CN107699935B - Micro-arc oxidation electrolyte for preparing iron-containing coating on surface of magnesium alloy and method - Google Patents

Micro-arc oxidation electrolyte for preparing iron-containing coating on surface of magnesium alloy and method Download PDF

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CN107699935B
CN107699935B CN201710968066.3A CN201710968066A CN107699935B CN 107699935 B CN107699935 B CN 107699935B CN 201710968066 A CN201710968066 A CN 201710968066A CN 107699935 B CN107699935 B CN 107699935B
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arc oxidation
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CN107699935A (en
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张荣发
朱园园
张淑芳
王亚萍
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Jiangxi Science and Technology Normal University
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    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02—Anodisation
    • C25D11/30—Anodisation of magnesium or alloys based thereon
    • A—HUMAN NECESSITIES
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    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
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    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02—Anodisation
    • C25D11/024—Anodisation under pulsed or modulated current or potential
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
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    • A—HUMAN NECESSITIES
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Abstract

The invention relates to magnesium alloy micro-arc oxidation electrolyte and a micro-arc oxidation method. The electrolyte includes: fluoride, amine salt (or ammonia), iron-containing and phosphorus-containing electrolytes, and one or more of the following electrolytes can also be added: boric acid or borates, potassium fluorozirconate, carbonates. The micro-arc oxidation method comprises the following steps: pretreatment, micro-arc oxidation and post-treatment. The invention does not use strong alkali, and the used micro-arc oxidation electrolyte is neutral or weakly alkaline. The oxide film prepared by the invention contains a proper amount of fluorine and high content of iron, and has compact structure, good corrosion resistance and good biocompatibility.

Description

Micro-arc oxidation electrolyte for preparing iron-containing coating on surface of magnesium alloy and method
Technical Field
The invention relates to a magnesium alloy surface treatment technology, in particular to a process for preparing a biocompatible coating on the surface of a medical magnesium alloy by adopting micro-arc oxidation.
Background
With the development of science and technology, the aging of population and the increase of trauma caused by industry, traffic, sports and the like, people have more and more demands on biomedical materials and products thereof. At present, the fracture internal fixation device widely used in clinic is mostly made of stainless steel and titanium alloy. Compared with the above metal materials, the magnesium alloy has the following advantages: (1) the elastic modulus (40-45GP) of the magnesium alloy is closer to that of human bones, and the stress shielding effect can be effectively relieved. (2) The stainless steel or titanium alloy may release toxic ions or particles after corrosion or abrasion in body fluids; magnesium is one of the necessary macro elements of human body, and participates in a series of metabolic processes in the body, accelerates bone healing and the like. (3) The metal implants commonly used at present are inert materials and need to be removed by a secondary operation after being used for bone repair. The magnesium alloy is used as a degradable material, so that secondary operation can be avoided, and the pain and economic burden of a patient are reduced. It is particularly appreciated that magnesium alloys have been found to have antibacterial properties in recent years. Although the magnesium alloy has a unique application prospect in the field of biomedicine, the corrosion and degradation speed of the magnesium alloy in body fluid is too high, and the magnesium alloy cannot meet the standard of serving as a degradable biological implant material. Therefore, the improvement of the corrosion resistance of the magnesium alloy and the perfection of the surface modification technology become the key points of the application of the magnesium alloy in the field of orthopedic implant materials.
The micro-arc oxidation is an effective magnesium alloy surface treatment technology, and the formed film has the characteristics of high corrosion resistance, good wear resistance, good combination with a matrix and the like. The micro-arc oxidation is adopted to generate an oxide film on the surface of the magnesium alloy in situ, so that the corrosion degradation rate of the magnesium alloy in body fluid can be delayed, and a porous structure formed on the surface of the coating by spark discharge is favorable for the adhesion, proliferation and differentiation of osteoblasts, and the biocompatibility of the magnesium alloy is improved.
Since the properties of the ceramic membrane prepared by micro-arc oxidation, such as surface appearance, components, structure and corrosion resistance, are mainly determined by the composition of the electrolyte, the matrix material and electrical parameters, an oxide membrane with certain properties can be obtained by adjusting the above influence factors. At present, for magnesium alloy micro-arc oxidation, on the premise of improving the corrosion resistance, if trace elements indispensable in human bones are introduced into a coating, the trace elements are better, and the performances of the coating, such as biocompatibility, osteogenesis, bioactivity or antibacterial property, can be further improved.
