CN112176338A - Preparation method of ZnAL-LDHs film with amino acid ion intercalation - Google Patents
Preparation method of ZnAL-LDHs film with amino acid ion intercalation Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 238000009830 intercalation Methods 0.000 title abstract description 9
- 230000002687 intercalation Effects 0.000 title abstract description 9
- 229910000861 Mg alloy Inorganic materials 0.000 claims abstract description 86
- -1 amino acid ion Chemical class 0.000 claims abstract description 40
- 239000000243 solution Substances 0.000 claims abstract description 33
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 24
- 239000011259 mixed solution Substances 0.000 claims abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000001035 drying Methods 0.000 claims abstract description 13
- 238000010438 heat treatment Methods 0.000 claims abstract description 13
- 239000008367 deionised water Substances 0.000 claims abstract description 12
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 12
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims abstract description 9
- 239000004810 polytetrafluoroethylene Substances 0.000 claims abstract description 9
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical compound C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 claims abstract description 8
- XNDZQQSKSQTQQD-UHFFFAOYSA-N 3-methylcyclohex-2-en-1-ol Chemical compound CC1=CC(O)CCC1 XNDZQQSKSQTQQD-UHFFFAOYSA-N 0.000 claims abstract description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 7
- 239000002904 solvent Substances 0.000 claims abstract description 5
- 229940024606 amino acid Drugs 0.000 claims description 36
- 235000001014 amino acid Nutrition 0.000 claims description 36
- CKLJMWTZIZZHCS-REOHCLBHSA-N aspartic acid group Chemical group N[C@@H](CC(=O)O)C(=O)O CKLJMWTZIZZHCS-REOHCLBHSA-N 0.000 claims description 15
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 12
- 150000001413 amino acids Chemical class 0.000 claims description 9
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 9
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 7
- 229960005261 aspartic acid Drugs 0.000 claims description 5
- BTURAGWYSMTVOW-UHFFFAOYSA-M sodium dodecanoate Chemical compound [Na+].CCCCCCCCCCCC([O-])=O BTURAGWYSMTVOW-UHFFFAOYSA-M 0.000 claims description 5
- 229940082004 sodium laurate Drugs 0.000 claims description 5
- CKLJMWTZIZZHCS-UWTATZPHSA-N D-aspartic acid Chemical compound OC(=O)[C@H](N)CC(O)=O CKLJMWTZIZZHCS-UWTATZPHSA-N 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 239000011701 zinc Substances 0.000 claims description 4
- CKLJMWTZIZZHCS-UHFFFAOYSA-N D-OH-Asp Natural products OC(=O)C(N)CC(O)=O CKLJMWTZIZZHCS-UHFFFAOYSA-N 0.000 claims description 3
- 244000137852 Petrea volubilis Species 0.000 claims description 3
- 238000007605 air drying Methods 0.000 claims description 3
- 238000005498 polishing Methods 0.000 claims description 3
- 235000003704 aspartic acid Nutrition 0.000 claims description 2
- OQFSQFPPLPISGP-UHFFFAOYSA-N beta-carboxyaspartic acid Natural products OC(=O)C(N)C(C(O)=O)C(O)=O OQFSQFPPLPISGP-UHFFFAOYSA-N 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 229910000144 sodium(I) superoxide Inorganic materials 0.000 claims description 2
- 238000005260 corrosion Methods 0.000 abstract description 53
- 230000007797 corrosion Effects 0.000 abstract description 52
- 239000000758 substrate Substances 0.000 abstract description 18
- 239000007788 liquid Substances 0.000 abstract description 5
- 238000001027 hydrothermal synthesis Methods 0.000 abstract description 3
- 238000011065 in-situ storage Methods 0.000 abstract description 3
- 150000007524 organic acids Chemical class 0.000 abstract description 2
- 238000004140 cleaning Methods 0.000 abstract 1
- 239000010408 film Substances 0.000 description 82
- 239000010409 thin film Substances 0.000 description 16
- 238000000576 coating method Methods 0.000 description 15
- 150000001450 anions Chemical class 0.000 description 11
- 238000010521 absorption reaction Methods 0.000 description 9
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 8
- 239000003112 inhibitor Substances 0.000 description 7
- 239000011248 coating agent Substances 0.000 description 6
- 230000006872 improvement Effects 0.000 description 5
- 239000011229 interlayer Substances 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 4
- 238000000724 energy-dispersive X-ray spectrum Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000011780 sodium chloride Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 229910001410 inorganic ion Inorganic materials 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 230000001681 protective effect Effects 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 150000001449 anionic compounds Chemical class 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 229910001412 inorganic anion Inorganic materials 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 description 2
- 239000002135 nanosheet Substances 0.000 description 2
- 231100000956 nontoxicity Toxicity 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 229910018512 Al—OH Inorganic materials 0.000 description 1
- 102000003839 Human Proteins Human genes 0.000 description 1
