CN113584470A - Magnesium-lithium alloy surface anticorrosion treatment method - Google Patents
Magnesium-lithium alloy surface anticorrosion treatment method Download PDFInfo
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- 239000001989 lithium alloy Substances 0.000 title claims abstract description 91
- 229910000733 Li alloy Inorganic materials 0.000 title claims abstract description 85
- GCICAPWZNUIIDV-UHFFFAOYSA-N lithium magnesium Chemical compound [Li].[Mg] GCICAPWZNUIIDV-UHFFFAOYSA-N 0.000 title claims abstract description 85
- 238000000034 method Methods 0.000 title claims abstract description 18
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 60
- 238000006243 chemical reaction Methods 0.000 claims abstract description 25
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 16
- 229910000029 sodium carbonate Inorganic materials 0.000 claims abstract description 16
- 238000001816 cooling Methods 0.000 claims abstract description 7
- 230000035484 reaction time Effects 0.000 claims description 24
- 238000005406 washing Methods 0.000 claims description 22
- 239000012153 distilled water Substances 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 6
- 239000003513 alkali Substances 0.000 claims description 6
- 238000004140 cleaning Methods 0.000 claims description 6
- 244000137852 Petrea volubilis Species 0.000 claims description 2
- 238000000227 grinding Methods 0.000 claims description 2
- 238000002203 pretreatment Methods 0.000 claims 1
- 238000005260 corrosion Methods 0.000 abstract description 25
- 230000007797 corrosion Effects 0.000 abstract description 24
- 239000000758 substrate Substances 0.000 abstract description 18
- 239000000243 solution Substances 0.000 description 41
- 239000011159 matrix material Substances 0.000 description 15
- 238000004381 surface treatment Methods 0.000 description 10
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 9
- 230000005587 bubbling Effects 0.000 description 8
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical group [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 8
- 238000005498 polishing Methods 0.000 description 8
- 238000005336 cracking Methods 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 229910019400 Mg—Li Inorganic materials 0.000 description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 6
- 239000000347 magnesium hydroxide Substances 0.000 description 5
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 5
- 239000012535 impurity Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 239000003518 caustics Substances 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000000840 electrochemical analysis Methods 0.000 description 3
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 3
- 229910052808 lithium carbonate Inorganic materials 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000002791 soaking Methods 0.000 description 3
- 239000011780 sodium chloride Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- 229910000861 Mg alloy Inorganic materials 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 238000005536 corrosion prevention Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000000627 alternating current impedance spectroscopy Methods 0.000 description 1
- 238000000231 atomic layer deposition Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000007772 electroless plating Methods 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 229910001234 light alloy Inorganic materials 0.000 description 1
- 239000003562 lightweight material Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 238000007745 plasma electrolytic oxidation reaction Methods 0.000 description 1
- 238000007750 plasma spraying Methods 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
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- 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
- C23C22/60—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 alkaline aqueous solutions with pH greater than 8
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- Chemical & Material Sciences (AREA)
- General 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 magnesium-lithium alloy surface anticorrosion treatment method, which comprises the following steps: step one, preparing 0.1-2 wt% Na2CO3The solution is used as a hydrothermal reaction solution; and secondly, immersing the magnesium-lithium alloy into the hydrothermal reaction solution, carrying out hydrothermal reaction for 1-3 h at the reaction temperature of 110-130 ℃, cooling to room temperature, and obtaining a film on the surface of the magnesium-lithium alloy. The method can generate a uniform and compact film layer on the surface of the magnesium-lithium alloy substrate so as to improve the corrosion resistance of the magnesium-lithium alloy.
Description
Technical Field
The invention relates to magnesium-lithium alloy surface treatment, in particular to a magnesium-lithium alloy surface anticorrosion treatment method.
