CN116535884B - Compact corrosion-resistant wear-resistant SWF/LDHs composite coating on magnesium-lithium alloy surface and preparation method thereof - Google Patents
Compact corrosion-resistant wear-resistant SWF/LDHs composite coating on magnesium-lithium alloy surface and preparation method thereof Download PDFInfo
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- 238000000576 coating method Methods 0.000 title claims abstract description 81
- 239000011248 coating agent Substances 0.000 title claims abstract description 78
- 229910000733 Li alloy Inorganic materials 0.000 title claims abstract description 77
- 239000001989 lithium alloy Substances 0.000 title claims abstract description 77
- GCICAPWZNUIIDV-UHFFFAOYSA-N lithium magnesium Chemical compound [Li].[Mg] GCICAPWZNUIIDV-UHFFFAOYSA-N 0.000 title claims abstract description 77
- 239000002131 composite material Substances 0.000 title claims abstract description 58
- 238000005260 corrosion Methods 0.000 title claims abstract description 40
- 230000007797 corrosion Effects 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 61
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- 230000035484 reaction time Effects 0.000 claims description 8
- 239000000243 solution Substances 0.000 description 39
- 238000001035 drying Methods 0.000 description 37
- 239000008367 deionised water Substances 0.000 description 30
- 229910021641 deionized water Inorganic materials 0.000 description 30
- -1 polytetrafluoroethylene Polymers 0.000 description 25
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 25
- 239000004810 polytetrafluoroethylene Substances 0.000 description 25
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 18
- 238000005406 washing Methods 0.000 description 18
- 239000010410 layer Substances 0.000 description 14
- 238000001816 cooling Methods 0.000 description 11
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- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 10
- 238000004140 cleaning Methods 0.000 description 10
- 229910052739 hydrogen Inorganic materials 0.000 description 10
- 239000001257 hydrogen Substances 0.000 description 10
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 244000137852 Petrea volubilis Species 0.000 description 6
- 238000002474 experimental method Methods 0.000 description 6
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- 101100422881 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) swf-1 gene Proteins 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 230000004580 weight loss Effects 0.000 description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 238000005299 abrasion Methods 0.000 description 4
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- 238000005349 anion exchange Methods 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D1/00—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a compact corrosion-resistant wear-resistant SWF/LDHs composite coating on a magnesium-lithium alloy surface and a preparation method thereof, and belongs to the technical field of coatings. The preparation method of the invention comprises the following steps: removing an oxide film on the surface of the magnesium-lithium alloy to obtain a pretreated magnesium-lithium alloy; taking a reaction kettle as a reaction container, taking water as a steam source, placing the pretreated magnesium-lithium alloy above the water surface, and carrying out in-situ steam reaction at 100-150 ℃ to obtain an SWF coating contained on the surface of the magnesium-lithium alloy after the reaction is completed; with Al (NO) 3 ) 3 And (3) as a reaction solution, regulating the pH to be 10-13, and carrying out hydrothermal reaction at 80-140 ℃ by taking an SWF coating contained on the surface of the magnesium-lithium alloy as a precursor film layer to obtain the compact corrosion-resistant wear-resistant SWF/LDHs composite coating on the surface of the magnesium-lithium alloy. The method of the invention generates a compact and complete SWF/LDHs composite film layer on the surface of the magnesium-lithium alloy, and can effectively improve the corrosion resistance and the wear resistance of the magnesium-lithium alloy.
Description
Technical Field
The invention relates to the technical field of coatings, in particular to a compact corrosion-resistant wear-resistant SWF/LDHs composite coating on the surface of a magnesium-lithium alloy and a preparation method thereof.
Background
Energy and environmental pollution are two major problems facing countries around the world in the 21 st century. The magnesium-lithium alloy is an ideal material for realizing light weight, and has wide application prospect in the aspects of weight reduction, energy conservation and emission reduction. However, its active chemistry and poor corrosion and wear resistance severely limit its wide application. It is important to improve the corrosion resistance and the wear resistance of the magnesium-lithium alloy by adopting a proper surface protection technology. In recent years, materials of the intercalation structure type have been used as an environment-friendly protective material in the field of corrosion prevention of alloy materials because of their diversified structures and easy control.