- 108090000144 Human Proteins Proteins 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- 229910007542 Zn OH Inorganic materials 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- SOCTUWSJJQCPFX-UHFFFAOYSA-N dichromate(2-) Chemical compound [O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O SOCTUWSJJQCPFX-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000010406 interfacial reaction Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002064 nanoplatelet Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 150000002891 organic anions Chemical class 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
Images
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
- C23C26/00—Coating not provided for in groups C23C2/00 - C23C24/00
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemical Treatment Of Metals (AREA)
Abstract
The invention discloses a preparation method of an amino acid ion intercalated ZnAl-LDHs film, which comprises the following steps: step S001, pretreating the surface of the magnesium alloy; step S002, dissolving the zinc nitrate hexahydrate solution and the aluminum nitrate nonahydrate solution in deionized water under the protection of nitrogen to form a mixed solution; step S003, dripping an organic acid solvent into the mixed solution; step S004, adding a sodium hydroxide solution into the solution, and adjusting the pH value of the solution to 10; step S005, placing the solution in a polytetrafluoroethylene autoclave for heating treatment; and S006, cleaning and drying to obtain the amino acid ion intercalated ZnAl-LDHs film. The preparation method is simple in preparation process, and the ZnAl-LDHs film with the ASP and La intercalation is prepared in situ on the magnesium alloy substrate by adopting a hydrothermal method, so that the corrosion liquid can be effectively prevented from permeating the magnesium alloy substrate, and the corrosion resistance of the magnesium alloy can be obviously improved.
Description
Technical Field
The invention relates to a preparation process of an ion intercalated ZnAl-LDHs film, in particular to a preparation method of an amino acid ion intercalated ZnAl-LDHs film.
Background
The magnesium alloy has excellent comprehensive performance and wide application, but the magnesium alloy has poor corrosion resistance in a humid environment due to active chemical properties, and an oxide film of the common magnesium alloy is generally loose and porous and cannot play an effective protection role. In order to overcome the defect of poor corrosion resistance of magnesium alloy, a protective film is coated on the surface of the magnesium alloy by adopting anodic oxidation treatment, surface coating treatment and chemical conversion film treatment technologies to prevent a magnesium alloy matrix from being oxidized, although the corrosion resistance of the magnesium alloy can be obviously improved, the obtained oxide film has strong binding capacity with the magnesium alloy matrix, but a large amount of electrolyte is used in the treatment process, so that potential harm is caused to human health and environment.
Layered Double Hydroxide (LDH) can exchange anions in the corrosive liquid with anions (such as Cl-) in the interlayer, so that the concentration of corrosive ions is reduced, and the corrosion resistance of the material is improved. The LDH film layer with the nano structure has good corrosion resistance effect on the magnesium alloy, and the LDH coating deposited on the surface of the magnesium alloy has simple process and environmental protection, and is expected to replace the traditional magnesium alloy surface treatment method. At present, magnesium alloy LDH coatings which are more researched are mainly MgAl-LDH coatings. In recent years, there has been interest in improving the corrosion resistance of magnesium alloys by preparing LDH coatings thereon (e.g. the documents Feng Peng, et al acs Applied Materials & Interfaces,2016.8, 35033-. A big disadvantage of LDH coatings is that there are very many pores between the stereo-linked LDH sheets and corrosive solutions easily penetrate into the coating, which will cause the LDH membrane layers to lose their protective effect on the substrate. The MgAl-LDH corrosion-resistant coatings prepared by the existing documents are all in a typical three-dimensional sheet structure, and the existence of the porous gaps greatly reduces the corrosion-resistant effect of the MgAl-LDH corrosion-resistant coatings. Therefore, some documents focus on methods for improving the corrosion resistance of magnesium alloys by inserting corrosion inhibitors into MgAl-LDH coatings, such as Rong-Chang Zeng, et al. journal of Materials Chemistry A,2014.2,13049-13057 and Chinese patent 201310368527.5, which describe magnesium alloy corrosion resistance improved by molybdate intercalated MgAl-LDH coatings. The corrosion inhibitor intercalated LDH coating absorbs chloride ions with erosion capacity in a corrosion medium by utilizing the exchange action between interlaminar corrosion inhibitors such as molybdate and chloride ions, so that the corrosion resistance of the corrosion inhibitor intercalated LDH coating in a NaCl medium is enhanced.