Background
The magnesium-lithium alloy belongs to magnesium alloys, is the alloy with the smallest density at present, is the lightest metal structural material in the current industrial application, and is called as ultra-light alloy. The composite material has the advantages of high specific strength, high specific rigidity, large specific modulus, strong impact load bearing capacity, good shock resistance and high-energy particle penetration resistance, good ductility and plasticity and the like. The development of lightweight materials and products is one of effective measures for solving the current resource shortage, the magnesium-lithium alloy can be subjected to plastic processing forming at normal temperature, casting forming and semi-solid injection molding, the defect that other magnesium alloys cannot be subjected to cold processing is overcome, the excellent comprehensive performance of the magnesium-lithium alloy becomes one of the most ideal weight-reducing structural materials, more possibilities are provided for aerospace, automobile, weapon industry, nuclear industry, 3C industry and medical treatment which have urgent needs for material weight reduction, and the magnesium-lithium alloy has huge development potential and industrial application prospect.
However, since the magnesium-lithium alloy consists of magnesium and lithium, and the chemical activity of magnesium and lithium and the standard electrode potential thereof are both at a low level, the corrosion resistance of magnesium-lithium alloy is poor, and a loose and porous oxide film is easily formed on the surface of the magnesium-lithium alloy in the atmosphere, so atmospheric corrosion and contact corrosion are easily caused. And the magnesium-lithium alloy has the defects of soft texture, low hardness and the like, and the large-scale application of the magnesium-lithium alloy in industry and civilian use is greatly restricted, so that the research of the surface protection method of the magnesium-lithium alloy is indispensable. At present, the surface protection and corrosion prevention method of the magnesium-lithium alloy mainly comprises the following steps: anodic oxidation, micro-arc oxidation, chemical conversion, metal plating (electroplating, electroless plating), coating application, and the like. Other methods are as follows: plasma spraying, plasma vapor deposition, atomic layer deposition, diffusion treatment, laser surface alloy modification and the like.
Disclosure of Invention
The invention aims to provide a magnesium-lithium alloy surface anticorrosion treatment method, which can generate a uniform and compact film layer on the surface of a magnesium-lithium alloy substrate so as to improve the corrosion resistance of the magnesium-lithium alloy.
The magnesium-lithium alloy surface anticorrosion treatment method comprises the following steps:
step one, preparing 0.1-2 wt% Na2CO3The solution is used as a hydrothermal reaction solution;
and secondly, immersing the magnesium-lithium alloy into the hydrothermal reaction solution, carrying out hydrothermal reaction for 1-3 h at the reaction temperature of 110-130 ℃, cooling to room temperature, and obtaining a film layer on the surface of the magnesium-lithium alloy.
Further, Na in the step one2CO3The concentration of the solution was 1 wt%.
Further, the reaction temperature in the second step is 120 ℃, and the reaction time is 1 h.
Further, the magnesium-lithium alloy is pretreated before being immersed in the hydrothermal reaction solution, and the pretreatment comprises the following specific steps: firstly, grinding the surface of the magnesium-lithium alloy by using sand paper, then ultrasonically cleaning the magnesium-lithium alloy by using absolute ethyl alcohol, then carrying out acid washing and alkali washing on the magnesium-lithium alloy, washing the magnesium-lithium alloy by using distilled water, and drying the magnesium-lithium alloy for later use.
Compared with the prior art, the invention has the following beneficial effects.
1. According to the invention, through special limitation on the hydrothermal reaction temperature, the reaction time, the reaction solution and the concentration, a compact and uniform anticorrosive film layer is ensured to be generated on the surface of the magnesium-lithium alloy substrate, the film layer is magnesium hydroxide, the film value is higher, the anticorrosive performance is stronger, the purpose of protecting the magnesium-lithium alloy substrate is achieved, and the anticorrosive performance of the magnesium-lithium alloy is improved.
2. The invention adopts a hydrothermal method to prepare the film layer on the surface of the magnesium-lithium alloy, has simple operation and low requirement on equipment, and adopts Na2CO3The solution is used as a hydrothermal reaction solution, is convenient to prepare, has low cost, has small harm to the environment and meets the requirement of environmental protection. The generated film is more compact, the bonding force between the film and the substrate is strong, the size is basically not changed, and the corrosion resistance and the insulating property of the magnesium-lithium alloy are greatly improved by simple operation.