Layered Double Hydroxides (LDHs) have unique layered structure, interlayer anion exchange and other characteristics, and have great potential for being used as protective coatings on the surfaces of magnesium-lithium alloys. At present, many researches on directly preparing LDHs coating on the surface of magnesium-lithium alloy are reported, but few researches on wear resistance are involved. Because the single LDHs coating is usually loose and has a small thickness, the corrosive solution easily permeates into the coating, and the LDHs coating loses the protection effect on the substrate, so the corrosion resistance of the single LDHs coating is not ideal and the single LDHs coating does not have long-term corrosion resistance. In addition, the wear resistance of single LDHs coating is very limited, so that the single LDHs coating still cannot be practically applied. Therefore, the research of the novel effective method is of great significance in further improving the corrosion resistance and the wear resistance of the magnesium-lithium alloy.
Disclosure of Invention
Aiming at the problems, the invention provides a compact corrosion-resistant wear-resistant SWF/LDHs composite coating on the surface of a magnesium-lithium alloy and a preparation method thereof.
The invention provides a preparation method of a compact corrosion-resistant wear-resistant SWF/LDHs composite coating on the surface of a magnesium-lithium alloy, which comprises the following steps:
step 1, removing an oxide film on the surface of a magnesium-lithium alloy to obtain a pretreated magnesium-lithium alloy; taking a reaction kettle as a reaction container, taking water as a steam source, placing the pretreated magnesium-lithium alloy above the water surface, and carrying out in-situ steam reaction at 100-150 ℃ to obtain an SWF coating contained on the surface of the magnesium-lithium alloy after the reaction is completed;
step 2, using Al (NO) 3 ) 3 And (3) as a reaction solution, regulating the pH to be 10-13, and carrying out hydrothermal reaction at 80-140 ℃ by taking an SWF coating contained on the surface of the magnesium-lithium alloy as a precursor film layer to obtain the compact corrosion-resistant wear-resistant SWF/LDHs composite coating on the surface of the magnesium-lithium alloy.
Preferably, in step 1, the reaction time of the in-situ steam reaction is 3-12 hours.
Preferably, in the step 1, the distance between the water surface and the pretreated magnesium-lithium alloy is 3-4cm.
Preferably, in the step 1, water accounts for 15% -30% of the volume of the reaction kettle.
Preferably, in step 2, the reaction time of the hydrothermal reaction is 10-36 hours.
Preferably, in step 2, the reaction time of the hydrothermal reaction is 18-30 hours.
Preferably, in step 2, al (NO 3 ) 3 The concentration of (2) is 0.05-0.1M.
The second purpose of the invention is to provide the compact corrosion-resistant wear-resistant SWF/LDHs composite coating on the surface of the magnesium-lithium alloy prepared by the preparation method.
Compared with the prior art, the invention has the following beneficial effects:
preparing a vapor film (SWF) on the surface of the LA43M magnesium-lithium alloy, and taking the vapor film as a precursor film layer, and using alkaline Al (NO 3 ) 3 The solution is used as a hydrothermal solution to carry out hydrothermal treatment on the precursor film SWF, and MgO and Mg (OH) in the SWF are subjected to the hydrothermal reaction process 2 More soluble to provide Mg 2+ ，Mg 2+ And the alkaline solution is introduced, so that the LDHs film layer is easier to directly generate in the reaction process than the LDHs film layer on the surface of the magnesium-lithium alloy, and the generated film layer is denser.
Meanwhile, after the hydrothermal treatment, defects such as micropores and cracks in the SWF are effectively sealed by LDHs which grow subsequently, and the LDHs nanosheets are increased in size and are more compact in growth, so that the thickness and the compactness of the whole film are obviously improved, and a compact and complete SWF/LDHs composite film is generated. And as the LDHs seals micropores and cracks in the SWF, the LDHs can play a good physical barrier function and ion exchange function in the corrosive solution, and the corrosion resistance of the SWF and the alloy matrix is obviously improved. On the other hand, the obtained SWF/LDHs composite coating is firmly combined with the matrix, and the LDHs lamellar nano-sheet structure can play an effective role in antifriction and lubrication in the friction and abrasion process, and the abrasion resistance of the matrix can be obviously improved.