The iron element is a trace element indispensable to human health, and the content of the iron element in an adult human body is about 3 g-5 g, wherein 2/3 is concentrated in hemoglobin. Although the content of iron element in human body is small, it has important physiological action. If a human body is lack of iron element for a long time or absorption of the iron element is obstructed, hemoglobin is difficult to generate in the human body, so that hemoglobin is reduced, and even iron-deficiency anemia is generated. Iron deficiency can also have a significant effect on bone salt density, content and brittleness.
The preparation method applies the bionics principle, starts from the components of natural bones, adopts a one-step micro-arc oxidation method in neutral or alkalescent solution, introduces a proper amount of fluorine and higher iron into a micro-arc oxidation film, and realizes the preparation of the high-corrosion-resistance biocompatible coating on the surface of the magnesium alloy.
Disclosure of Invention
In order to overcome the defects, the invention aims to provide a magnesium alloy micro-arc oxidation electrolyte with a coating with higher corrosion resistance and better biocompatibility and a micro-arc oxidation method.
In order to achieve the purpose, the technical scheme of the invention is as follows:
a micro-arc oxidation electrolyte for preparing an iron-containing coating on the surface of a magnesium alloy comprises: fluoride, amine salt (or ammonia), iron-containing and phosphorus-containing electrolytes, and one or more of the following electrolytes can also be added: boric acid or borates, potassium fluorozirconate, carbonates. Wherein, fluoride is 3 g/L-20 g/L, amine salt (or ammonia water) is 50 g/L-500 g/L, iron-containing electrolyte is 2 g/L-50 g/L, phosphoric acid or phosphate is 3 g/L-50 g/L, boric acid or borate is 5 g/L-50 g/L, potassium fluozirconate is 5 g/L-30 g/L, and carbonate is 5 g/L-20 g/L. Boric acid, borate, potassium fluorozirconate, and carbonate may not be added to the electrolyte.
The fluoride is hydrofluoric acid, ammonium bifluoride, sodium fluoride or potassium fluoride; the amine salt is hexamethylenetetramine; the iron-containing electrolyte is one or more of ferric acetate, ferric sulfate and EDTAFeNa.
The phosphoric acid or phosphate is organic phytic acid or phytate such as sodium phytate, potassium phytate, ammonium phytate or inorganic phosphoric acid or phosphate such as sodium phosphate and sodium hydrogen phosphate; the borate is alkali metal salt sodium tetraborate or potassium tetraborate, or alkali metal metaborate sodium metaborate or potassium metaborate, or boric acid is adopted to replace borate; the carbonate is alkali metal salt sodium carbonate, potassium carbonate, lithium carbonate or their hydrogen carbonate.
The invention also relates to a magnesium alloy micro-arc oxidation method, which comprises the following steps:
1) pretreatment: sand blasting, grinding or degreasing, and acid washing;
2) micro-arc oxidation: immersing the pretreated workpiece into the micro-arc oxidation electrolyte, and then carrying out micro-arc oxidation; the power supply is a pulse power supply, the temperature of the electrolyte is controlled to be between 10 and 50 ℃, the time is 2 to 50 minutes, and the final voltage is 100 to 800V;
3) and (5) post-treatment.
Pretreatment: sand blasting, grinding or degreasing, and acid washing. Degreasing and pickling can be sequentially carried out on the machining and die-casting surfaces of the workpiece; for a workpiece with a sand mold casting surface, sand grains on the surface are removed by a sand blasting or grinding method, and then oil removal and acid washing are carried out; the sand blasting or grinding is used for removing foreign matters on the surface and reducing the surface roughness;
in order to achieve better technical effects:
the degreasing adopts one or a compound of 5-40 g/L sodium hydroxide, 5-35 g/L potassium hydroxide, 10-25 g/L sodium silicate, 10-30 g/L sodium carbonate and 10-20 g/L sodium phosphate as an alkali solution, the washing temperature is controlled between 50-95 ℃, and the washing time is 5-15 minutes; the pickling adopts a solution which is a compound solution of one or more acids of hydrofluoric acid with the concentration of 5-20 g/L, nitric acid with the concentration of 5-15 g/L, sulfuric acid with the concentration of 5-25 g/L and phosphoric acid with the concentration of 5-40 g/L, and the washing temperature is controlled to be 20-60 ℃ and the washing time is 0.5-5 minutes.