Besides MgAl-LDH, ZnAl-LDH is generally considered to have stronger corrosion resistance, so ZnAl-LDH can also be used for corrosion resistance of magnesium alloy. However, at present, inorganic anions such as nitrate, nitrite, chromate, dichromate, sulfite, etc. are mostly used to intercalate ZnAl-LDHs (e.g. TangYan et al, Surface and Coatings Technology,2019,358: 594-. Most organic ions (such as amino acid, high molecular alcohol, amine and the like) are green, nontoxic and environment-friendly, so that the development of an environment-friendly and high-performance organic ion intercalated ZnAl-LDH coating is necessary for improving the corrosion resistance of the magnesium alloy.
Disclosure of Invention
In order to solve the technical problems, aiming at the defects that an inorganic ion corrosion inhibitor is not environment-friendly and is easy to pollute the environment, the invention provides the preparation method of the ZnAl-LDHs film with the amino acid ion intercalation, which adopts organic acid as the corrosion inhibitor (such as amino acid) and can be degraded in the natural environment, has the advantages of green, no toxicity and the like, and can overcome the defect of poor environment-friendly performance of the inorganic ion corrosion inhibitor in the prior art.
The technical scheme adopted by the invention for solving the technical problem is as follows: a preparation method of an amino acid ion intercalated ZnAl-LDHs film comprises the following steps:
step S001, pretreating the surface of the magnesium alloy;
step S002, under the protection of nitrogen, zinc nitrate hexahydrate (Zn (NO)3)2·6H2O) and aluminum nitrate nonahydrate (Al (NO)3)3·9H2O) is dissolved in deionized water according to the mass ratio of 1.5:1 to prepare a mixed solution of 0.02-0.06 mol/L zinc nitrate and 0.01-0.04 mol/L aluminum nitrate;
step S003, dripping an amino acid solvent into the mixed solution obtained in the step S002;
step S004, adding a sodium hydroxide (Na (OH)) solution into the solution obtained in the step S003, and adjusting the pH value of the solution to 9-11;
step S005, placing the magnesium alloy obtained by the pretreatment in the step S001 and the solution obtained in the step S004 into a polytetrafluoroethylene autoclave for heating treatment;
and S006, washing the magnesium alloy treated in the step S005 by using deionized water, and drying in vacuum at the drying temperature of 50-70 ℃ for 10-14 hours to obtain the amino acid ion intercalated ZnAl-LDHs film.
As a further improvement of the invention, the amino acid solvent is aspartic acid (C)4H7NO4) Or sodium laurate (C)12H23NaO2) The corresponding amino acid ion intercalated ZnAl-LDHs film is ZnAl-ASP-LDHs film and ZnAl-La-LDHs film.
As a further improvement of the present invention, in step S002, 0.595g of zinc nitrate hexahydrate and 0.375g of aluminum nitrate nonahydrate are specifically weighed and dissolved in 50ml of deionized water, respectively, to form a mixed solution of 0.04mol/L of zinc nitrate and 0.02mol/L of aluminum nitrate; in the step S003, 0.266g of 0.04mol/L aspartic acid is specifically added dropwise to the mixed solution.
As a further improvement of the present invention, in step S002, 0.595g of zinc nitrate hexahydrate and 0.375g of aluminum nitrate nonahydrate are specifically weighed and dissolved in 50ml of deionized water, respectively, to form a mixed solution of 0.04mol/L of zinc nitrate and 0.02mol/L of aluminum nitrate; in the step S003, 0.444g of 0.04mol/L sodium laurate is specifically added dropwise to the mixed solution.
As a further improvement of the present invention, the step S001 specifically includes the following steps:
step S0011, selecting magnesium alloy with required size and polishing the magnesium alloy with sand paper;
s0012, placing the polished magnesium alloy in an ethanol solution for ultrasonic cleaning for 10-20 minutes, and carrying out air drying treatment;
step S0013, placing the magnesium alloy obtained in the step S0012 in 2mol/L sodium hydroxide solution for ultrasonic cleaning;
and step S0014, placing the magnesium alloy obtained in the step S0013 in an ethanol solution for ultrasonic cleaning for 5-15 minutes, and placing the magnesium alloy in an oven for drying, wherein the drying temperature is 50-70 ℃.
As a further improvement of the invention, the heating temperature of the polytetrafluoroethylene autoclave is 350-450K, and the heating time is 10-14 hours.