In addition, the method has the advantages of simplicity, environmental protection, convenience in operation, low cost and the like on the premise of effectively improving the corrosion resistance and the wear resistance of the LA43M magnesium lithium alloy, and can provide reference for the wide application of the LA43M magnesium lithium alloy.
Drawings
Fig. 1 shows the surface (a) and the cross-sectional morphology (b) of a conventional LDHs coating of LA43M magnesium lithium alloy.
FIG. 2 shows the surface (a) and cross-sectional morphology (b) of the precursor SWF prepared in example 1.
FIG. 3 shows the surface (a) and cross-sectional morphology (b) of the SWF/LDHs composite coating of example 1.
FIG. 4 shows the surface (a) and cross-sectional morphology (b) of the SWF/LDHs composite coating in example 2.
FIG. 5 shows the surface (a) and cross-sectional morphology (b) of the SWF/LDHs composite coating in example 3.
Fig. 6 shows polarization curves of the magnesium-lithium alloy matrices of examples 1, LDHs and LA 43M.
FIG. 7 is the coefficient of friction of SWF/LDHs composite coating in example 2.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
Step 1: and (3) selecting a LA43M magnesium-lithium alloy sheet with the size of 25mm multiplied by 3mm, sequentially polishing the sample by using water sand paper 400#, 800#, 1500#, 2000#, 3000#, 5000# to remove an oxide film on the surface of the sample, washing the sample cleanly by using deionized water, then placing the sample into absolute ethyl alcohol, washing the sample for 12min by using ultrasonic waves, taking out the sample, washing the sample by using deionized water, and then drying the sample to obtain the pretreated LA43M magnesium-lithium alloy for later use.
Step 2: measuring 5mL of deionized water, placing the deionized water at the bottom of a 25mL hydrothermal synthesis reaction kettle liner as a steam source, fixing a bracket above the deionized water, keeping the distance between the water surface and the bracket to be 4cm, placing a pretreated LA43M magnesium-lithium alloy sample above the bracket, transferring the reaction kettle into a constant-temperature blast drying box, heating to 120 ℃ at a speed of 4 ℃/min, carrying out in-situ steam pretreatment, preserving the temperature for 6 hours, taking out the reaction kettle after the reaction is finished, cooling the reaction kettle to room temperature by air, flushing the sample with deionized water, drying by cold air, and recording the surface of the LA43M magnesium-lithium alloy to contain an SWF coating which is SWF-1;
FIG. 2 shows the surface (a) and cross-sectional morphology (b) of a sample of the resulting SWF-1 coating, which was relatively dense, uniform, with few micropores and a thickness of about 3.5. Mu.m. The resins mentioned in the b diagrams of fig. 1 to 5 refer to materials for embedding metallographic samples.
And 3, carrying out hydrothermal treatment on the SWF-1 sample by adopting a 101-1BS constant temperature blast drying box and a polytetrafluoroethylene hydrothermal reaction kettle. The method comprises the following specific steps:
configuration 0.05MAl (NO) 3 ) 3 The solution was used as a reaction solution, and the pH was adjusted to 12.3 using NaOH solution. The SWF-1 pretreated in the second step is obliquely placed in a polytetrafluoroethylene reaction kettle liner, and Al (NO) with the concentration of 0.05M is added dropwise 3 ) 3 The solution was allowed to soak until the solution immersed the SWF-1 specimen. Transferring the polytetrafluoroethylene reaction kettle into a constant-temperature blast drying oven, heating to 100 ℃ at the speed of 3 ℃/min, keeping the temperature for 18 hours, preparing the SWF/LDHs composite coating, taking out the composite coating, cooling to room temperature by air after the reaction is finished, cleaning the sample with deionized water, and drying by cold air. The prepared sample is marked as SWF/LDHs-1.
FIG. 3 shows the surface (a) and cross-sectional morphology (b) of the SWF/LDHs-1 composite coating, wherein the compactness and thickness of the SWF/LDHs composite film layer are greatly improved and the thickness is about 8 μm compared with the single LDHs coating in FIG. 1.
As shown in fig. 6, the present embodiment has more positive corrosion potential and lower corrosion current density than the magnesium-lithium alloy substrate, and the corrosion resistance is superior to that of the magnesium-lithium alloy substrate and LDHs coating.