Drawings
FIG. 1 is a microscopic morphology of a film layer prepared under different reaction times in the first embodiment of the present invention, wherein the reaction time of (a) is 1h, the reaction time of (b) is 2h, and the reaction time of (c) is 3 h;
FIG. 2 is an XRD pattern of a film prepared under different reaction times in the substrate and in the first example;
FIG. 3 is a Bode plot of the impedance of the matrix and the Mg-Li alloy produced in example one at different reaction times;
FIG. 4 is a graph of the phase angle of the resistivity of the matrix and the magnesium lithium alloy produced in example one at different reaction times;
FIG. 5 is a microscopic morphology of a film layer obtained at different reaction temperatures in example two of the present invention, wherein the reaction temperature in (d) is 110 ℃, (e) is 120 ℃, and (f) is 130 ℃;
FIG. 6 is XRD patterns of the substrate and the film prepared in example two under different reaction temperatures;
FIG. 7 is a Bode plot of the impedance of the matrix and the Mg-Li alloy prepared in example II at different reaction temperatures;
FIG. 8 is a graph of the phase angle of the resistance of the magnesium lithium alloy produced at different reaction temperatures in the matrix and example two;
FIG. 9 is a microscopic morphology of a film formed by the reaction solution with a concentration of 0.1 wt% in the third example of the present invention;
FIG. 10 is a microscopic morphology of a film formed by the reaction solution with a concentration of 0.5 wt% in the third example of the present invention;
FIG. 11 is a microscopic morphology of a film prepared by the reaction solution with a concentration of 1 wt% in the third example of the present invention;
FIG. 12 is a microscopic morphology of a film prepared by the reaction solution with a concentration of 2 wt% in the third example of the present invention;
FIG. 13 is XRD patterns of the substrate and the film prepared in example III under different concentrations of the reaction solution;
FIG. 14 is a Bode plot of the impedance of the matrix and the Mg-Li alloy prepared in example III at different concentrations of the reaction solution;
FIG. 15 is a graph of the phase angle of the impedance of the matrix and the Mg-Li alloy prepared in example III under different concentrations of the reaction solution;
FIG. 16 is a graph showing polarization comparison between a Mg-Li alloy and a matrix according to example four;
FIG. 17 is a graph showing the corrosion performance results of the surface film layer of the Mg-Li alloy prepared in example IV of the present invention.
Detailed Description
The present invention will be described in detail with reference to the accompanying drawings.
The embodiment I is a magnesium-lithium alloy surface anticorrosion treatment method, which comprises the following steps:
step one, preparing 1 wt% Na2CO3The solution is used as a hydrothermal reaction solution, and the Na2CO3The solution is composed of distilled water and Na2CO3Composition is carried out;
and step two, pretreating the magnesium-lithium alloy, sequentially polishing the surface of the magnesium-lithium alloy by using 400-1000 # abrasive paper, ultrasonically cleaning the magnesium-lithium alloy by using absolute ethyl alcohol after polishing, then carrying out acid washing and alkali washing on the magnesium-lithium alloy to remove oil stains and impurities, washing the magnesium-lithium alloy by using distilled water, and drying the magnesium-lithium alloy for later use.
And (3) immersing the pretreated magnesium-lithium alloy into an inner container of an autoclave filled with 30ml of the hydrothermal reaction solution prepared in the first step, putting the inner container into an oven, setting the hydrothermal reaction temperature to be 120 ℃, setting the hydrothermal reaction time to be 1h, 2h and 3h respectively, and heating along with the oven. And after the hydrothermal reaction is finished, cooling the sample to room temperature along with the box, taking out the sample, washing the sample with a large amount of distilled water, and drying the sample with cold air.