The power supply is a pulse power supply, and has the characteristics of continuously adjustable positive and negative pulses, frequency and pulse duty ratio, and the current density is 10mA/cm2～80mA/cm2The frequency range is 100 Hz-2000 Hz, the duty ratio of the positive pulse and the negative pulse is respectively 5-40%, the positive final voltage is 100-800V, and the negative final voltage is 50-150V.
The post-treatment comprises the steps of washing with tap water and distilled water, then drying with hot air, and sealing holes in phytic acid (or phytate) aqueous solution or sodium silicate aqueous solution. Sealing holes in phytic acid or phytate aqueous solution: the solution is composed of phytic acid or phytate such as sodium phytate, potassium phytate or ammonium phytate, and appropriate amount of sodium hydroxide or potassium hydroxide is added, the solution temperature is controlled at 60-95 deg.C, and the hole sealing time is 5-20 minutes. Sealing holes in a sodium silicate aqueous solution: the aqueous solution of sodium silicate having a concentration of 50g/L was treated at 95 ℃ for 15 minutes and then allowed to stand in the air to cool for 30 minutes.
And (3) micro-arc oxidation is carried out until the thickness of the oxide film layer is 5-30 mu m, and the color of the oxide film is gray.
During micro-arc oxidation, the workpiece is sealed by neutral silica gel to leave an oxidation surface, and stainless steel is used as a cathode. The oxidation apparatus also includes a stirring and cooling device because the solution temperature rises upon spark discharge. Stirring the electrolyte and low electrolyte temperature allows better cooling of the oxide/electrolyte surface, resulting in less porosity and more uniform morphology of the film.
When the oil stain of the magnesium alloy sample is serious, petroleum, aromatic, hydrocarbon or chlorine-containing solvents can be adopted for solvent treatment before the degreasing of the (alkali liquor) in the method, so as to achieve the optimal degreasing effect; and each operation step of the invention requires water washing.
The invention has the following advantages:
1. the invention uses fluoride as a strong passivant of magnesium alloy, hexamethylenetetramine or ammonia water to adjust the pH value of the solution, iron acetate, ferric sulfate or EDTAFeNa as an iron-containing electrolyte, the micro-arc oxidation electrolyte is neutral or weakly alkaline, strong base is not used, and the final oxidation voltage is high.
2. The micro-arc oxidation electrolyte has simple solution components, is easy to control, does not contain easily decomposed components, and has stable process.
3. The phytic acid or phytate used in the invention is nontoxic and harmless. Phytic acid, also known as phytate, is widely found in oils and cereal seeds. Only one of 6 phosphate groups in the molecular structure of the phytic acid is at the a position, and the other 5 phosphate groups are at the e position. Wherein 4 phosphate groups are positioned on the same plane, so when phytic acid is complexed with metal on the metal surface, a layer of compact monomolecular protective film is easily formed on the metal surface, and O can be effectively prevented2Etc. into the metal surface, thereby slowing the corrosion of the metal.
4. The oxide film prepared by the method contains a proper amount of fluorine and high iron, and has high biocompatibility.
5. The oxide film prepared by the method has the advantages of uniform and compact thickness, smooth surface, small diameter of holes, ceramic appearance, good bonding force with a substrate, 5-30 mu m thickness and good corrosion resistance.
6. The oxide film prepared by the invention contains a proper amount of fluorine and higher iron, can promote the growth of bone cells and improve the biocompatibility of the magnesium alloy.
7. The invention has easily obtained raw materials and is suitable for industrial production.
DETAILED DESCRIPTION OF EMBODIMENT (S) OF INVENTION
The present invention will be described in detail with reference to examples.