Example 2
Step 1, selecting a LA43M magnesium-lithium alloy sheet with the size of 25mm multiplied by 3mm, sequentially polishing the sample by adopting water sand paper 400#, 800#, 1500#, 2000#, 3000#, 5000# to remove an oxide film on the surface of the sample, washing the sample cleanly by deionized water, then placing the sample into absolute ethyl alcohol, washing the sample for 10min by ultrasonic waves, taking out the sample, washing the sample by deionized water, and then drying the sample to obtain the pretreated LA43M magnesium-lithium alloy for standby.
And 2, performing steam treatment on the LA43M magnesium lithium alloy by adopting a 101-1BS constant-temperature blast drying box and a polytetrafluoroethylene hydrothermal reaction kettle. 4mL of deionized water is measured and placed at the bottom of a hydrothermal synthesis reaction kettle liner (25 mL) to serve as a steam source, a bracket is fixed above the steam source, and the distance between the water surface and the bracket is kept to be 3cm. And (2) placing the pretreated LA43M magnesium-lithium alloy sheet in the step (1) above a bracket, after assembling a polytetrafluoroethylene reaction kettle, transferring the sheet into a constant-temperature blast drying oven, heating to 120 ℃ at a speed of 4 ℃/min, keeping the temperature for 9 hours, preparing an SWF coating, taking out the sheet and air-cooling the sheet to room temperature after the reaction is finished, cleaning a sample with deionized water, and drying the sample with cold air. The prepared sample was labeled SWF-2.
And 2, carrying out hydrothermal treatment on the SWF-2 by adopting a 101-1BS constant temperature blast drying box and a polytetrafluoroethylene hydrothermal reaction kettle. The method comprises the following specific steps:
configuration 0.05MAl (NO) 3 ) 3 The solution was used as a reaction solution, and the pH was adjusted to 11.8 using NaOH solution. The SWF-2 sheet obtained in the step 2 is obliquely placed in a polytetrafluoroethylene reaction kettle liner, and Al (NO) with the concentration of 0.05M is added dropwise 3 ) 3 The solution was allowed to soak until the solution immersed the SWF-2 specimen. Transferring the polytetrafluoroethylene reaction kettle into a constant-temperature blast drying oven, heating to 100 ℃ at the speed of 4 ℃/min, keeping the temperature for 24 hours, preparing the MgAl SWF/LDHs composite coating, taking out the MgAl SWF/LDHs composite coating after the reaction is finished, air-cooling to room temperature, cleaning the sample with deionized water, and drying with cold air. The prepared sample is marked as SWF/LDHs-2.
FIG. 4 shows the surface (a) and cross-sectional morphology (b) of the resulting composite coating SWF/LDHs-2. As can be seen from FIG. 4, the obtained SWF/LDHs composite coating is compact and uniform, is firmly combined with the matrix, and has a thickness of about 10 μm.
As shown in FIG. 7, the friction coefficient curves of the SWF/LDHs-2 composite coating, the LA43M magnesium-lithium alloy and the LDHs coating obtained in the embodiment under the room temperature dry friction condition show that the wear resistance of the SWF/LDHs-2 composite coating is far better than that of the magnesium-lithium alloy matrix and the LDHs coating.
Example 3
Step 1, selecting a LA43M magnesium-lithium alloy sheet with the size of 25mm multiplied by 3mm, sequentially polishing the sample by adopting water sand paper 400#, 800#, 1500#, 2000#, 3000#, 5000# to remove an oxide film on the surface of the sample, washing the sample cleanly by deionized water, then placing the sample into absolute ethyl alcohol, washing the sample for 10min by ultrasonic waves, taking out the sample, washing the sample by deionized water, and then drying the sample to obtain the pretreated LA43M magnesium-lithium alloy for standby.
And 2, performing steam treatment on the LA43M magnesium lithium alloy by adopting a 101-1BS constant-temperature blast drying box and a polytetrafluoroethylene hydrothermal reaction kettle. 4mL of deionized water is measured and placed at the bottom of a hydrothermal synthesis reaction kettle liner (25 mL) to serve as a steam source, a bracket is fixed above the steam source, and the distance between the water surface and the bracket is kept to be 3cm. And (2) placing the pretreated LA43M magnesium-lithium alloy sheet in the step (1) above a bracket, after assembling a polytetrafluoroethylene reaction kettle, transferring the sheet into a constant-temperature blast drying oven, heating to 120 ℃ at a speed of 4 ℃/min, keeping the temperature for 9 hours, preparing an SWF coating, taking out the sheet and air-cooling the sheet to room temperature after the reaction is finished, cleaning a sample with deionized water, and drying the sample with cold air. The prepared sample was labeled SWF-3.