The sample after the hydrothermal reaction is not subjected to any treatment, and the microstructure morphology of the film layer is observed by adopting a scanning electron microscope, referring to fig. 1, on the premise that the reaction temperature and the concentration of the reaction solution are not changed, the microstructure morphology of the film layer is different due to different reaction times. The same points under different reaction time conditions were observed under high power conditions: the film layer is in a leaf-shaped structure, is a typical magnesium hydroxide structure, and is generated by flower-cluster-shaped bubbles. The difference is that when the hydrothermal reaction time is 1h, the film layer is uniform and compact, bubbles are generated on the surface of the film layer, but the bubble cracking phenomenon does not exist. When the hydrothermal reaction time is 2 hours, the number of blisters on the surface of the film layer becomes large relative to the 1 hour condition, and a small number of blisters are cracked. When the hydrothermal reaction time is 3 hours, the surface of the film layer is covered by a large number of bubbles, the bubbles are basically completely cracked to form a large number of cracks, the openings of the cracks are large, the bonding force between the film layer and a matrix is reduced, new corrosive substances are generated at the cracked parts of the bubbles, and the substances are loose and are not dense.
The crystal structure and the components of the film layer are tested by XRD, the detection result is shown in figure 2, and compared with a matrix which is not subjected to surface treatment, the samples subjected to hydrothermal reaction at different times have more substances such as lithium hydroxide, magnesium hydroxide and lithium carbonate.
The corrosion resistance was evaluated by electrochemical tests using 0.05mol/L NaCl solution to simulate marine corrosive environment, and the results are shown in fig. 3 and 4, where the samples treated with different reaction times had higher impedance values than the substrate compared to the substrate without surface treatment, and the film value of the sample prepared with 2h hydrothermal reaction time was improved by three orders of magnitude compared to the substrate. The resistance value of the film layer is increased and the corrosion resistance is enhanced along with the increase of the hydrothermal reaction time, but after 2 hours, the time is increased, the resistance value of the film layer is reduced and the corrosion resistance is reduced, but compared with a matrix, the film still has certain corrosion resistance in a short time.
In a second embodiment, a magnesium-lithium alloy surface corrosion prevention treatment method includes the following steps:
step one, preparing 1 wt% Na2CO3The solution is used as a hydrothermal reaction solution, and the Na2CO3The solution is composed of distilled water and Na2CO3Composition is carried out;
and step two, pretreating the magnesium-lithium alloy, sequentially polishing the surface of the magnesium-lithium alloy by using 400-1000 # abrasive paper, ultrasonically cleaning the magnesium-lithium alloy by using absolute ethyl alcohol after polishing, then carrying out acid washing and alkali washing on the magnesium-lithium alloy to remove oil stains and impurities, washing the magnesium-lithium alloy by using distilled water, and drying the magnesium-lithium alloy for later use.
And (3) immersing the pretreated magnesium-lithium alloy into an inner container of an autoclave filled with 30ml of the hydrothermal reaction solution prepared in the first step, putting the inner container into an oven, setting the hydrothermal reaction temperature at 110 ℃, 120 ℃ and 130 ℃, setting the hydrothermal reaction time at 2h respectively, and raising the temperature along with the oven. And after the hydrothermal reaction is finished, cooling the sample to room temperature along with the box, taking out the sample, washing the sample with a large amount of distilled water, and drying the sample with cold air.
The sample after the hydrothermal reaction is not subjected to any treatment, and the microstructure morphology of the film layer is observed by using a scanning electron microscope, referring to fig. 5, similar to the example, on the premise that the reaction time and the concentration of the reaction solution are not changed, the microstructure morphology of the film layer is different due to different reaction temperatures. Under the condition of a high power lens, the film layer is observed to be in a lamellar structure, is a typical magnesium hydroxide structure and is generated by flower-like bubbles. When the hydrothermal reaction temperature is 110 ℃, the film layer is uniform and compact, bubbles are generated on the surface of the film layer, and the cracking phenomenon exists. When the hydrothermal reaction temperature is 120 ℃, the bubbling on the surface of the film layer is less relative to the cracking phenomenon under the condition of 110 ℃. When the hydrothermal reaction temperature is 130 ℃, the film surface can be observed to be completely cracked, a large number of cracks are formed, the openings of the cracks are huge, new corrosive substances are generated at the bubbling cracking part, and the substances are loose and are not dense.
