CN107699935A - A kind of Mg alloy surface prepares the micro-arc oxidation electrolyte and method of iron content coating - Google Patents

A kind of Mg alloy surface prepares the micro-arc oxidation electrolyte and method of iron content coating Download PDF

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CN107699935A
CN107699935A CN201710968066.3A CN201710968066A CN107699935A CN 107699935 A CN107699935 A CN 107699935A CN 201710968066 A CN201710968066 A CN 201710968066A CN 107699935 A CN107699935 A CN 107699935A
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electrolyte
arc oxidation
sodium
iron content
acid
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CN107699935B (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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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • 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
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • 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
    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/02—Inorganic materials
    • A61L27/04—Metals or alloys
    • A61L27/047—Other specific metals or alloys not covered by A61L27/042 - A61L27/045 or A61L27/06
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • 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
    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/28—Materials for coating prostheses
    • A61L27/30—Inorganic materials
    • A61L27/306—Other specific inorganic materials not covered by A61L27/303 - A61L27/32
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • 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
    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
    • A61L27/54—Biologically active materials, e.g. therapeutic substances
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • 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
    • C25D11/024—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
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02—Anodisation
    • C25D11/026—Anodisation with spark discharge
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • 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
    • A61L2400/00—Materials characterised by their function or physical properties
    • A61L2400/18—Modification of implant surfaces in order to improve biocompatibility, cell growth, fixation of biomolecules, e.g. plasma treatment
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • 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
    • A61L2430/00—Materials or treatment for tissue regeneration
    • A61L2430/02—Materials or treatment for tissue regeneration for reconstruction of bones; weight-bearing implants

Abstract

The present invention relates to magnesium alloy differential arc oxidation electrolyte and differential arc oxidation method.Electrolyte includes：Fluoride, amine salt (or ammoniacal liquor), iron content and phosphorous electrolyte, can also add following one or more of electrolyte：Boric acid or borate, potassium fluorozirconate, carbonate.The differential arc oxidation method includes：Pre-treatment, differential arc oxidation, post processing.For the present invention without using highly basic, micro-arc oxidation electrolyte used is neutral or alkalescent.The iron of oxide-film prepared by the present invention containing appropriate fluorine and high content, and compact structure, corrosion resistance are good, have good biocompatibility.

Description

A kind of Mg alloy surface prepares the micro-arc oxidation electrolyte and method of iron content coating
Technical field
The present invention relates to magnesium alloy surface treatment, specifically medical magnesium alloy surface is prepared using differential arc oxidation The technique of biocompatible coating.
Background technology
With wound increase, people couple caused by scientific technological advance, aging population and industry, traffic, physical culture etc. The demand of bio-medical material and its product is increasing.Current clinically widely used Fracture internal fixaiion equipment is more by stainless Steel and titanium alloy manufacture.Compared with above metal material, magnesium alloy has the advantage that：(1) modulus of elasticity (40- of magnesium alloy It is 45GP) closer with people's bone, it can effectively alleviate stress-shielding effect.(2) stainless steel or titanium alloy corrode or worn in body fluid Poisonous ion or particle may be discharged afterwards；And magnesium is one of necessary macroelement of human body, participate in a series of new old in vivo Metabolic process, accelerate knitting etc..(3) currently used metal implant is inert material, is needed after for Bone Defect Repari through two Secondary operation is taken out.Magnesium alloy is avoided that second operation, reduces patient suffering and financial burden as degradation material.Especially make People it is joyful be that discovered in recent years magnesium alloy has anti-microbial property.Although magnesium alloy has unique application in bio-medical field Prospect, but its corrosion degradation excessive velocities in body fluid, it is impossible to meet the standard as degradable biological implantation material.Therefore, Improving magnesium alloy decay resistance in itself and perfect surface modification technology turns into magnesium alloy in orthopaedics inner implantation material field The key of application.
Differential arc oxidation is a kind of effective magnesium alloy surface treatment, and the film layer formed has corrosion resisting property high, resistance to The features such as mill performance is good and is well combined with matrix.Using differential arc oxidation in Mg alloy surface in-situ preparation oxide-film, not only It can delay corrosion degradation speed of the magnesium alloy in body fluid, and because spark discharge has in the loose structure that coating surface is formed Beneficial to the adhesion of Gegenbaur's cell, propagation and differentiation, the biocompatibility of magnesium alloy is improved.