And step 3, carrying out hydrothermal treatment on the SWF-3 by adopting a 101-1BS constant temperature blast drying box and a polytetrafluoroethylene hydrothermal reaction kettle. The method comprises the following specific steps:
configuration 0.05MAl (NO) 3 ) 3 The solution was used as a reaction solution, and the pH was adjusted to 12.1 using NaOH solution. The SWF-3 sheet obtained in the step 2 is obliquely placed in a polytetrafluoroethylene reaction kettle liner, and Al (NO) with the concentration of 0.05M is added dropwise 3 ) 3 The solution was allowed to soak until the solution immersed the SWF-3 specimen. Transferring the polytetrafluoroethylene reaction kettle into a constant-temperature blast drying oven, heating to 100 ℃ at the speed of 4 ℃/min, keeping the temperature for 30 hours, preparing the MgAl SWF/LDHs composite coating, taking out the MgAl SWF/LDHs composite coating after the reaction is finished, air-cooling to room temperature, cleaning the sample with deionized water, and drying with cold air. The prepared sample is marked as SWF/LDHs-3.
FIG. 5 shows the surface (a) and cross-sectional morphology (b) of the resulting composite coating SWF/LDHs-3. As can be seen from FIG. 5, the obtained SWF/LDHs composite coating is compact and uniform, is firmly combined with the matrix, and has a thickness of about 13 μm.
Example 4
Step 1, selecting a LA43M magnesium-lithium alloy sheet with the size of 25mm multiplied by 3mm, sequentially polishing the sample by adopting water sand paper 400#, 800#, 1500#, 2000#, 3000#, 5000# to remove an oxide film on the surface of the sample, washing the sample cleanly by deionized water, then placing the sample into absolute ethyl alcohol, washing the sample for 15min by ultrasonic waves, taking out the sample, washing the sample by deionized water, and then drying the sample to obtain the pretreated LA43M magnesium-lithium alloy for standby.
And 2, performing steam treatment on the LA43M magnesium lithium alloy by adopting a 101-1BS constant-temperature blast drying box and a polytetrafluoroethylene hydrothermal reaction kettle. 3.8mL of deionized water is measured and placed at the bottom of a hydrothermal synthesis reaction kettle liner (25 mL) to serve as a steam source, a bracket is fixed above the steam source, and the distance between the water surface and the bracket is kept to be 4cm. And (2) placing the pretreated LA43M magnesium-lithium alloy sheet in the step (1) above a bracket, transferring the sheet to a constant-temperature blast drying oven, heating to 100 ℃ at a speed of 3 ℃/min after assembling a polytetrafluoroethylene reaction kettle, and carrying out heat preservation for 12 hours to prepare an SWF coating, taking out the sheet after the reaction is finished, cooling to room temperature by air, cleaning a sample with deionized water, and drying by cold air. The prepared sample was labeled SWF-4.
And step 3, carrying out hydrothermal treatment on the SWF-4 by adopting a 101-1BS constant temperature blast drying box and a polytetrafluoroethylene hydrothermal reaction kettle. The method comprises the following specific steps:
configuration 0.1MAl (NO) 3 ) 3 The solution was used as a reaction solution, and the pH was adjusted to between 10 using NaOH solution. The SWF-4 sheet obtained in the step 2 is obliquely placed in a polytetrafluoroethylene reaction kettle liner, and Al (NO) with the concentration of 0.1M is added dropwise 3 ) 3 The solution was allowed to soak until the solution immersed the SWF-4 specimen. Transferring the polytetrafluoroethylene reaction kettle into a constant-temperature blast drying oven, heating to 80 ℃ at a speed of 5 ℃/min, keeping the temperature for 36h, preparing the MgAl SWF/LDHs composite coating, taking out the MgAl SWF/LDHs composite coating after the reaction is finished, air-cooling to room temperature, cleaning the sample with deionized water, and drying with cold air. The prepared sample is marked as SWF/LDHs-4.