The crystal structure and the components of the film layer are tested by XRD, the detection result is shown in figure 6, compared with a matrix which is not subjected to surface treatment, the sample subjected to hydrothermal reaction at different temperatures has more lithium hydroxide, magnesium hydroxide and lithium carbonate, but only the magnesium hydroxide is detected in an XRD diffraction peak under the condition of 130 ℃.
The corrosion resistance was evaluated by electrochemical tests using 0.05mol/L NaCl solution to simulate marine corrosive environment, and the results are shown in fig. 7 and 8, where the samples treated at different reaction temperatures were higher than the resistance of the substrate compared to the substrate without surface treatment, and the film value of the sample prepared at 120 ℃ was improved by three orders of magnitude compared to the substrate. The resistance value of the film layer is increased and the corrosion resistance is enhanced along with the increase of the hydrothermal reaction temperature, but after the temperature reaches 120 ℃, the resistance value of the film layer is reduced and the corrosion resistance is reduced, but compared with a matrix, the film layer still has certain corrosion resistance in a short time.
In a third embodiment, a magnesium-lithium alloy surface anticorrosion treatment method includes the following steps:
step one, preparing Na with the concentration of 0.1 wt%, 0.5 wt%, 1 wt% and 2 wt%2CO3The solution is used as a hydrothermal reaction solution, and the Na2CO3The solution is composed of distilled water and Na2CO3Composition is carried out;
and step two, pretreating the magnesium-lithium alloy, sequentially polishing the surface of the magnesium-lithium alloy by using 400-1000 # abrasive paper, ultrasonically cleaning the magnesium-lithium alloy by using absolute ethyl alcohol after polishing, then carrying out acid washing and alkali washing on the magnesium-lithium alloy to remove oil stains and impurities, washing the magnesium-lithium alloy by using distilled water, and drying the magnesium-lithium alloy for later use.
And (3) immersing the pretreated magnesium-lithium alloy into an inner container of an autoclave filled with 30ml of the hydrothermal reaction solution prepared in the first step, putting the inner container into an oven, setting the hydrothermal reaction temperature at 120 ℃, setting the hydrothermal reaction time at 2 hours respectively, and raising the temperature along with the oven. And after the hydrothermal reaction is finished, cooling the sample to room temperature along with the box, taking out the sample, washing the sample with a large amount of distilled water, and drying the sample with cold air.
The sample after the hydrothermal reaction is not subjected to any treatment, and the microstructure of the film layer is observed by using a scanning electron microscope, as shown in fig. 9 to 12, similar to the embodiment, on the premise that the reaction time and the reaction temperature are not changed, the hydrothermal reaction solutions with different concentrations cause the difference in the microstructure of the film layer. Under the condition of a high power lens, the film layer is observed to be in a lamellar structure, is a typical magnesium hydroxide structure and is generated by flower-like bubbles. When the concentration of the hydrothermal reaction solution is 0.1 wt%, a large amount of bubbles are generated on the surface of the film layer, and a large amount of cracks are generated; when the hydrothermal reaction concentration is 0.5 wt%, bubbling on the surface of the film layer is reduced relative to the 0.1 wt% condition cracking phenomenon, and small bubbles aggregate and grow. When the hydrothermal reaction concentration is 1 wt%, the bubbling on the surface of the film layer is less prone to cracking phenomenon with respect to the 0.5 wt% condition, and the bubbling becomes large. When the hydrothermal reaction concentration is 2 wt%, it can be observed that the bubbling on the surface of the film layer becomes large, the bubbling cracks seriously, and new corrosive substances are generated at the bubbling cracking part, and the substances are loose and not dense.
The crystal structure and the components of the film layer are tested by XRD, and the detection results are shown in FIG. 13, compared with the matrix without surface treatment, the samples treated by the hydrothermal reaction solution with different concentrations have more substances such as lithium hydroxide, magnesium hydroxide and lithium carbonate.
