CN108707889B - Method for growing LDH conversion film in magnesium alloy in situ - Google Patents
Method for growing LDH conversion film in magnesium alloy in situ Download PDFInfo
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- 238000006243 chemical reaction Methods 0.000 title claims abstract description 68
- 229910000861 Mg alloy Inorganic materials 0.000 title claims abstract description 48
- 238000000034 method Methods 0.000 title claims abstract description 34
- 238000011065 in-situ storage Methods 0.000 title claims abstract description 20
- 238000005406 washing Methods 0.000 claims abstract description 88
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000002253 acid Substances 0.000 claims abstract description 23
- 230000004913 activation Effects 0.000 claims abstract description 11
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000005554 pickling Methods 0.000 claims abstract description 7
- 238000005498 polishing Methods 0.000 claims abstract description 7
- 238000004506 ultrasonic cleaning Methods 0.000 claims abstract description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 72
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 48
- 239000007788 liquid Substances 0.000 claims description 44
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 24
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 24
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 24
- 229910017604 nitric acid Inorganic materials 0.000 claims description 24
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 24
- 239000012528 membrane Substances 0.000 claims description 14
- 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 12
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 claims description 12
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 12
- 239000001488 sodium phosphate Substances 0.000 claims description 12
- 229910000162 sodium phosphate Inorganic materials 0.000 claims description 12
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 239000003513 alkali Substances 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 6
- 230000007797 corrosion Effects 0.000 abstract description 13
- 238000005260 corrosion Methods 0.000 abstract description 13
- 230000003213 activating effect Effects 0.000 description 18
- 238000007654 immersion Methods 0.000 description 3
- 239000002052 molecular layer Substances 0.000 description 3
- 238000004381 surface treatment Methods 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000000975 co-precipitation Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000013535 sea water Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 244000137852 Petrea volubilis Species 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 235000005770 birds nest Nutrition 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 230000003075 superhydrophobic effect Effects 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000010891 toxic waste Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 235000005765 wild carrot Nutrition 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
-
- 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
- C23C22/73—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 characterised by the process
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Abstract
本发明公开了一种镁合金原位生长LDH转化膜的方法，步骤一：将镁合金打磨后在丙酮中超声波震洗得到震洗样品；步骤二：将震洗样品放入碱洗液中进行碱洗得到碱洗样品；步骤三：将碱洗样品放入酸洗液中进行酸洗得到酸洗样品；步骤四：将酸洗样品浸入活化液中进行活化处理，得到预处理镁合金；步骤五：将预处理镁合金置于水热转化处理液中进行水热反应，反应结束后得到转化处理样品；步骤六：将转化处理样品置于酒精中进行超声清洗，然后于空气中干燥，即得到镁合金原位生长LDH转化膜。本发明经过合适的预处理之后，直接在镁合金表面制备出均匀致密的LDH转化膜，不但可以大幅度提高耐蚀性，同时工艺简单有效，还可应用于各种零部件结构。
The invention discloses a method for in-situ growth of an LDH conversion film on a magnesium alloy. Step 1: after polishing the magnesium alloy, ultrasonically shake the magnesium alloy in acetone to obtain a shock-washed sample; alkaline washing to obtain an alkaline washing sample; step 3: placing the alkaline washing sample in an acid washing solution for pickling to obtain an acid washing sample; step 4: immersing the acid washing sample in an activation solution for activation treatment to obtain a pretreated magnesium alloy; step Five: place the pretreated magnesium alloy in the hydrothermal conversion treatment solution for hydrothermal reaction, and obtain the converted sample after the reaction; Step 6: put the converted sample in alcohol for ultrasonic cleaning, and then dry it in the air, that is, The magnesium alloy in-situ growth LDH conversion film was obtained. After proper pretreatment, the invention directly prepares a uniform and dense LDH conversion film on the surface of the magnesium alloy, which can not only greatly improve the corrosion resistance, but also has a simple and effective process, and can also be applied to various component structures.
Description
Technical Field
The invention belongs to the field of material corrosion and protection, and particularly relates to a method for growing an LDH conversion film in situ on magnesium alloy.
