosion of metals brings about a great economic loss. The hydrophobic coating is covered on the metal surface, so that the aim of modifying and protecting the metal surface can be fulfilled. Fatty acid is a surfactant with high quality and low cost, and has high surface activity. the-COOH group in the fatty acid molecule can interact with ions on the metal surface, and the hydrophobic chain can repel water. Therefore, the metal with the fatty acid coating is super-hydrophobic and can well play a role in corrosion resistance.
At present, fluorine-containing fatty acid or fluorine-containing fatty acid salt is generally adopted to weave a super-hydrophobic coating on the metal surface, but the fluorine-containing fatty acid or fluorine-containing fatty acid salt has high toxicity and high price, so that the super-hydrophobic coating is not suitable for popularization and application. The fatty acid is soaked in ethanol solution or the fatty acid is dissolved by adding alkali, the super-hydrophobic coating is woven on the metal surface, the weaving time of the process is long, usually several days, and the ethanol has great potential safety hazard in industrial production; and a large amount of heat is generated in the process of adding alkali for dissolution, which is unfavorable for mass production.
Therefore, the development process of the super-hydrophobic metal surface anti-corrosion coating with simple and safe technology is urgent.
Disclosure of Invention
The invention aims to provide a metal covered with a fatty acid salt coating, wherein the thickness of the super-hydrophobic metal surface coating is uniform, and the corrosion resistance is good.
To achieve the above object, the present invention provides, in one aspect, a metal covered with a fatty acid salt coating, including a metal and a fatty acid salt coating covered on a surface of the metal, the fatty acid salt coating being formed by: sequentially etching, cleaning and drying the metal; the dried metal is soaked in the aqueous solution of fatty acid salt, and the surface of the metal is covered with the fatty acid salt coating.
Optionally, the fatty acid salt aqueous solution is obtained by the following preparation method: adding fatty acid salt into water, and heating to dissolve to obtain fatty acid salt aqueous solution; the fatty acid salt is one of sodium caprate, sodium laurate, sodium myristate, sodium palmitate, sodium stearate, potassium caprate, potassium laurate, potassium myristate, potassium palmitate and potassium stearate.
Optionally, the concentration of the aqueous solution of fatty acid salt is 6mmol/L-200mmol/L.
Optionally, the metal is copper, iron, aluminum, zinc or lead.
Compared with the prior art, the invention has the following beneficial effects: according to the embodiment of the invention, the etched, cleaned and dried metal is soaked in the fatty acid salt aqueous solution, the metal reacts with oxygen in the fatty acid salt aqueous solution to generate metal oxide, hydrogen ions which are ionized by water in the fatty acid salt aqueous solution react with the metal oxide to generate metal cations, the metal cations and fatty acid anions can form new fatty acid salt through coordination, the new fatty acid salt grows on the metal surface, and the super-hydrophobic metal surface coating is formed on the metal surface.
According to the embodiment of the invention, the super-hydrophobic metal surface coating is woven on the metal surface by a one-step soaking method, the ionization degree of the fatty acid salt in the aqueous solution is far greater than that of the fatty acid salt in ethanol, the preparation method of the super-hydrophobic metal surface coating can be carried out at the ambient temperature, the reaction is rapid, the prepared super-hydrophobic metal surface coating is uniform in thickness and good in corrosion resistance, and the metal is soaked in the fatty acid salt aqueous solution for reaction, so that the preparation method is safe. Wherein the ambient temperature is the temperature of the environment where the reaction system is located.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings that are needed in the embodiments or the description of the prior art will be briefly described below, it being obvious that the drawings in the following description are only some embodiments of the present invention, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a representation of water droplets on a superhydrophobic metal surface coating according to an embodiment of the invention.
FIG. 2 is an infrared spectrum comparing the super-hydrophobic metal surface coating with fatty acid salt in the example of the present invention.
FIG. 3 is a scanning electron microscope image of a super-hydrophobic metal surface coating according to an embodiment of the present invention.
FIG. 4 is a second scanning electron microscope image of the super-hydrophobic metal surface coating according to the embodiment of the invention.
FIG. 5 is an X-ray diffraction pattern of a superhydrophobic metal surface coating in an embodiment of the invention.
FIG. 6 is a Nyquist plot of the electrochemical performance of a superhydrophobic metal surface coating according to an embodiment of the invention.