The corrosion resistance was evaluated by electrochemical tests using 0.05mol/L NaCl solution to simulate marine corrosive environment, and the results are shown in fig. 14 and 15, and compared with the substrate without surface treatment, the samples treated with the hydrothermal reaction solutions of different concentrations all had higher impedance values than the substrate, wherein the film value of the sample prepared under the condition of 1 wt% hydrothermal reaction concentration was improved by three orders of magnitude compared with the substrate. The resistance value of the film layer is increased and the corrosion resistance is enhanced along with the increase of the concentration of the hydrothermal reaction solution, but after the concentration reaches 1 wt%, the resistance value of the film layer is reduced and the corrosion resistance is reduced, but compared with a matrix, the film layer still has certain corrosion resistance in a short time.
The fourth embodiment provides a magnesium-lithium alloy surface anticorrosion treatment method, which comprises the following steps:
step one, preparing 1 wt% Na2CO3The solution is used as a hydrothermal reaction solution, and the Na2CO3The solution is composed of distilled water and Na2CO3Composition is carried out;
and step two, pretreating the magnesium-lithium alloy, sequentially polishing the surface of the magnesium-lithium alloy by using 400-1000 # abrasive paper, ultrasonically cleaning the magnesium-lithium alloy by using absolute ethyl alcohol after polishing, then carrying out acid washing and alkali washing on the magnesium-lithium alloy to remove oil stains and impurities, washing the magnesium-lithium alloy by using distilled water, and drying the magnesium-lithium alloy for later use.
And (3) immersing the pretreated magnesium-lithium alloy into an inner container of an autoclave filled with 30ml of the hydrothermal reaction solution prepared in the first step, putting the inner container into an oven, setting the hydrothermal reaction temperature at 120 ℃, setting the hydrothermal reaction time at 2 hours respectively, and raising the temperature along with the oven. And after the hydrothermal reaction is finished, cooling the sample to room temperature along with the box, taking out the sample, washing the sample with a large amount of distilled water, and drying the sample with cold air.
The prepared sample is subjected to potentiodynamic polarization test, and the result is shown in fig. 16, and the self-corrosion current density of the treated magnesium-lithium alloy is reduced by nearly 3 orders of magnitude compared with that of a matrix without surface treatment, which indicates that a film layer obtained through hydrothermal reaction has obvious corrosion protection effect.
Performing alternating current impedance spectroscopy test, soaking the prepared sample in a chloride ion-containing corrosion medium for a long time, and obtaining a result shown in FIG. 17. the film value of the sample subjected to hydrothermal reaction treatment is increased by 3 orders of magnitude, and the film layer has certain durability in the chloride ion-containing corrosion medium, the corrosion resistance of the sample after soaking for 36h is still obviously higher than that of a substrate without surface treatment, and the film layer does not lose protection effect until soaking for 48h, which also shows that the hydrothermal reaction surface treatment can obviously improve the corrosion resistance of the magnesium-lithium alloy
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (4)
1. The magnesium-lithium alloy surface anticorrosion treatment method is characterized by comprising the following steps:
step one, preparing 0.1-2 wt% Na2CO3The solution is used as a hydrothermal reaction solution;
and secondly, immersing the magnesium-lithium alloy into the hydrothermal reaction solution, carrying out hydrothermal reaction for 1-3 h at the reaction temperature of 110-130 ℃, cooling to room temperature, and obtaining a film layer on the surface of the magnesium-lithium alloy.
2. The magnesium-lithium alloy surface anticorrosion treatment method according to claim 1, characterized in that: in the step I, Na2CO3The concentration of the solution was 1 wt%.
3. The magnesium-lithium alloy surface anticorrosion treatment method according to claim 1 or 2, characterized in that: in the second step, the reaction temperature is 120 ℃, and the reaction time is 2 hours.
4. The magnesium-lithium alloy surface anticorrosion treatment method according to claim 1 or 2, characterized in that: the magnesium-lithium alloy is pretreated before being immersed in the hydrothermal reaction solution, and the pretreatment method specifically comprises the following steps: firstly, grinding the surface of the magnesium-lithium alloy by using sand paper, then ultrasonically cleaning the magnesium-lithium alloy by using absolute ethyl alcohol, then carrying out acid washing and alkali washing on the magnesium-lithium alloy, washing the magnesium-lithium alloy by using distilled water, and drying the magnesium-lithium alloy for later use.
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