Background
Poor corrosion resistance is always a key factor which seriously restricts the application of magnesium alloy, and the surface treatment technology is the main method for improving the corrosion resistance of the magnesium alloy at present. Chemical conversion methods and anodic oxidation methods are the most widely used magnesium alloy surface treatment techniques due to the relatively mature and simple treatment processes. However, these methods have their own drawbacks: for example, although the chemical conversion method has simple process and strong applicability, the corrosion resistance effect is not ideal and is accompanied by toxic waste liquid, which is not beneficial to environmental protection; although anodic oxidation can yield a relatively corrosion resistant ceramic film, the film has many pores, is not mechanically bonded to the substrate, and cannot handle structural members having complex shapes. Layered Double Hydroxide (LDH) is a two-dimensional layered nanomaterial that is small in size, high in capacity, and easy to modify, and thus is considered to be an excellent surface treatment technique. However, the current common methods for synthesizing LDH conversion membranes, such as coprecipitation method, steam method and in-situ growth method, have obvious disadvantages. The LDH conversion film generated by the coprecipitation method has poor crystallinity and poor binding force and causes a great deal of waste of products; LDH components in the LDH membrane generated by the steam method are few, and even no LDH product is generated; the film generated by the common in-situ growth method is not uniform enough and has a large number of defects (such as cracks) on the surface.
Disclosure of Invention
The invention provides a method for growing LDH conversion film in situ on magnesium alloy, which overcomes the problems in the prior art.
In order to achieve the purpose, the invention adopts the following technical scheme:
a method for growing LDH conversion membranes in situ by magnesium alloy comprises the following steps:
the method comprises the following steps: polishing the magnesium alloy, and then ultrasonically shaking and washing in acetone to obtain a shaking and washing sample;
step two: putting the vibration washing sample into alkaline washing liquid for alkaline washing to obtain an alkaline washing sample;
step three: placing the alkali washing sample into a pickling solution for pickling to obtain a pickled sample;
step four: immersing the acid-washed sample into an activation solution for activation treatment to obtain a pretreated magnesium alloy;
step five: placing the pretreated magnesium alloy in a hydrothermal conversion treatment solution for hydrothermal reaction to obtain a conversion treatment sample after the reaction is finished;
step six: and (3) placing the conversion treatment sample in alcohol for ultrasonic cleaning, and then drying in the air to obtain the magnesium alloy in-situ growth LDH conversion membrane.
Further, in the step one, the magnesium alloy is polished to 5000# sand paper, the power of ultrasonic vibration washing is 150W, and the time is 15 min.
Further, the alkaline washing solution in the second step is obtained by dissolving sodium hydroxide, sodium carbonate and sodium phosphate in water, wherein the concentration of the sodium hydroxide in the alkaline washing solution is 80g/L, the concentration of the sodium carbonate is 40g/L, and the concentration of the sodium phosphate is 30 g/L.
Further, the temperature of the alkali washing in the second step is 60 ℃, and the time is 8-10 min.
Further, the pickling solution in the third step is composed of 65% by mass of nitric acid, 85% by mass of phosphoric acid and 60% by mass of hydrochloric acid, and the volume ratio of the nitric acid to the phosphoric acid to the hydrochloric acid is (20-30): (400-500): (15-20).
Further, in the third step, the pickling temperature is room temperature, and the pickling time is 30-45 s.
Further, the activating solution in the fourth step is composed of acetone and 65% by mass of nitric acid, and the volume fraction of the nitric acid in the activating solution is 10%.
Furthermore, in the fourth step, the activation temperature is room temperature, and the time is 50-60 s.
Further, the hydrothermal conversion treatment liquid in the fourth step is obtained by dissolving aluminum nitrate, sodium carbonate, sodium hydroxide and ammonium nitrate in water, and the concentration of the aluminum nitrate in the hydrothermal conversion treatment liquid is (19-20.5) g/L, the concentration of the sodium carbonate is (8-11) g/L, the concentration of the sodium hydroxide is (8-11) g/L, and the concentration of the ammonium nitrate is (4-5.5) g/L.
Further, the hydrothermal reaction in the fifth step is specifically as follows: the pretreated magnesium alloy and the hydrothermal conversion treatment liquid are put into a hydrothermal reaction kettle, the filling amount of the hydrothermal conversion treatment liquid is 40%, and then the temperature is kept for 12 hours under the pressure of 3Mpa and at the temperature of 100 ℃.