The invention has the beneficial effects that: the invention provides a preparation method of an amino acid ion intercalated ZnAl-LDHs film, which has simple preparation process, prepares an ASP and La intercalated ZnAl-LDHs film on a magnesium alloy substrate in situ by adopting a hydrothermal method, has compact and uniform thickness and good bonding force with the magnesium alloy substrate, and both films grow on the surface of the magnesium alloy uniformly and compactly, the ZnAl-ASP-LDHs film presents a vertically-grown nano lamellar structure, and the ZnAl-La-LDHs film presents an interlaced inclined nano lamellar structure, both have strong capacities of absorbing Cl < - > and releasing interlayer anions, can effectively prevent corrosive liquid from permeating the magnesium alloy substrate, and can obviously improve the corrosion resistance of the magnesium alloy; meanwhile, the amino acid has excellent performance, is an important raw material for forming human protein, can be degraded in natural environment, has the advantages of green and non-toxicity, and the like, compared with ZnAl-LDHs of an inorganic ion intercalation, the ZnAl-LDHs of the amino acid intercalation is green and environment-friendly, and can also protect metal, different amino acid R groups contain polar groups which take N, S, P, O and the like as central atoms, can form coordinate bonds with a metal transition state, and are adsorbed to the surface of the metal to form an organic protective film, so that the metal is prevented from being further corroded, and the self-healing function is realized.
Drawings
FIG. 1 is a diagram showing the morphology, cross-section and EDS spectra of a ZnAl-ASP-LDHs film prepared by the first embodiment of the preparation method of an amino acid ion intercalated ZnAl-LDHs film of the present invention;
FIG. 2 is a diagram showing the morphology, cross-section and EDS spectra of a ZnAl-La-LDHs film prepared by the second preparation method of an amino acid ion intercalated ZnAl-LDHs film of the present invention;
FIG. 3 is a Fourier transform infrared absorption (FT-IR) chart of ZnAl-ASP-LDHs films and ZnAl-La-LDHs films prepared correspondingly in the first embodiment and the second embodiment of the preparation method of ZnAl-LDHs films intercalated with amino acid ions of the present invention;
FIG. 4 is potentiodynamic polarization curves of ZnAl-ASP-LDHs thin films and ZnAl-La-LDHs thin films and magnesium alloy substrates prepared correspondingly in the first embodiment and the second embodiment of the preparation method of amino acid ion intercalated ZnAl-LDHs thin films of the present invention;
FIG. 5 is a graph showing the morphology and EDS spectra of a ZnAl-ASP-LDHs film prepared by the first preparation method of an amino acid ion intercalated ZnAl-LDHs film of the present invention after corrosion;
FIG. 6 is a graph showing the morphology and EDS spectra of a ZnAl-La-LDHs film prepared by the second preparation method of an amino acid ion intercalated ZnAl-LDHs film of the present invention after corrosion;
FIG. 7 shows Fourier transform infrared absorption spectra (FT-IR) of ZnAl-ASP-LDHs thin films and ZnAl-La-LDHs thin films prepared correspondingly in the first and second embodiments of the preparation method of ZnAl-LDHs thin films intercalated with amino acid ions of the present invention after corrosion.
Detailed Description
A preferred embodiment of the present invention will be described in detail below with reference to the accompanying drawings.
The first embodiment is as follows:
a preparation method of an amino acid ion intercalated ZnAl-LDHs film is characterized by comprising the following steps:
step S001, pretreating the surface of the magnesium alloy, and specifically comprises the following steps: step S0011, selecting magnesium alloy with required size and polishing the magnesium alloy with sand paper; the selected magnesium alloy was AZ31 magnesium alloy, and was cut to a size of 20mm × 25mm × 2.0mm, and then ground using 400, 800, 1200, 2000 mesh SiC sandpaper. And step S0012, placing the polished magnesium alloy in an ethanol solution for ultrasonic cleaning for 15 minutes, and carrying out cold air drying treatment. And step S0013, placing the magnesium alloy obtained in the step S0012 in a 2mol/L sodium hydroxide solution for ultrasonic cleaning. And step S0014, placing the magnesium alloy obtained in the step S0013 in an ethanol solution for ultrasonic cleaning for 10 minutes, and placing the magnesium alloy in an oven for drying, wherein the drying temperature is 60 ℃. By adopting the step to treat the surface of the magnesium alloy, impurities and oxides on the surface of the magnesium alloy can be removed, so that a film can be better prepared on the surface of the magnesium alloy.
Step S002, under the protection of nitrogen, 0.595g of zinc nitrate hexahydrate and 0.375g of aluminum nitrate nonahydrate are respectively weighed and dissolved in 50ml of deionized water to form a mixed solution of 0.04mol/L of zinc nitrate and 0.02mol/L of aluminum nitrate.
In step S003, 0.04mol/L aspartic acid (0.266 g) was added dropwise to the mixed solution obtained in step S002.
And step S004, adding 2mol/L sodium hydroxide solution into the solution obtained in the step S003, and adjusting the pH value of the solution to 10.