Example 1
The sample is an as-cast WE43 magnesium alloy with a size of 50 × 50 × 10mm3The cuboid comprises the following specific operation steps:
1. pretreatment: removing burrs, strong oxides, foreign matters such as a lubricant for extrusion, a mold release agent, casting sand, cutting oil and the like by sand blasting or grinding, and reducing the surface roughness; washing with water;
2. degreasing: washing with a compound solution of 10g/L sodium hydroxide, 15g/L sodium phosphate and 15g/L sodium carbonate to remove common dirt, lubricant, cutting agent and the like attached to sintering; controlling the temperature at 70 ℃ for 5 minutes; washing with water;
3. acid washing: concentrated hydrofluoric acid and phosphoric acid are used according to the volume ratio of 1: 1 washing with a compound acid solution, wherein the mass percent concentration of HF in hydrofluoric acid is not less than 40%, and H in phosphoric acid3PO4The mass percentage concentration of the degreasing agent is not less than 85 percent, and scale, corrosion products, sintering attached lubricants, introduced lubricants, steel particles, casting sand and other dirt which are not removed in degreasing are removed; the temperature is 30 ℃, and the time is 1 minute; washing with water;
4. micro-arc oxidation
Immersing the magnesium alloy sample after pretreatment in a micro-arc oxidation electrolyte, wherein the micro-arc oxidation electrolyte consists of 360g/L hexamethylene tetramine, 6g/L hydrofluoric acid, 35g/L phosphoric acid, 12g/L phytic acid and 18g/L EDTAFeNa, the temperature of the solution is controlled to be 10-50 ℃, positive pulse current is used, and the current density is 60mA/cm2The frequency is 2000Hz, the duty ratio is 35 percent, the oxidation time is 3 minutes, and the final voltage is 475V. The thickness of the oxide film layer is 15 μm, the color of the oxide film is gray, and the surface is smooth.
5. And (5) post-treatment. The samples were washed with tap water, distilled water and blown dry with hot air.
By EDS and XRD analysis, the oxide film contains magnesium, iron, phosphorus, fluorine and other components, and the iron content is 6.57 wt.%. The oxide film is composed of iron oxide, magnesium oxide and magnesium hydroxide.
In the presence of 8g/L NaCl, 0.4g/L KCl and 0.14g/L CaCl2、0.35g/L NaHCO3、1.0g/L C6H12O6、0.2g/L MgSO4.7H2O、0.1g/L KH2PO4.H2O 0.06g/L Na2HPO4.7H2In the simulated body fluid of O, the corrosion resistance of the oxidation sample is improved compared with the matrix by adopting electrochemical polarization curve detection5 times or more.
In vitro cytotoxicity tests show that the magnesium alloy after micro-arc oxidation treatment has better biocompatibility.
Example 2
The cast WE43 magnesium alloy is adopted, and the test sample is cut into 50 × 50 × 10mm by wire cutting3And (3) grinding the cuboid sequentially from coarse to fine by using 180-1000 # waterproof abrasive paper, then cleaning the cuboid in distilled water, finally scrubbing the cuboid with acetone, drying the cuboid in air and putting the cuboid into a dryer for later use.
The difference from the embodiment 1 is that:
the post-treatment is hole sealing in a sodium silicate aqueous solution, and specifically comprises the following steps: sealing holes in aqueous solution of sodium silicate: in 50g/L sodium silicate aqueous solution, heated at 95 ℃ for 15 minutes, and then left in the air to cool for 30 minutes.
Example 3
The cast WE43 magnesium alloy is adopted, and the test sample is cut into 50 × 50 × 10mm by wire cutting3The cuboid is sequentially polished from coarse to fine by 180-1000 # waterproof abrasive paper, then is cleaned in distilled water, and finally is scrubbed by acetone and is placed in a dryer for later use after being dried in air.
The difference from the embodiment 1 is that:
the micro-arc oxidation solution consists of 360g/L hexamethylene tetramine, 6g/L ammonium bifluoride, 35g/L phosphoric acid, 8g/L phytic acid and 6g/L EDTAFeNa. Oxidizing for 3 min to reach 453V final voltage. EDS analysis showed that the oxide film contained 2.31 wt% Fe. As the edtafina concentration decreases, the iron content in the oxide film decreases; but the diameter of the micropores of the coating is reduced, and the oxidation sample has good corrosion resistance which is improved by more than ten times compared with the corrosion resistance of the matrix. In vitro cytotoxicity tests show that the magnesium alloy after micro-arc oxidation treatment has better biocompatibility.