Compared with the prior art, the invention has the following beneficial technical effects:
the LDH conversion film obtained by the method of the invention has compact and uniform surface, the thickness can reach about 40 mu m, and a great amount of bird nest type nano lamellar structures are distributed on the surface of the film layer. LDH is used as an inorganic nano layer with extremely high corrosion resistance, and the higher the LDH content, the more the corrosion resistance of the film layer can be improved. Also, because LDH has a unique ion exchange mechanism, interlaminar stored anions can be exposed to corrosive ions (e.g., Cl)-) The LDH conversion film is released and absorbs and stores corrosive ions between layers, a large number of nano-layer sheets distributed on the surface have a certain hydrophobic effect, and the super-hydrophobic effect can be achieved after the nano-layer sheets are modified by a high surfactant, so that the LDH conversion film grown in situ by the method disclosed by the invention has excellent corrosion resistance. Compared with an AZ33 magnesium alloy matrix, under the condition of simulated seawater immersion for two hours, the corrosion resistance of the AZ33 magnesium alloy is improved from-1.5 Komega to-1000 Komega, and the corrosion current is reduced by two orders of magnitude from 10-5A/cm2Down to 10-7A/cm2. Even if the soaking time is more than 96h, the impedance still exceeds 500K omega.
Drawings
Figure 1 is an XRD pattern of the in situ grown LDH conversion film prepared in example 3;
figure 2 is an SEM image of the in situ grown LDH conversion membrane prepared in example 3.
Detailed Description
The invention is described in further detail below:
a method for growing LDH conversion membranes in situ by magnesium alloy comprises the following steps:
the method comprises the following steps: polishing magnesium alloy to 5000# abrasive paper, and ultrasonically shaking and washing in acetone to obtain a shaking and washing sample, wherein the ultrasonic shaking and washing power is 150W, and the time is 15 min;
step two: placing the shake-washing sample into alkaline washing liquid to carry out alkaline washing for 8-10min at 60 ℃ to obtain an alkaline washing sample, wherein the alkaline washing liquid is obtained by dissolving sodium hydroxide, sodium carbonate and sodium phosphate into water, the concentration of the sodium hydroxide in the alkaline washing liquid is 80g/L, the concentration of the sodium carbonate is 40g/L, and the concentration of the sodium phosphate is 30 g/L;
step three: placing the alkali washing sample into acid washing liquid to be subjected to acid washing for 30-45s at room temperature to obtain an acid washing sample, wherein the acid washing liquid is composed of 65% by mass of nitric acid, 85% by mass of phosphoric acid and 60% by mass of hydrochloric acid, and the volume ratio of the nitric acid to the phosphoric acid to the hydrochloric acid is (20-30): (400-500): (15-20);
step four: immersing an acid-washed sample into an activating solution for activating treatment for 50-60s at room temperature to obtain a pretreated magnesium alloy, wherein the activating solution consists of acetone and 65% by mass of nitric acid, and the volume fraction of the nitric acid in the activating solution is 10%;
step five: putting the pretreated magnesium alloy into a hydrothermal reaction kettle, wherein the filling amount of a hydrothermal conversion treatment liquid is 40%, then keeping the temperature at 100 ℃ under the pressure of 3MPa for 12h, and obtaining a conversion treatment sample after the reaction is finished, wherein the hydrothermal conversion treatment liquid is obtained by dissolving aluminum nitrate, sodium carbonate, sodium hydroxide and ammonium nitrate into water, the concentration of the aluminum nitrate in the hydrothermal conversion treatment liquid is (19-20.5) g/L, the concentration of the sodium carbonate is (8-11) g/L, the concentration of the sodium hydroxide is (8-11) g/L, and the concentration of the ammonium nitrate is (4-5.5) g/L;
step six: and (3) placing the conversion treatment sample in alcohol for ultrasonic cleaning, and then drying in the air to obtain the magnesium alloy in-situ growth LDH conversion membrane.