Step S005, placing the magnesium alloy obtained by the pretreatment in the step S001 and the solution obtained in the step S004 into a polytetrafluoroethylene autoclave for heating treatment; wherein the heating temperature of the polytetrafluoroethylene autoclave is 393K, and the heating time is 12 hours.
And S006, washing the magnesium alloy treated in the step S005 with deionized water, and drying in vacuum at 60 ℃ for 12 hours to obtain the ZnAl-ASP-LDHs film.
Example two:
the difference between this embodiment and the first embodiment is: in the step S003, 0.444g of 0.04mol/L sodium laurate is specifically added dropwise to the mixed solution. And step S004, adding 2mol/L sodium hydroxide solution into the solution obtained in the step S003, and adjusting the pH value of the solution to 10. Step S005, placing the magnesium alloy obtained by the pretreatment in the step S001 and the solution obtained in the step S004 into a polytetrafluoroethylene autoclave for heating treatment; wherein the heating temperature of the polytetrafluoroethylene autoclave is 393K, and the heating time is 12 hours. And S006, washing the magnesium alloy treated in the step S005 by using deionized water, and drying in vacuum at 60 ℃ for 12 hours to obtain the ZnAl-La-LDHs film.
The ZnAl-ASP-LDHs films and the ZnAl-La-LDHs films prepared correspondingly in the first and second examples were subjected to corrosion resistance tests:
referring to fig. 1 and 2, (a) and 2) of fig. 1 and 2 show that the ZnAl-ASP-LDHs film and the ZnAl-La-LDHs film are densely grown on the surface of the magnesium alloy, respectively, and it can be seen from (b) and 2 (e) of their microscopic structures that the structures of the ZnAl-ASP-LDHs film and the ZnAl-La-LDHs film respectively show uniform and dense nano-platelet structures. The nano sheets of the ZnAl-ASP-LDHs film vertically and alternately grow on the surface of the magnesium alloy, and the ZnAl-La-LDHs film presents an inclined and alternate structure, so that the permeation of corrosive ions can be effectively blocked, and the substrate is prevented from being exposed to corrosive environment, thereby improving the corrosion resistance of the magnesium alloy. By analyzing the chemical compositions of the ASP and La anion intercalated ZnAl-LDHs films (fig. 1 (C) and fig. 2 (f)) by dot scanning, it can be seen that the ZnAl-ASP-LDHs films are mainly composed of Zn, Al, C, N and O elements, and the Mg content is mainly derived from the substrate. The main components of the ZnAl-La-LDHs film are Zn, Al, C, N and O elements. Although the organic anions mainly consist of C, O, H elements, although a large amount of the elements exist in the air, the C, O peak position of the ZnAl-LDHs film intercalated by the ASP and the La is obviously stronger than that of the ZnAl-LDHs film intercalated by the inorganic anions in the prior work, which shows that the ZnAl-LDHs film intercalated by the ASP and the La is successfully synthesized on the surface of the magnesium alloy. As can be seen from the sectional views of the ZnAl-ASP-LDHs film and the ZnAl-La-LDHs film, the LDHs film grows on the surface of the magnesium alloy compactly and uniformly, and has strong adhesive force to the magnesium alloy substrate. The thicknesses of the ZnAl-ASP-LDHs film and the ZnAl-La-LDHs film are respectively 15.65 mu m and 17.39 mu m, and the thicker the film is, the more the corrosive Cl-can be prevented from permeating into the magnesium alloy substrate, which shows that the ZnAl-LDHs film can effectively protect the magnesium alloy.
Referring to FIG. 3, at 3694cm-1Absorption band ofM-OH (e.g., Zn-OH, Al-OH, and Mg-OH) caused by lattice vibrations of LDHs laminates is approximately 3450cm in length by surface absorption, water molecules, and interlayer water molecules-1The absorption band at (B) corresponds to O-H at 1637cm-1The absorption band of (b) can be attributed to bending vibration of water molecules. The spectrum of the ZnAl-ASP-LDHs film is 1378cm-1There are characteristic absorption bands of asymmetric and symmetric tensile vibration of-COOH. 2849cm in ZnAl-La-LDHs film-1、2918cm-1The spectrum of (A) is due to tensile vibration of the alkyl C-H group at 1409cm-1The absorption peaks at (a) are related to the symmetric and asymmetric oscillations of the COO-group. The result shows that ASP and La anions are successfully intercalated into the ZnAl-LDHs film.