Because ceramic film properties such as surface topography, composition, structure and the corrosion resistance of differential arc oxidation preparation are mainly by electrolyte Composition, matrix material and electrical parameter are determined, therefore can obtain the oxide-film of certain performance by adjusting above influence factor. At present for magnesium alloy differential arc oxidation, under the premise of its corrosion resistance is improved, if indispensable trace element in people's bone is drawn Enter in coating more preferably, can further improve performance such as biocompatibility, osteogenic, bioactivity or antibiotic property etc. of coating.
Ferro element is the indispensable trace element of health, and the content of ferro element is about 3g~5g in adult human body, Wherein 2/3 concentrates in hemoglobin.Though the content of ferro element is few in human body, there is important physiological action.If human body It is long-term to lack ferro element, or when absorption to ferro element is by obstacle, is just difficult to produce hemoglobin in human body, causes hemochrome Reduce, or even hypoferric anemia occurs.Asiderosis can also produce great influence to Bone mineral density, content and fragility.
This patent application bionics principle, from the composition of nature bone, in neutral or weakly alkaline solution, using a step Differential arc oxidation method, appropriate fluorine and higher iron are introduced into micro-arc oxidation films, realized high anti-corrosion in Mg alloy surface preparation Property biocompatible coating.
The content of the invention
It is a kind of with compared with high corrosion-resistant, preferable biocompatibility present invention aims at providing in order to overcome above-mentioned deficiency The magnesium alloy differential arc oxidation electrolyte and differential arc oxidation method of coating.
To achieve these goals, the technical scheme is that：
The micro-arc oxidation electrolyte that a kind of Mg alloy surface prepares iron content coating includes：Fluoride, amine salt (or ammoniacal liquor), contain Iron and phosphorous electrolyte, it can also add following one or more of electrolyte：Boric acid or borate, potassium fluorozirconate, carbonate.Wherein Fluoride 3g/L~20g/L, amine salt (or ammoniacal liquor) 50-500g/L, iron content electrolyte 2-50g/L, phosphorous acid or phosphate 3g/ L~50g/L, boric acid or borate 5g/L~50g/L, potassium fluorozirconate 5-30g/L, carbonate 5g/L~20g/L.In electrolyte Boric acid or borate, potassium fluorozirconate, carbonate can not be added.
The fluoride is hydrofluoric acid, ammonium acid fluoride, sodium fluoride or potassium fluoride；Amine salt is hexamethylenetetramine；Containing ferroelectricity Solution matter be ferric acetate, ferric sulfate, EDTAFeNa one or more.
The phosphorous acid or phosphate be organic phytic acid or phytate as sodium phytate, POTASSIUM PHYTATE, phytic acid ammonium or it is inorganic Phosphoric acid or phosphate such as sodium phosphate, dibastic sodium phosphate；The borate is the salt sodium tetraborate or dipotassium tetraborate of alkali metal, either The metaborate kodalk or potassium metaborate of alkali metal, or borate is replaced using boric acid；Carbonate is alkali metal salt carbon Sour sodium, potassium carbonate, lithium carbonate or their bicarbonate.
The invention further relates to a kind of magnesium alloy differential arc oxidation method, comprise the following steps：
1) pre-treatment：Sandblasting, grinding or degreasing, pickling；
2) differential arc oxidation：Workpiece after pre-treatment is immersed in above-mentioned micro-arc oxidation electrolyte, then differential arc oxidation；It is used Power supply is the pulse power, and electrolyte temperature is controlled between 10-50 DEG C, and the time is 2~50 minutes, and whole voltage is 100~800V；
3) post-process.