Example 4
The test sample is cut into 50 × 50 × 10mm by using an extruded WE43 magnesium alloy3The cuboid is sequentially polished from coarse to fine by 180-1000 # waterproof abrasive paper, then is cleaned in distilled water, and finally is scrubbed by acetone and is placed in a dryer for later use after being dried in air.
The difference from the embodiment 1 is that:
using a double pulse current with a frequency of 2000Hz and a positive current density of 50mA/cm2Positive duty ratio of 5% and negative current density of 30mA/cm2The negative duty ratio is 20%, the oxidation time is 20 minutes, the positive final voltage is 300V, and the negative final voltage is 120V. The thickness of the oxide film layer is 12 μm, and the color is gray.
Example 5
An extruded WE43 magnesium alloy was used.
The test specimens were cut to 50 × 50 × 10mm3The cuboid is sequentially polished from coarse to fine by 180-1000 # waterproof abrasive paper, then is cleaned in distilled water, and finally is scrubbed by acetone and is placed in a dryer for later use after being dried in air.
The difference from the embodiment 1 is that:
the micro-arc oxidation solution consists of 350g/L hexamethylene tetramine, 6g/L ammonium bifluoride, 35g/L phosphoric acid, 8g/L phytic acid and 24g/L EDTAFeNa, and the iron content in the oxidation film is high and reaches 8.16 wt%.
Example 6
The difference from the embodiment 1 is that:
the cast Mg-1.0Ca alloy is adopted, and the sample is cut into 50 × 50 × 10mm by a wire3The cuboid is sequentially polished from coarse to fine by 180-1000 # waterproof abrasive paper, then is cleaned in distilled water, and finally is scrubbed by acetone and is placed in a dryer for later use after being dried in air.
When the matrix is Mg-1.0Ca alloy, a micro-arc oxidation method can be adopted to generate a coating containing a proper amount of fluorine and higher iron on the surface.
Example 7
Degreasing by using one or a compound of 5-40 g/L sodium hydroxide, 5-35 g/L potassium hydroxide, 10-25 g/L sodium silicate, 10-30 g/L sodium carbonate and 10-20 g/L sodium phosphate as an alkali solution, wherein the washing temperature is controlled between 50-95 ℃, and the washing time is 5-15 minutes;
the pickling adopts a solution which is a compound solution of one or more acids of hydrofluoric acid with the concentration of 5-20 g/L, nitric acid with the concentration of 5-15 g/L, sulfuric acid with the concentration of 5-25 g/L and phosphoric acid with the concentration of 5-40 g/L, and the washing temperature is controlled to be 20-60 ℃ and the washing time is 0.5-5 minutes.
The rest is the same as example 1.
Example 8
The cast WE43 magnesium alloy is adopted, and the test sample is cut into 50 × 50 × 10mm by wire cutting3The cuboid is sequentially polished from coarse to fine by 180-1000 # waterproof abrasive paper, then is cleaned in distilled water, and finally is scrubbed by acetone and is placed in a dryer for later use after being dried in air.
The difference from the embodiment 1 is that:
the post-treatment is hole sealing in phytic acid aqueous solution: the solution consists of 4g/L sodium hydroxide and 12g/L sodium phytate, the temperature of the solution is controlled at 60 ℃, and the hole sealing time is 10 minutes.
Example 9
An extruded WE43 magnesium alloy was used.
The micro-arc oxidation electrolyte consists of 6g/L ammonium bifluoride, 25g/L phosphoric acid, 12g/L phytic acid, 350g/L hexamethylenetetramine and 20g/L Fe2(SO)3The composition of the composition enables smooth formation of an oxide film.