Referring to FIG. 4, the corrosion potentials (E) of the AZ31 magnesium alloy, ZnAl-ASP-LDHs thin film and ZnAl-La-LDHs thin film, the AZ31 magnesium alloy substrate, ZnAl-ASP-LDHs thin film and ZnAl-La-LDHs thin film, and the polarization curve of zeta potential were measured by immersing the AZ31 magnesium alloy, ZnAl-ASP-LDHs thin film and ZnAl-La-LDHs thin film in 3.5 wt.% NaCl aqueous solutioncorr) The corrosion potential is gradually increased from-1.511V to-1.074V (V/SCE), which indicates that the interfacial reaction is more difficult, and the corrosion resistance is gradually enhanced, wherein the corrosion resistance of the ZnAl-La-LDHs film is the best. By observing the corrosion current density (i)corr) A variation of (a) which iscorrFrom 7.472X 10-5Reduced to 2.772 × 10-7A/cm2The corrosion current density is gradually reduced, which shows that the reaction speed between interfaces is gradually reduced and the corrosion resistance is gradually enhanced. Wherein, compared with the corrosion current density of the magnesium alloy substrate, the corrosion current density of the ZnAl-LDHs film with the inserted ASP and La anions is reduced by two orders of magnitude. The result shows that the LDHs prepared on the surface of the magnesium alloy by the one-step method effectively improves the corrosion resistance of the AZ31 magnesium alloy substrate, and the corrosion resistance of the ZnAl-LDHs film with the ASP/La intercalation is superior to that of the ZnAl-NO film in the prior art3 -Corrosion resistance of LDHs films; the corrosion resistance of the LDHs film prepared by inserting amino acid ions is further enhanced, and the performance of the ZnAl-LDHs film with La anions inserted is optimal.
Referring to FIGS. 5 and 6, the ZnAl-ASP-LDHs film prepared in example one and the ZnAl-La-LDHs film prepared in example two were immersed in 3After soaking in a 5 wt.% NaCl aqueous solution for 168 hours, scanning by an electron microscope, and scanning morphology graphs of intercalated ZnAl-LDHs films of ASP (shown in (a) in FIG. 5) and La (shown in (d) in FIG. 6) under the electron microscope, so that the surface morphology of the magnesium alloy after corrosion is very flat and has no obvious corrosion traces. The morphology graphs of ZnAl-ASP-LDHs thin films of 5 mu m (figure 5 (b)) and 1 mu m (figure 5 (c)) can show that the surfaces of the nanosheets are basically and completely dissolved, which is attributed to the dissolution of the Mg alloy substrate and the LDH, and the dissolved crystals are flatly covered on the surface of the magnesium alloy, which can also slow down the corrosion degree of the magnesium alloy. The morphology graphs of the ZnAl-La-LDHs film with the thickness of 5 mu m (figure 6 (e)) and the film with the thickness of 1 mu m (figure 6 (f)) can show that the nano flaky structure is still a complete nano flaky structure and is uniformly and densely covered on the surface of the magnesium alloy. Compared with the shape before corrosion, the nano flaky structure tends to be flat and can be attributed to ionic Cl in the corrosion process-The result of the exchange also shows that after interlayer anions of the ZnAl-La-LDHs film are destroyed, Cl in the corrosive liquid is absorbed by anion exchange-Thereby playing a role in protecting the magnesium alloy. It can be seen from the point scan analysis that the chemical composition of the etched ASP/La intercalated ZnAl-LDHs film (fig. 5 (c) and fig. 6 (f)) has Cl element in comparison with the film before etching, which is attributed to the fact that the amino acid ion intercalated ZnAl-LDHs film has Cl element when there is aggressive Cl element-When the adhesive is used, the adhesive can be effectively absorbed and retained between the laminates.
Referring to FIG. 7, after immersing the ZnAl-ASP-LDHs thin film prepared in example one and the ZnAl-La-LDHs thin film prepared in example two in a 3.5 wt.% NaCl aqueous solution for 168 hours, an infrared diffraction pattern was obtained using a Fourier transform infrared spectrometer, and it can be seen that the ZnAl-LDHs thin films of different anions were found to be 3696cm in thickness-1Has a distinct absorption band due to Mg (OH) formed after etching2After precipitation and corrosion, the absorption band of amino acid ions still exists, which shows that the structure of the film can effectively resist corrosion. Wherein, the corrosion resistance of the ZnAl-LDHs film with the La intercalation is better than that of the ZnAl-LDHs film with the ASP intercalation.