Fig. 7 is a Nyquist plot of the electrochemical performance of bare metal in an embodiment of the invention.
Wherein, 1-water drop; 2-superhydrophobic metal surface coating.
Detailed Description
In order to make the technical problems, technical schemes and beneficial effects to be solved more clear, the invention is further described in detail below with reference to the embodiments. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
In one aspect, the embodiment of the invention provides a preparation method of a super-hydrophobic metal surface coating, which comprises the following steps:
s01, sequentially etching, cleaning and drying the metal;
s02, soaking the dried metal in a fatty acid salt aqueous solution, and covering a fatty acid salt coating on the surface of the metal;
and S03, cleaning and drying the metal covered with the fatty acid salt coating in sequence to obtain the super-hydrophobic metal surface coating.
According to the embodiment of the invention, the etched, cleaned and dried metal is soaked in the fatty acid salt aqueous solution, the metal reacts with oxygen in the fatty acid salt aqueous solution to generate metal oxide, hydrogen ions which are ionized by water in the fatty acid salt aqueous solution react with the metal oxide to generate metal cations, the metal cations and fatty acid anions can form new fatty acid salt through coordination, the new fatty acid salt grows on the metal surface, and the super-hydrophobic metal surface coating is formed on the metal surface.
According to the embodiment of the invention, the super-hydrophobic metal surface coating is woven on the metal surface by a one-step soaking method, the ionization degree of the fatty acid salt in the aqueous solution is far greater than that in ethanol, the preparation method of the super-hydrophobic metal surface coating can be carried out at the ambient temperature, the reaction is rapid, and the prepared super-hydrophobic metal surface coating is uniform in thickness and good in corrosion resistance. Wherein the ambient temperature is the temperature of the environment where the reaction system is located.
Specifically, in step S01, the metal is sequentially etched, cleaned, and dried; the surface of the metal is pretreated to remove oil stains and rust stains on the surface of the metal, so that preparation is made for the subsequent steps.
Wherein the etching comprises: placing the metal in an organic solvent, ultrasonically cleaning to remove oil stains on the surface of the metal, placing the metal in an acid solution after the oil stains are removed, and ultrasonically soaking to remove rust on the surface of the metal. The organic solvent can be ethanol, methanol or ethyl acetate; but are not limited to, the above organic solvents; the acid solution is a solution with solute as acid, and can be hydrochloric acid, nitric acid, dilute sulfuric acid or acetic acid. Ultrasonic cleaning accelerates the oil stain removal speed; ultrasonic soaking accelerates the rust removal speed.
As a specific embodiment of the invention, the metal is placed in absolute ethyl alcohol and is ultrasonically cleaned for 10-30 min, so as to remove oil stains on the surface of the metal.
As a specific embodiment of the invention, the acid solution is hydrochloric acid, the mass fraction of the hydrochloric acid is 10% -20%, and the time for ultrasonic soaking of the metal in the hydrochloric acid is 10min-30min. Hydrochloric acid is a common strong acid used to etch metal surfaces and is not oxidizing.
In the step of cleaning the metal, the metal is sequentially cleaned by water and absolute ethyl alcohol. The final step of metal cleaning is absolute ethyl alcohol cleaning, so that the metal surface drying can be accelerated.
The metal is dried by nitrogen gas, argon gas, helium gas, freeze drying, blower drying, vacuum drying or low-temperature heating drying; but are not limited to, the drying modes described above. Preferably, nitrogen is blown dry, and is an inert gas, low in price and easy to obtain.
Specifically, in step S02, the dried metal is immersed in a fatty acid salt aqueous solution, and a fatty acid salt coating is covered on the surface of the metal; the soaking time of the metal in the fatty acid salt aqueous solution is more than 3 hours, and the soaking temperature is more than 15 ℃. The soaking temperature can be ambient temperature, and the reaction of the metal and the fatty acid salt aqueous solution can be carried out spontaneously at the ambient temperature, so that the fatty acid salt coating is woven on the surface of the metal. If the soaking time of the metal in the aqueous solution of fatty acid salt is too short, the metal cations on the metal surface and the fatty acid anions cannot be fully reacted, resulting in incomplete coverage of the coating. If the soaking temperature is too low, the reaction rate is too slow, and even the fatty acid salt aqueous solution can precipitate out to influence the growth of the coating.