Claims (6)

1. A micro-arc oxidation electrolyte for preparing an iron-containing coating on the surface of a magnesium alloy is characterized in that: the method comprises the following steps: the micro-arc oxidation electrolyte is neutral or weakly alkaline, and comprises fluoride, amine salt or ammonia water, iron-containing electrolyte and phosphorus-containing electrolyte, wherein the fluoride is hydrofluoric acid, ammonium bifluoride, sodium fluoride or potassium fluoride, the amine salt is hexamethylene tetramine, the iron-containing electrolyte is one or more of iron acetate, ferric sulfate and EDTAFeNa, and the phosphorus-containing electrolyte is organic phytic acid, sodium phytate, potassium phytate, ammonium phytate, inorganic phosphoric acid, sodium phosphate or sodium hydrogen phosphate;
wherein the concentration of fluoride is 3 g/L-20 g/L, the concentration of amine salt or ammonia water is 50-500g/L, the concentration of iron-containing electrolyte is 2-50g/L, and the concentration of phosphorus-containing electrolyte is 3 g/L-50 g/L;
the electrolyte also comprises one or more electrolytes of boric acid or borate, potassium fluozirconate and carbonate; the borate is sodium tetraborate, potassium tetraborate, sodium metaborate or potassium metaborate; the carbonate is sodium carbonate, potassium carbonate or lithium carbonate;
the concentration of the boric acid or the borate is 5g/L to 50g/L, the concentration of the potassium fluozirconate is 5g/L to 30g/L, and the concentration of the carbonate is 5g/L to 20 g/L.
2. A micro-arc oxidation method for preparing an iron-containing coating on the surface of a magnesium alloy is characterized by comprising the following steps: the method comprises the following steps:
1) pretreatment: sand blasting, grinding or degreasing and acid washing are carried out on the workpiece;
2) micro-arc oxidation: immersing the pretreated workpiece into the electrolyte of claim 1, and then carrying out micro-arc oxidation; the power supply is a pulse power supply, the temperature of the electrolyte is controlled to be between 10 and 50 ℃, the time is 2 to 30 minutes, and the final voltage is 100 to 800V;
3) and (5) post-treatment.
3. The micro-arc oxidation method for preparing the iron-containing coating on the surface of the magnesium alloy according to claim 2, wherein the micro-arc oxidation method comprises the following steps: the sand blasting and grinding can remove burrs on the surface of a workpiece, firm oxides, a lubricant for extrusion, a release agent, casting sand, cutting oil foreign matters and reduce the surface roughness; degreasing by using one or a compound of 5-40 g/L sodium hydroxide, 5-35 g/L potassium hydroxide, 10-25 g/L sodium silicate, 10-30 g/L sodium carbonate and 10-20 g/L sodium phosphate as an alkali solution, wherein the washing temperature is controlled between 50-95 ℃, and the washing time is 5-15 minutes; the pickling adopts a solution which is a compound solution of one or more acids of hydrofluoric acid with the concentration of 5-20 g/L, nitric acid with the concentration of 5-15 g/L, sulfuric acid with the concentration of 5-25 g/L and phosphoric acid with the concentration of 5-40 g/L, and the washing temperature is controlled to be 20-60 ℃ and the washing time is 0.5-5 minutes.
4. The micro-arc oxidation method for preparing the iron-containing coating on the surface of the magnesium alloy according to claim 2, wherein the micro-arc oxidation method comprises the following steps: the power supply is a pulse power supply, and has the characteristics of continuously adjustable positive and negative pulses, frequency and pulse duty ratio, and the current density is 10mA/cm2～80mA/cm2The frequency range is 100 Hz-2000 Hz, the duty ratio of the positive pulse and the negative pulse is respectively 5-40%, the positive final voltage is 100-800V, and the negative final voltage is 50-200V.
5. The micro-arc oxidation method for preparing the iron-containing coating on the surface of the magnesium alloy according to claim 2, wherein the micro-arc oxidation method comprises the following steps: the post-treatment is that tap water and distilled water are used for washing, and then hot air is used for drying, or hole sealing is adopted in phytic acid or phytate aqueous solution or sodium silicate aqueous solution.
6. The micro-arc oxidation method for preparing the iron-containing coating on the surface of the magnesium alloy according to claim 5, wherein the micro-arc oxidation method comprises the following steps: sealing holes in phytic acid or phytate aqueous solution: the solution is composed of phytic acid, sodium phytate, potassium phytate or ammonium phytate, sodium hydroxide or potassium hydroxide is added, the temperature of the solution is controlled at 60-95 ℃, and the hole sealing time is 5-20 minutes; sealing holes in a sodium silicate aqueous solution: the aqueous solution of sodium silicate having a concentration of 50g/L was treated at 95 ℃ for 15 minutes and then left to cool in the air for 30 minutes.
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