The invention provides a preparation method of an amino acid ion intercalated ZnAl-LDHs film, which has simple preparation process, prepares an ASP and La intercalated ZnAl-LDHs film on a magnesium alloy substrate in situ by adopting a hydrothermal method, has compact and uniform thickness and good bonding force with the magnesium alloy substrate, and both films grow on the surface of the magnesium alloy uniformly and compactly, the ZnAl-ASP-LDHs film presents a vertically-grown nano flaky structure, and the ZnAl-La-LDHs film presents a mutually staggered inclined nano flaky structure, both have strong capacities of absorbing Cl < - > and releasing interlayer anions, can effectively prevent corrosive liquid from permeating the magnesium alloy substrate, and can obviously improve the corrosion resistance of the magnesium alloy.
In the previous description, numerous specific details were set forth in order to provide a thorough understanding of the present invention. The foregoing description is only a preferred embodiment of the invention, which can be embodied in many different forms than described herein, and therefore the invention is not limited to the specific embodiments disclosed above. And that those skilled in the art may, using the methods and techniques disclosed above, make numerous possible variations and modifications to the disclosed embodiments, or modify equivalents thereof, without departing from the scope of the claimed embodiments. Any simple modification, equivalent change and modification of the above embodiments according to the technical essence of the present invention are within the scope of the technical solution of the present invention.
Claims (6)
1. A preparation method of an amino acid ion intercalated ZnAl-LDHs film is characterized by comprising the following steps:
step S001, pretreating the surface of the magnesium alloy;
step S002, under the protection of nitrogen, zinc nitrate hexahydrate (Zn (NO)3)2·6H2O) and aluminum nitrate nonahydrate (Al (NO)3)3·9H2O) is dissolved in deionized water according to the mass ratio of 1.5:1 to prepare a mixed solution of 0.02-0.06 mol/L zinc nitrate and 0.01-0.04 mol/L aluminum nitrate;
step S003, dripping an amino acid solvent into the mixed solution obtained in the step S002;
step S004, adding a sodium hydroxide (Na (OH)) solution into the solution obtained in the step S003, and adjusting the pH value of the solution to 9-11;
step S005, placing the magnesium alloy obtained by the pretreatment in the step S001 and the solution obtained in the step S004 into a polytetrafluoroethylene autoclave for heating treatment;
and S006, washing the magnesium alloy treated in the step S005 by using deionized water, and drying in vacuum at the drying temperature of 50-70 ℃ for 10-14 hours to obtain the amino acid ion intercalated ZnAl-LDHs film.
2. The method for preparing ZnAl-LDHs film intercalated by amino acid ions as claimed in claim 1, which is characterized in that: the amino acid solvent is aspartic acid (C)4H7NO4) Or sodium laurate (C)12H23NaO2) The corresponding amino acid ion intercalated ZnAl-LDHs film is ZnAl-ASP-LDHs film and ZnAl-La-LDHs film.
3. The method for preparing ZnAl-LDHs film intercalated by amino acid ions as claimed in claim 2, which is characterized in that: in the step S002, 0.595g of zinc nitrate hexahydrate and 0.375g of aluminum nitrate nonahydrate are respectively weighed and dissolved in 50ml of deionized water to form a mixed solution of 0.04mol/L of zinc nitrate and 0.02mol/L of aluminum nitrate; in the step S003, 0.266g of 0.04mol/L aspartic acid is specifically added dropwise to the mixed solution.
4. The method for preparing ZnAl-LDHs film intercalated by amino acid ions as claimed in claim 2, which is characterized in that: in the step S002, 0.595g of zinc nitrate hexahydrate and 0.375g of aluminum nitrate nonahydrate are respectively weighed and dissolved in 50ml of deionized water to form a mixed solution of 0.04mol/L of zinc nitrate and 0.02mol/L of aluminum nitrate; in the step S003, 0.444g of 0.04mol/L sodium laurate is specifically added dropwise to the mixed solution.
5. The method for preparing ZnAl-LDHs film intercalated by amino acid ions as claimed in claim 1, which is characterized in that: the step S001 specifically includes the steps of:
step S0011, selecting magnesium alloy with required size and polishing the magnesium alloy with sand paper;
s0012, placing the polished magnesium alloy in an ethanol solution for ultrasonic cleaning for 10-20 minutes, and carrying out air drying treatment;
step S0013, placing the magnesium alloy obtained in the step S0012 in 2mol/L sodium hydroxide solution for ultrasonic cleaning;
and step S0014, placing the magnesium alloy obtained in the step S0013 in an ethanol solution for ultrasonic cleaning for 5-15 minutes, and placing the magnesium alloy in an oven for drying, wherein the drying temperature is 50-70 ℃.