Example 5
Step 1, selecting a LA43M magnesium-lithium alloy sheet with the size of 25mm multiplied by 3mm, sequentially polishing the sample by adopting water sand paper 400#, 800#, 1500#, 2000#, 3000#, 5000# to remove an oxide film on the surface of the sample, washing the sample cleanly by deionized water, then placing the sample into absolute ethyl alcohol, washing the sample for 15min by ultrasonic waves, taking out the sample, washing the sample by deionized water, and then drying the sample to obtain the pretreated LA43M magnesium-lithium alloy for standby.
And 2, performing steam treatment on the LA43M magnesium lithium alloy by adopting a 101-1BS constant-temperature blast drying box and a polytetrafluoroethylene hydrothermal reaction kettle. 7.5mL of deionized water is measured and placed at the bottom of a hydrothermal synthesis reaction kettle liner (25 mL) to serve as a steam source, a bracket is fixed above the steam source, and the distance between the water surface and the bracket is kept to be 4cm. And (2) placing the pretreated LA43M magnesium-lithium alloy sheet in the step (1) above a bracket, transferring the sheet to a constant-temperature blast drying oven, heating to 150 ℃ at a speed of 5 ℃/min after assembling a polytetrafluoroethylene reaction kettle, and carrying out heat preservation for 3 hours to prepare an SWF coating, taking out and cooling to room temperature after the reaction is finished, cleaning a sample with deionized water, and drying with cold air. The prepared sample was labeled SWF-5.
And 3, carrying out hydrothermal treatment on the SWF-5 by adopting a 101-1BS constant temperature blast drying box and a polytetrafluoroethylene hydrothermal reaction kettle. The method comprises the following specific steps:
configuration 0.08MAl (NO) 3 ) 3 The solution was used as a reaction solution, and the pH was adjusted to between 13 using NaOH solution. The SWF-5 sheet obtained in the step 2 is obliquely placed in a polytetrafluoroethylene reaction kettle liner, and Al (NO) with the concentration of 0.05M is added dropwise 3 ) 3 The solution was allowed to soak until the solution immersed the SWF-3 specimen. Transferring the polytetrafluoroethylene reaction kettle into a constant-temperature blast drying oven, heating to 140 ℃ at a speed of 5 ℃/min, keeping the temperature for 10 hours, preparing the MgAl SWF/LDHs composite coating, taking out the MgAl SWF/LDHs composite coating after the reaction is finished, air-cooling to room temperature, cleaning the sample with deionized water, and drying with cold air. The prepared sample is marked as SWF/LDHs-5.
Comparative example 1
And (3) selecting an LA43M magnesium-lithium alloy sheet with the size of 25mm multiplied by 3mm, sequentially polishing the sample by using water sand paper 400#, 800#, 1500#, 2000#, 3000#, 5000# to remove an oxide film on the surface of the sample, washing the sample cleanly by using deionized water, then placing the sample into absolute ethyl alcohol, washing the sample for 12min by using ultrasonic waves, taking out the sample, washing the sample by using deionized water, and drying the sample to obtain the pretreated LA43M magnesium-lithium alloy (marked as LA 43M).
Comparative example 2
The same as in example 1, except that the treatment step of step 2 was not performed.
The method comprises the following specific steps:
configuration 0.05MAl (NO) 3 ) 3 The solution was used as a reaction solution and the pH was adjusted between 12.3 using NaOH solution. Obliquely placing the pretreated LA43M magnesium-lithium alloy in the step 1 into a polytetrafluoroethylene reaction kettle liner, and dropwise adding Al (NO) with the concentration of 0.05M 3 ) 3 The solution was allowed to soak until the sample was immersed in the solution. Transferring the polytetrafluoroethylene reaction kettle into a constant-temperature blast drying oven, heating to 100 ℃ at a speed of 3 ℃/min, keeping the temperature for 18 hours, preparing an LDHs coating, taking out the LDHs coating, cooling to room temperature by air after the reaction is finished, cleaning a sample with deionized water, and drying by cold air. The prepared sample is marked as LDHs-1.