Pre-treatment：Sandblasting, grinding or degreasing, pickling.For workpiece machine add with die casting surface, can carry out successively degreasing and Pickling；For the workpiece with sand casting surface, surface sand grains first should be removed with sandblasting or Ginding process, then carry out oil removing And pickling；The sandblasting or grinding, Superficial Foreign Body is removed, reduce surface roughness；
In order to reach superior technique effect：
The degreasing uses aqueous slkali as 5~40g/l of concentration sodium hydroxides, 5~35g/L potassium hydroxide, 10~25g/L silicon Sour sodium, 10~30g/L sodium carbonate, 10~20g/L sodium phosphates one of which or its compound, its wash temperature are controlled 50~95 Between DEG C, the time is 5~15 points；The pickling use solution for 5~20g/L of concentration hydrofluoric acid, 5~15g/L nitric acid, 5~ A kind of sour or a variety of sour combination solutions in 25g/L sulfuric acid, 5~40g/L phosphoric acid, its wash temperature are controlled at 20~60 DEG C, when Between be 0.5~5 point.
Power supply used is the pulse power, and it has the characteristics of positive negative pulse stuffing, frequency and pulse duty factor continuously adjustabe, electric current Density is 10mA/cm2~80mA/cm2, frequency range is 100Hz~2000Hz, positive and negative pulse duty factor each 5~40%, positive whole Voltage is 100~800V, bears whole 50~150V of voltage.
The post processing includes using running water and distilled water flushing, then with hot blast drying, can also use again in phytic acid Sealing of hole in (or phytate) aqueous solution or in sodium silicate aqueous solution.The sealing of hole in phytic acid or phytic acid saline solution：Solution by Phytic acid or phytate such as sodium phytate, POTASSIUM PHYTATE or phytic acid ammonium composition, add appropriate sodium hydroxide or potassium hydroxide, solution temperature At 60-95 DEG C, the sealing of hole time is 5-20 minutes for control.The sealing of hole in sodium silicate aqueous solution：Sodium silicate aqueous solution concentration is 50g/L, handled in 95 DEG C 15 minutes, then place and 30 points are cooled down in air.
Differential arc oxidation to oxidation film layer thickness is 5~30 μm, and oxide-film color is grey.
During differential arc oxidation, workpiece reserves oxide side with neutral silica gel approved sample, and stainless steel is negative electrode.During due to spark discharge, Solution temperature can raise, thus oxidation unit also includes stirring cooling device.Stir electrolyte and low electrolyte temperature can So that oxide/electrolyte surface preferably cools down, thus the hole of film is less, and pattern is evenly.
When magnesium alloy sample greasy dirt is serious, petroleum-type, aromatics can be used before above-mentioned (alkali lye) degreasing of the inventive method Class, hydro carbons or chloride class solvent carry out solvent processing, to reach optimal degreasing effect；And each operating procedure of the present invention After be both needed to wash.
The invention has the advantages that：
1. the present invention adjusts solution ph using the strong passivator that fluoride is magnesium alloy, hexamethylenetetramine or ammoniacal liquor, Ferric acetate, ferric sulfate or EDTAFeNa are iron content electrolyte, and micro-arc oxidation electrolyte is neutral or alkalescent, without using highly basic, It is high to aoxidize whole voltage.
2. the micro-arc oxidation electrolyte of the present invention, solution composition is simple, easily controllable, decomposes composition without easy, technique is steady It is fixed.
3. phytic acid or phytate used in the present invention, nontoxic.Phytic acid is also known as phytic acid, is widely present in oil In class and seed corn.6 phosphates only have one to be in a positions in phytate molecule structure, and other 5 on e positions.Wherein have 4 phosphates are in the same plane, therefore phytic acid easily forms one layer of cause when metal surface is with metal complex in metal surface Close unimolecule diaphragm, can effectively prevent O2Deng metal surface is entered, so as to slow down corrosion of metal.
4. the oxidation film layer prepared using the present invention, containing appropriate fluorine and higher iron, has preferable biocompatibility.
5. using oxidation film layer produced by the present invention, thickness is uniformly, fine and close, surface is smooth, hole diameter is small, has ceramics Outward appearance, good with basal body binding force, oxidation film layer thickness is 5~30 μm, has good corrosion resistance.
6. bone cell growth can be promoted containing appropriate fluorine and higher iron in oxidation film layer produced by the present invention, improve magnesium The biocompatibility of alloy.
7. raw material of the present invention is easy to get, suitable for industrialized production.
Specific embodiment
The present invention is described in detail with reference to embodiment.