Preferably, the soaking time may be 3 to 24 hours. As a specific embodiment of the invention, the soaking time can be 3h, 5h, 6h, 8h, 10h, 11h, 12h, 14h, 16h, 18h or 24h.
The fatty acid salt aqueous solution can be obtained by the following preparation method: adding fatty acid salt into water, and heating for dissolving to obtain fatty acid salt water solution.
When the carbon chain number of the fatty acid is more than 8, the surface activity is enhanced, and even fatty acids with the carbon chain number of 10-18, namely, capric acid, lauric acid, myristic acid, palmitic acid and stearic acid, have stronger surface activity. And the fatty acid potassium salt and the fatty acid sodium salt are more common and readily available.
The fatty acid salt may be one of sodium caprate, sodium laurate, sodium myristate, sodium palmitate, sodium stearate, potassium caprate, potassium laurate, potassium myristate, potassium palmitate and potassium stearate. Preferably, the concentration of the aqueous solution of fatty acid salt is 6mmol/L-200mmol/L. If the concentration of the fatty acid salt is too low, the reaction speed of the metal cations on the metal surface and the fatty acid anions is too slow, and even a complete coating cannot be formed; if the concentration of the fatty acid salt is too high, the fatty acid salt cannot be completely dissolved, or the metal cations react with the fatty acid anions to rapidly generate precipitates, which affect the growth of the coating.
As a specific example of the present invention, the concentration of the aqueous fatty acid salt solution may be 6mmol/L, 10mmol/L, 20mmol/L, 30mmol/L, 40mmol/L, 50mmol/L, 70mmol/L, 100mmol/L, 120mmol/L, 150mmol/L, 170mmol/L, 180mmol/L, 190mmol/L or 200mmol/L.
Specifically, in step S03, the metal covered with the fatty acid salt coating is sequentially cleaned and dried to obtain a superhydrophobic metal surface coating.
Wherein, the metal covered with the fatty acid salt coating is washed by water and absolute ethyl alcohol in turn; the final step of the cleaning is to clean with absolute ethyl alcohol, on the one hand to accelerate the drying of the metal surface and on the other hand to further remove the free fatty acid salt on the surface of the fatty acid salt coating.
Wherein, the drying mode can be nitrogen drying, argon drying, helium drying, freeze drying, blower drying, vacuum drying or low-temperature heating drying; preferably, nitrogen is blown dry, and is an inert gas, low in price and easy to obtain.
In the above embodiments, the water may be deionized water.
In the above embodiments, the metal may be copper, iron, aluminum, zinc, or lead.
As a specific embodiment of the present invention, the metal is copper, and the fatty acid salt is sodium laurate. Adding copper into the sodium laurate aqueous solution, and covering the surface of the copper with a sodium laurate coating;
the reaction mechanism of copper and sodium laurate is as follows:
2Cu+O 2 →2CuO
CuO+2H + →Cu 2+ +H 2 O
Cu 2+ +2CH 3 (CH 2 ) 10 COO - →Cu[CH 3 (CH 2 ) 10 COO] 2
copper reacts with oxygen in the sodium laurate aqueous solution to generate copper oxide, hydrogen ions which are ionized by water in the sodium laurate aqueous solution react with the copper oxide to generate copper ions, and the copper ions and lauric acid anions can form copper laurate through coordination, so that the copper laurate grows on the surface of the copper.
The ionization degree of sodium laurate in aqueous solution is far greater than that of sodium laurate in ethanol, and the reaction rate of the coordination reaction of copper ions and lauric acid anions is also quicker in aqueous solution than that of sodium laurate in ethanol, so that the preparation method of the super-hydrophobic metal surface coating in the embodiment of the invention is simple and quick, and has a short period.
The embodiment of the invention further provides a super-hydrophobic metal surface coating, which is prepared by the preparation method in any one of the above embodiments.
The following description is made with reference to specific embodiments.
Example 1
S101, adding sodium laurate into water, heating and dissolving at 50 ℃ to prepare 10mmol/L sodium laurate aqueous solution;
s102, taking out copper, placing the copper in absolute ethyl alcohol, and performing ultrasonic cleaning for 10min to remove oil stains; then placing copper in hydrochloric acid with the mass fraction of 15%, and ultrasonically cleaning for 10min to remove rust;
and S103, cleaning the rust removed copper with water and absolute ethyl alcohol in sequence, and drying with nitrogen.