The present invention is described in further detail below with reference to examples:
example 1
The method comprises the following steps: polishing magnesium alloy to 5000# abrasive paper, and ultrasonically shaking and washing in acetone to obtain a shaking and washing sample, wherein the ultrasonic shaking and washing power is 150W, and the time is 15 min;
step two: placing the shake-washing sample into alkaline washing liquid to carry out alkaline washing for 8min at the temperature of 60 ℃ to obtain an alkaline washing sample, wherein the alkaline washing liquid is obtained by dissolving sodium hydroxide, sodium carbonate and sodium phosphate into water, the concentration of the sodium hydroxide in the alkaline washing liquid is 80g/L, the concentration of the sodium carbonate is 40g/L, and the concentration of the sodium phosphate is 30 g/L;
step three: placing the alkali washing sample into acid washing liquid to be subjected to acid washing for 30s at room temperature to obtain an acid washing sample, wherein the acid washing liquid is composed of 65% by mass of nitric acid, 85% by mass of phosphoric acid and 60% by mass of hydrochloric acid, and the volume ratio of the nitric acid to the phosphoric acid to the hydrochloric acid is 20: 400: 15;
step four: immersing an acid-washed sample into an activating solution for activating treatment for 50s at room temperature to obtain a pretreated magnesium alloy, wherein the activating solution consists of acetone and 65% nitric acid by mass, and the volume fraction of the nitric acid in the activating solution is 10%;
step five: putting the pretreated magnesium alloy into a hydrothermal reaction kettle, wherein the filling amount of a hydrothermal conversion treatment liquid is 40%, then keeping the temperature at 100 ℃ under the pressure of 3MPa for 12h, and obtaining a conversion treatment sample after the reaction is finished, wherein the hydrothermal conversion treatment liquid is obtained by dissolving aluminum nitrate, sodium carbonate, sodium hydroxide and ammonium nitrate into water, the concentration of the aluminum nitrate in the hydrothermal conversion treatment liquid is 19g/L, the concentration of the sodium carbonate is 8g/L, the concentration of the sodium hydroxide is 8g/L, and the concentration of the ammonium nitrate is 4 g/L;
step six: and (3) placing the conversion treatment sample in alcohol for ultrasonic cleaning, and then drying in the air to obtain the magnesium alloy in-situ growth LDH conversion membrane.
Example 2
The method comprises the following steps: polishing magnesium alloy to 5000# abrasive paper, and ultrasonically shaking and washing in acetone to obtain a shaking and washing sample, wherein the ultrasonic shaking and washing power is 150W, and the time is 15 min;
step two: placing the shake-washing sample into alkaline washing liquid for alkaline washing at 60 ℃ for 10min to obtain an alkaline washing sample, wherein the alkaline washing liquid is obtained by dissolving sodium hydroxide, sodium carbonate and sodium phosphate into water, the concentration of the sodium hydroxide in the alkaline washing liquid is 80g/L, the concentration of the sodium carbonate is 40g/L, and the concentration of the sodium phosphate is 30 g/L;
step three: placing the alkali washing sample into acid washing liquid to be subjected to acid washing for 45s at room temperature to obtain an acid washing sample, wherein the acid washing liquid is composed of 65% by mass of nitric acid, 85% by mass of phosphoric acid and 60% by mass of hydrochloric acid, and the volume ratio of the nitric acid to the phosphoric acid to the hydrochloric acid is 30: 500: 20;
step four: immersing an acid-washed sample into an activating solution for activating treatment for 50-60s at room temperature to obtain a pretreated magnesium alloy, wherein the activating solution consists of acetone and 65% by mass of nitric acid, and the volume fraction of the nitric acid in the activating solution is 10%;
step five: putting the pretreated magnesium alloy into a hydrothermal reaction kettle, wherein the filling amount of a hydrothermal conversion treatment liquid is 40%, then keeping the temperature at 100 ℃ under the pressure of 3MPa for 12h, and obtaining a conversion treatment sample after the reaction is finished, wherein the hydrothermal conversion treatment liquid is obtained by dissolving aluminum nitrate, sodium carbonate, sodium hydroxide and ammonium nitrate into water, the concentration of the aluminum nitrate in the hydrothermal conversion treatment liquid is 20.5g/L, the concentration of the sodium carbonate is 11g/L, the concentration of the sodium hydroxide is 11g/L, and the concentration of the ammonium nitrate is 5.5 g/L;
step six: and (3) placing the conversion treatment sample in alcohol for ultrasonic cleaning, and then drying in the air to obtain the magnesium alloy in-situ growth LDH conversion membrane.