6. The method for preparing ZnAl-LDHs film intercalated by amino acid ions as claimed in claim 1, which is characterized in that: the heating temperature of the polytetrafluoroethylene autoclave is 350-450K, and the heating time is 10-14 hours.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113073322A (en) * | 2021-03-29 | 2021-07-06 | 中国科学院宁波材料技术与工程研究所 | Magnesium alloy surface corrosion-resistant super-hydrophobic film layer and preparation method and application thereof |
| CN113549913A (en) * | 2021-07-22 | 2021-10-26 | 重庆大学 | Preparation method and application of ternary MgAlLa-LDHs film layer on surface of magnesium alloy |
| CN113846289A (en) * | 2021-09-24 | 2021-12-28 | 厦门大学 | Method for preparing layered double-hydroxide film based on co-sputtering intermediate film in-situ conversion |
| CN114774863A (en) * | 2022-04-13 | 2022-07-22 | 佛山科学技术学院 | Li-Al LDH membrane on surface of magnesium alloy and rapid preparation method thereof |
| CN115613103A (en) * | 2022-11-07 | 2023-01-17 | 南京工程学院 | Micro-arc magnesium oxide alloy surface hydrophobic Mg-Al hydrotalcite film and one-step preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20120322647A1 (en) * | 2011-06-16 | 2012-12-20 | Beijing University Of Chemical Technology | Method for enhancing heterogeneous asymmetric selectivity and catalytic activity |
| CN103695871A (en) * | 2013-08-22 | 2014-04-02 | 山东科技大学 | Corrosion-inhibition anion intercalation hydrotalcite film prepared by magnesium alloy surface hydro-thermal deposition method |
| CN105439188A (en) * | 2015-11-11 | 2016-03-30 | 山西大学 | Preparation method of hydrotalcite-like compound nanosheet |
| CN106693044A (en) * | 2016-12-29 | 2017-05-24 | 山东科技大学 | Method for preparing glutamate intercalation hydrotalcite medicinal magnesium alloy coating |
-
2020
- 2020-09-04 CN CN202010920501.7A patent/CN112176338A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20120322647A1 (en) * | 2011-06-16 | 2012-12-20 | Beijing University Of Chemical Technology | Method for enhancing heterogeneous asymmetric selectivity and catalytic activity |
| CN103695871A (en) * | 2013-08-22 | 2014-04-02 | 山东科技大学 | Corrosion-inhibition anion intercalation hydrotalcite film prepared by magnesium alloy surface hydro-thermal deposition method |
| CN105439188A (en) * | 2015-11-11 | 2016-03-30 | 山西大学 | Preparation method of hydrotalcite-like compound nanosheet |
| CN106693044A (en) * | 2016-12-29 | 2017-05-24 | 山东科技大学 | Method for preparing glutamate intercalation hydrotalcite medicinal magnesium alloy coating |
Non-Patent Citations (3)
| Title |
|---|
| JIALING CHEN ，ET AL: "Corrosion resistance of a self-healing rose-like MgAl-LDH coating intercalated with aspartic acid on AZ31 Mg alloy", 《PROGRESS IN ORGANIC COATINGS》 * |
| YAN TANG，ET AL: "A comparative study and optimization of corrosion resistance of ZnAl", 《SURFACE & COATINGS TECHNOLOGY》 * |
| 全贞兰: "天冬氨酸插层ZnAl双金属氢氧化物的制备及其对铜的缓蚀性能研究", 《腐蚀科学与防护技术》 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113073322A (en) * | 2021-03-29 | 2021-07-06 | 中国科学院宁波材料技术与工程研究所 | Magnesium alloy surface corrosion-resistant super-hydrophobic film layer and preparation method and application thereof |
| CN113549913A (en) * | 2021-07-22 | 2021-10-26 | 重庆大学 | Preparation method and application of ternary MgAlLa-LDHs film layer on surface of magnesium alloy |
| CN113846289A (en) * | 2021-09-24 | 2021-12-28 | 厦门大学 | Method for preparing layered double-hydroxide film based on co-sputtering intermediate film in-situ conversion |
| WO2023045042A1 (en) * | 2021-09-24 | 2023-03-30 | 厦门大学 | Method for preparing layered double hydroxide film on the basis of in situ conversion of co-sputtering intermediate film |
| CN114774863A (en) * | 2022-04-13 | 2022-07-22 | 佛山科学技术学院 | Li-Al LDH membrane on surface of magnesium alloy and rapid preparation method thereof |
| CN114774863B (en) * | 2022-04-13 | 2023-11-14 | 佛山科学技术学院 | Li-Al LDH film on magnesium alloy surface and rapid preparation method thereof |
| CN115613103A (en) * | 2022-11-07 | 2023-01-17 | 南京工程学院 | Micro-arc magnesium oxide alloy surface hydrophobic Mg-Al hydrotalcite film and one-step preparation method and application thereof |
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