S104, placing the copper cleaned and dried in the step S103 into a 10mmol/L sodium laurate aqueous solution prepared in the step S101, and soaking for 3 hours at 25 ℃.
And S105, taking out the copper soaked in the step S104, cleaning with water and absolute ethyl alcohol in sequence, and drying with nitrogen to obtain the super-hydrophobic metal surface coating.
Referring to fig. 1 to 7, characterization analysis was performed on the superhydrophobic metal coating prepared in example 1.
In fig. 1, water droplets 1 are dropped on the superhydrophobic metal coating 2 on the copper surface, illustrating that the superhydrophobic metal coating 2 has superhydrophobic properties.
In FIG. 2, curve a represents the infrared spectrum of sodium laurate, and b represents the infrared spectrum of the superhydrophobic metal coating 2. As is evident from FIG. 2, sodium laurate is found at wave number (Wavenumber) 1563cm -1 The peak at the position red-shifted to 1586cm -1 Here, it is explained that lauric acid anions interact with copper ions.
In fig. 3 and 4, the scanning electron microscope pictures show that the microstructure of the superhydrophobic metal coating 2 is arranged in a lamellar structure.
In fig. 5, the X-ray diffraction spectrum is a plot of peak Intensity (Intensity) versus diffraction angle (2θ), three stronger X-ray diffraction peaks appear, according to the bragg equation, 2dsin θ=nλ, where d is the interplanar spacing, n is the number of reflection orders, λ is the wavelength, and the ratio of the interplanar spacing d corresponding to the three diffraction peaks is calculated to be 1:1/2:1/3, indicating that the microstructure of the superhydrophobic metal surface coating is an ordered lamellar structure.
In FIGS. 6 and 7, the scatter plot represents the Nyquist curve, ordinate Z, for the metal surface tested i As the imaginary part of the impedance, the abscissa Z r The curve is fitted (Semicircle fitting) with a semicircle as the real part of the impedance, the resulting semicircle diameter representing the charge transfer resistance of the test metal (R t Represented by formula), R t The reciprocal of (2) reflects the corrosion rate of the metal in the corrosion solution, and therefore, a larger R t The metal with the value indicated has higher corrosion resistance. The inhibition efficiency of metal corrosion (represented by IE) can be calculated by the following formula:
IE＝(R t -R t0 )/R t ×100％
R t and R is t0 The charge transfer resistances of the superhydrophobic metal surface coating (Modified metal) and Bare metal (Bare metal) surfaces are represented, respectively, with an IE value of 99.05% calculated according to the formula. The super-hydrophobic metal surface coating prepared by the method has good corrosion resistance.
While the invention has been described in detail in connection with the specific embodiments described above, it should be understood that the foregoing is only illustrative of the preferred embodiments of the invention and is not intended to limit the scope of the invention, but is to be construed as limited to the following claims.
Claims (3)
1. A metal coated with a fatty acid salt coating, comprising a metal and a fatty acid salt coating coated on the surface of the metal, wherein the microstructure of the fatty acid salt coating is a sheet-like structure, and the fatty acid salt coating is formed by the following method: sequentially etching, cleaning and drying the metal; the dried metal is soaked in a fatty acid salt aqueous solution at the ambient temperature, and a fatty acid salt coating is covered on the surface of the metal, wherein the fatty acid salt coating is a super-hydrophobic metal surface coating, the metal is copper, and the fatty acid salt in the fatty acid salt aqueous solution is sodium laurate.
2. The metal covered with fatty acid salt coating according to claim 1, characterized in that said fatty acid salt aqueous solution is obtained by the following preparation method: adding fatty acid salt into water, and heating to dissolve to obtain fatty acid salt aqueous solution; the fatty acid salt is sodium laurate.
3. The metal covered with a fatty acid salt coating according to claim 1, characterized in that the concentration of the aqueous fatty acid salt solution is 6mmol/L-200mmol/L.
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| CN110983397B (en) * | 2019-12-19 | 2022-02-01 | 沈阳理工大学 | Method for preparing super-hydrophobic film on surface of aluminum matrix by sodium stearate aqueous solution |
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