Example 3
The method comprises the following steps: polishing magnesium alloy to 5000# abrasive paper, and ultrasonically shaking and washing in acetone to obtain a shaking and washing sample, wherein the ultrasonic shaking and washing power is 150W, and the time is 15 min;
step two: placing the shake-washing sample into alkaline washing liquid for alkaline washing at 60 ℃ for 9min to obtain an alkaline washing sample, wherein the alkaline washing liquid is obtained by dissolving sodium hydroxide, sodium carbonate and sodium phosphate into water, the concentration of the sodium hydroxide in the alkaline washing liquid is 80g/L, the concentration of the sodium carbonate is 40g/L, and the concentration of the sodium phosphate is 30 g/L;
step three: placing the alkali washing sample into acid washing liquid to be subjected to acid washing for 30-45s at room temperature to obtain an acid washing sample, wherein the acid washing liquid is composed of 65% by mass of nitric acid, 85% by mass of phosphoric acid and 60% by mass of hydrochloric acid, and the volume ratio of the nitric acid to the phosphoric acid to the hydrochloric acid is 25: 450: 18;
step four: immersing an acid-washed sample into an activating solution for activating treatment for 55s at room temperature to obtain a pretreated magnesium alloy, wherein the activating solution consists of acetone and 65% by mass of nitric acid, and the volume fraction of the nitric acid in the activating solution is 10%;
step five: putting the pretreated magnesium alloy into a hydrothermal reaction kettle, wherein the filling amount of a hydrothermal conversion treatment liquid is 40%, then keeping the temperature at 100 ℃ under the pressure of 3MPa for 12h, and obtaining a conversion treatment sample after the reaction is finished, wherein the hydrothermal conversion treatment liquid is obtained by dissolving aluminum nitrate, sodium carbonate, sodium hydroxide and ammonium nitrate into water, the concentration of the aluminum nitrate in the hydrothermal conversion treatment liquid is 20g/L, the concentration of the sodium carbonate is 10g/L, the concentration of the sodium hydroxide is 10g/L, and the concentration of the ammonium nitrate is 5 g/L;
step six: and (3) placing the conversion treatment sample in alcohol for ultrasonic cleaning, and then drying in the air to obtain the magnesium alloy in-situ growth LDH conversion membrane.
As can be seen from figures 1XRD and 2SEM, the LDH conversion membrane obtained by the method of the invention is basically composed of LDH, and the combination between the substrate and the membrane layer is good without crack defects and the like.
Comparing the example 3 with the AZ33 magnesium alloy matrix, under the condition of simulating seawater immersion for two hours, the corrosion resistance of the AZ33 magnesium alloy is improved from-1.5K omega to-1000K omega, and the corrosion current is reduced by two orders of magnitude from 10-5A/cm2Down to 10-7A/cm2Even if the immersion time is more than 96 hours, the impedance still exceeds 500K Ω.