The following corrosion resistance, frictional wear performance, and frictional wear performance indexes are shown in tables 1, 2 and 5, and the frictional wear performance indexes are shown in tables 3, 4 and 5, respectively, were tested for the composite coatings of LA43M magnesium-lithium alloy, LDHs and SWF/LDHs. Note that LA43M in tables 1 to 4 was prepared according to the method of comparative example 1, and LDHs was prepared according to the method of comparative example 2.
Table 1 example 1 corrosion resistance test results
TABLE 2 results of Corrosion resistance test of example 2
TABLE 3 results of the frictional wear test of example 1
Table 4 example 2 frictional wear test results
TABLE 5 example 3 Corrosion resistance and frictional wear test results
And (3) adopting a soaking corrosion experiment to represent the corrosion performance change of the LA43M magnesium-lithium alloy, the LDHs coating and the SWF/LDHs composite coating sample. Specifically: the samples with different treatment states are soaked in 3.5wt.% NaCl solution for 8-16 days to test the weight loss, the samples are weighed before the experiment, the surface area of the samples is calculated, then the samples are put into the solution, the samples are taken out every 24 hours, the corrosion products are washed off, the mass loss is tested, and the total of 8-16 days is accumulated. The weight loss rate (weight rate (mg cm) -2 ·h -1 ) See tables 1, 2). The result shows that the loss rate of the LA43M magnesium-lithium alloy and the LDHs coating after 192h immersion is 0.01083 mg.cm -2 ·h -1 、0.00226mg·cm -2 ·h -1 The method comprises the steps of carrying out a first treatment on the surface of the The weight loss rates of the SWF/LDHs composite coating are 0.00161mg cm respectively -2 ·h -1 、0.00184mg·cm -2 ·h -1 And the composite film layer is not damaged obviously. To further verify the corrosion resistance and long-acting performance, the soaking time is prolonged to 16 days (384 h) in the experiment, and the weight loss rates of the SWF/LDHs composite coating are respectively 0.00166mg cm -2 ·h -1 、0.00189mg·cm -2 ·h -1 The film layer is maintained at an extremely low value and is not obviously damaged, so that the composite film layer has excellent long-acting corrosion resistance.
Meanwhile, corrosion performance changes of LA43M magnesium lithium alloy, LDHs coating and SWF/LDHs composite coating samples are characterized through hydrogen evolution corrosion experiments. Specifically: will be differentThe hydrogen evolution rate of the treated sample is tested by immersing the treated sample in 3.5wt.% NaCl solution for 8-16 days, the surface area of the sample is calculated before the experiment, the sample is put into the solution, initial reading of a burette is recorded, timing is started, recording is carried out every 24 hours, and the hydrogen evolution rate is accumulated for 8-16 days. The hydrogen evolution rate of each sample after 8-16 days of soaking (hydrogen evolution rate (mL. Cm) -2 ·h -1 ) Values are shown in tables 1 and 2. The hydrogen evolution rates of the LA43M magnesium-lithium alloy and the LDHs coating 192h are 0.0611mL cm respectively -2 ·h -1 ，0.0262mL·cm -2 ·h -1 The hydrogen evolution rates of the SWF/LDHs composite coating sample 192h according to the invention were 0.0028mL cm -2 ·h -1 、0.0033mL·cm -2 ·h -1 And the hydrogen evolution rate after soaking for 16 days (384 h) is still maintained at a smaller value of 0.0032mL cm -2 ·h -1 、0.0035mL·cm -2 ·h -1 The composite coating has obvious protective effect on the magnesium-lithium alloy matrix and long-term corrosion-resistant protective effect.
In addition, the frictional wear properties of the substrates and each of the coated samples were characterized using an MFT-R4000 high speed reciprocating frictional wear tester. The friction pair is made of Cr15 small steel balls with the diameter of 4mm, the counter-grinding material is an LA43M alloy matrix and each film sample, and specific experimental parameters are as follows: the reciprocating frequency was 2Hz, the distance was 5mm, the loading load was 5N, and the friction time was 10min. Before the test starts, the machine is started and preheated for 20min, then the sample is placed, and after the load and the friction resistance are both set to zero by using a zero setting knob, the weight is added until the load is 5N. Finally, the contact area of the sample and the grinding ball is adjusted to keep the contact load between-1N and 1N. The friction coefficient and the wear scar width values of the respective samples are shown in tables 3, 4 and 5. The average friction coefficient of the LA43M magnesium-lithium alloy was 0.552, the abrasion mark width was 768 μm, while the friction coefficients of the test specimens using the SWF/LDHs composite coating according to the present invention were 0.122,0.121, respectively, and the abrasion mark widths were 431 μm and 428 μm, respectively. It can be seen that tribology performance is also improved significantly.