Claims (1)
1. A method for growing LDH conversion membrane in situ by magnesium alloy is characterized by comprising the following steps:
the method comprises the following steps: polishing magnesium alloy to 5000# abrasive paper, and then ultrasonically shaking and washing in acetone to obtain a shaking and washing sample, wherein the ultrasonic shaking and washing power is 150W, and the time is 15 min;
step two: putting the shake washing sample into an alkaline washing solution for alkaline washing to obtain an alkaline washing sample, wherein the alkaline washing solution is obtained by dissolving sodium hydroxide, sodium carbonate and sodium phosphate into water, the concentration of the sodium hydroxide in the alkaline washing solution is 80g/L, the concentration of the sodium carbonate is 40g/L, the concentration of the sodium phosphate is 30g/L, the temperature of the alkaline washing is 60 ℃, and the time is 8-10 min;
step three: putting the alkali washing sample into acid washing liquid for acid washing to obtain an acid washing sample, wherein the acid washing liquid consists of 65 mass percent of nitric acid, 85 mass percent of phosphoric acid and 60 mass percent of hydrochloric acid, and the volume ratio of the nitric acid to the phosphoric acid to the hydrochloric acid is (20-30): (400-500): (15-20), pickling at room temperature for 30-45 s;
step four: immersing an acid-washed sample into an activation solution for activation treatment, wherein the activation temperature is room temperature, and the activation time is 50-60s, so as to obtain the pretreated magnesium alloy, wherein the activation solution consists of acetone and nitric acid with the mass fraction of 65%, and the volume fraction of the nitric acid in the activation solution is 10%;
step five: placing the pretreated magnesium alloy in a hydrothermal conversion treatment solution for hydrothermal reaction, and specifically: placing the pretreated magnesium alloy and the hydrothermal conversion treatment liquid into a hydrothermal reaction kettle, wherein the filling amount of the hydrothermal conversion treatment liquid is 40%, then preserving heat for 12 hours at the temperature of 100 ℃ under the pressure of 3Mpa, and obtaining a conversion treatment sample after the reaction is finished; wherein, the hydrothermal conversion treatment liquid is obtained by dissolving aluminum nitrate, sodium carbonate, sodium hydroxide and ammonium nitrate in water, the concentration of the aluminum nitrate in the hydrothermal conversion treatment liquid is (19-20.5) g/L, the concentration of the sodium carbonate is (8-11) g/L, the concentration of the sodium hydroxide is (8-11) g/L, and the concentration of the ammonium nitrate is (4-5.5) g/L;
step six: and (3) placing the conversion treatment sample in alcohol for ultrasonic cleaning, and then drying in the air to obtain the magnesium alloy in-situ growth LDH conversion membrane.
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| CN110129791B (en) * | 2019-06-10 | 2021-05-25 | 辽宁工程技术大学 | Preparation method of molten aluminum corrosion resistant steel surface composite film |
| CN110158095B (en) * | 2019-06-28 | 2021-11-30 | 辽宁工业大学 | Preparation method of zinc-coated steel surface LDH |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101050539A (en) * | 2007-05-21 | 2007-10-10 | 北京化工大学 | Preparing even corrosion resistant hydrotalcite film through surface spin coating method for magnesium alloy, and preparation method |
| 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 |
| CN104611750A (en) * | 2015-01-23 | 2015-05-13 | 沈阳理工大学 | Electrochemical preparation method of black magnesium alloy conversion film |
| CN106086992A (en) * | 2016-06-07 | 2016-11-09 | 重庆大学 | A kind of preparation method of the double hydroxy metal oxide closing membrane layer of Mg alloy surface |
| CN107937900A (en) * | 2017-11-28 | 2018-04-20 | 西安交通大学 | A kind of magnesium alloy growth in situ Corrosion resistant surface treatment method |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100588743C (en) * | 2007-04-09 | 2010-02-10 | 比亚迪股份有限公司 | A kind of acidic solution and treatment process that is used to handle Mg alloy surface |
-
2018
- 2018-06-12 CN CN201810600958.2A patent/CN108707889B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101050539A (en) * | 2007-05-21 | 2007-10-10 | 北京化工大学 | Preparing even corrosion resistant hydrotalcite film through surface spin coating method for magnesium alloy, and preparation method |
| 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 |
| CN104611750A (en) * | 2015-01-23 | 2015-05-13 | 沈阳理工大学 | Electrochemical preparation method of black magnesium alloy conversion film |
| CN106086992A (en) * | 2016-06-07 | 2016-11-09 | 重庆大学 | A kind of preparation method of the double hydroxy metal oxide closing membrane layer of Mg alloy surface |
| CN107937900A (en) * | 2017-11-28 | 2018-04-20 | 西安交通大学 | A kind of magnesium alloy growth in situ Corrosion resistant surface treatment method |
Non-Patent Citations (3)
| Title |
|---|
| Corrosion resistance of in-situ Mg−Al hydrotalcite conversion film on AZ31 magnesium alloy by one-step formation;Rong-chang ZENG,et al.;《Trans. Nonferrous Met. Soc. China》;20151231;第25卷;1917-1925 * |
| 水滑石类化合物及其在腐蚀防护应用中的研究进展;陈君，等;《西华大学学报( 自然科学版)》;20140930;第33卷(第5期);64-69 * |
| 镁合金表面原位生长高耐蚀水碳铝镁石涂层;谢治辉;《兵器材料科学与工程》;20180531;第41卷(第3期);17-19 * |
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