By process adjustment (i.e., extension of the hydrothermal reaction time in step 3), the composite coating prepared according to the process of example 3 had a thickness of about 13 μm, as compared toThe SWF/LDHs composite coating prepared in example 1 and example 2 was increased in thickness and dense. The corrosion resistance and frictional wear test results of the SWF/LDHs composite coating are shown in Table 5. The hydrogen evolution rate of the sample after 192h soaking is 0.0031mL cm -2 ·h -1 And the hydrogen evolution rate after soaking for 16 days (384 h) is still kept at a small value (0.0034 mL cm) -2 ·h -1 ). On the other hand, the weight loss rate after 192 hours of soaking was 0.00182 mg.cm -2 ·h -1 And the composite film layer is not damaged obviously. Similarly, in order to further verify the corrosion resistance and long-acting property, the soaking time is prolonged to 16 days (384 h) in the experiment, and the loss rate of the SWF/LDHs composite coating is 0.00185 mg.cm -2 ·h -1 The film is maintained at an extremely low value, the film is not damaged obviously, and the composite film with the adjusted thickness has excellent long-acting corrosion resistance. In addition, the sample friction coefficient of the SWF/LDHs composite coating was 0.118, and the width of the grinding mark was 423 μm. It can be seen that tribology performance is also improved significantly. In addition, along with the extension of the hydrothermal reaction time in the step 3, the thickness of the SWF/LDHs composite film layer is increased, but the hydrothermal time (more than 30 h) is further prolonged, the thickness increase is not obvious, and the compactness of the film layer is reduced. As the compactness of the composite film layer is reduced, the corrosion resistance and the wear resistance of the composite film layer are reduced. Lengthening the treatment time also increases the energy consumption.
While preferred embodiments of the present invention have been described, additional variations and modifications in those embodiments may occur to those skilled in the art once they learn of the basic inventive concepts. It is therefore intended that the following claims be interpreted as including the preferred embodiments and all such alterations and modifications as fall within the scope of the invention.
It will be apparent to those skilled in the art that various modifications and variations can be made to the present invention without departing from the spirit or scope of the invention. Thus, it is intended that the present invention also include such modifications and alterations insofar as they come within the scope of the appended claims or the equivalents thereof.
Claims (3)
1. The preparation method of the compact corrosion-resistant wear-resistant SWF/LDHs composite coating on the surface of the magnesium-lithium alloy is characterized by comprising the following steps of:
step 1, removing an oxide film on the surface of a magnesium-lithium alloy to obtain a pretreated magnesium-lithium alloy; taking a reaction kettle as a reaction container, taking water as a steam source, placing the pretreated magnesium-lithium alloy above the water surface, and carrying out in-situ steam reaction at 100-150 ℃ to obtain an SWF coating contained on the surface of the magnesium-lithium alloy after the reaction is completed; the reaction time of the in-situ steam reaction is 3-12h; the distance between the water surface and the pretreated magnesium-lithium alloy is 3-4cm; water accounts for 15-30% of the volume of the reaction kettle;
step 2, using Al (NO) 3 ) 3 As a reaction solution, regulating the pH to 10-13, taking an SWF coating contained on the surface of the magnesium-lithium alloy as a precursor film layer, and carrying out hydrothermal reaction at 80-140 ℃ to obtain a compact corrosion-resistant wear-resistant SWF/LDHs composite coating on the surface of the magnesium-lithium alloy; al (NO) 3 ) 3 The concentration of (2) is 0.05-0.1M, and the reaction time of the hydrothermal reaction is 10-36h.
2. The method for preparing the compact corrosion-resistant wear-resistant SWF/LDHs composite coating on the surface of the magnesium-lithium alloy according to claim 1, wherein in the step 2, the reaction time of the hydrothermal reaction is 18-30h.
3. A compact corrosion-resistant wear-resistant SWF/LDHs composite coating on the surface of a magnesium-lithium alloy prepared by the preparation method of any one of claims 1-2.
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