Embodiment 1
Sample is the WE43 magnesium alloys of as cast condition, and size is 50 × 50 × 10mm3Cuboid, its concrete operation step are：
1. pre-treatment：With sandblasting or grinding, except deburring, firm oxide, extruding with lubricator, releasing agent, casting The foreign matters such as sand, cutting oil, reduce surface roughness；Washing；
2. degreasing：Washed, removed general dirty with 10g/L sodium hydroxides, 15g/L sodium phosphates, 15g/L sodium carbonate combination solutions Thing, the lubricant of sintering attachment, cutting agent etc.；For temperature control at 70 DEG C, the time is 5 points；Washing；
3. pickling：With dense hydrofluoric acid, phosphoric acid by volume 1：The acid solution wash of 1 compounding, HF wherein in hydrofluoric acid Mass percent concentration is no less than 40%, H in phosphoric acid3PO4Mass percent concentration be no less than 85%, remove degreasing in do not remove The oxide skin gone, corrosion product, the lubricant of sintering attachment, lubricant, steel grit, casting model powder and other dirts for bringing into；Temperature For 30 DEG C, the time is 1 point；Washing；
4. differential arc oxidation
Magnesium alloy sample through pre-treatment is immersed in micro-arc oxidation electrolyte, the micro-arc oxidation electrolyte is by 360g/L Hexamethylenetetramine, 6g/L hydrofluoric acid, 35g/L phosphoric acid, 12g/L phytic acid and 18g/L EDTAFeNa composition, control solution temperature 10-50 DEG C of degree, uses positive pulse electric current, current density 60mA/cm2, frequency 2000Hz, dutycycle 35%, oxidization time 3 Point, whole voltage 475V.Oxidation film layer thickness is 15 μm, and oxide-film color is grey, and surface is smooth.
5. post processing.Sample is washed with originally washing, distillation and uses hot blast drying respectively.
Using EDS and XRD analysis, contain the compositions such as magnesium, iron, phosphorus, fluorine, iron content 6.57wt.% in oxide-film.Oxide-film It is made up of iron oxide, magnesia and magnesium hydroxide.
In NaCl containing 8g/L, 0.4g/L KCl, 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 O simulated body fluid, using electrochemistry Polarization curve detects, and with matrix phase ratio, the corrosion resistance of oxidation sample improves more than 5 times.
Vitro cytotoxicity test shows that the magnesium alloy after differential arc oxidation processing has preferable biocompatibility.
Embodiment 2
Using as cast condition WE43 magnesium alloys.Sample wire cutting is into 50 × 50 × 10mm3Cuboid, with 180~1000# water Sand paper is from coarse to fine to be ground successively, is then cleaned in distilled water, is finally cleaned and is inserted after drying in atmosphere dry with acetone It is stand-by in dry device.
Difference from Example 1 is：
The post processing is the sealing of hole in sodium silicate aqueous solution, is specially：The sealing of hole in sodium silicate aqueous solution：In 50g/L Sodium silicate aqueous solution in, in 95 DEG C heat 15 minutes, then place air in cool down 30 points.
Embodiment 3
Using as cast condition WE43 magnesium alloys.Sample wire cutting is into 50 × 50 × 10mm3Cuboid, with 180~1000# water Sand paper is from coarse to fine to polish successively, is then cleaned in distilled water, is finally cleaned and is inserted after drying in atmosphere dry with acetone It is stand-by in dry device.
Difference from Example 1 is：
Microarc oxidation solution is by 360g/L hexamethylenetetramine, 6g/L ammonium acid fluorides, 35g/L phosphoric acid, 8g/L phytic acid and 6g/L EDTAFeNa are formed.Oxidation 3 minutes, whole voltage is up to 453V.EDS analysis shows, contain 2.31wt%Fe in oxide-film. As EDTAFeNa concentration is reduced, the iron content in oxide-film reduces；But coating micropore diameter reduces, oxidation sample has fine Corrosion resistance, than matrix corrosion resistance improve more than ten times.Vitro cytotoxicity test shows that the magnesium after differential arc oxidation processing closes Gold utensil has preferable biocompatibility.
Embodiment 4
Using extruding WE43 magnesium alloys.Sample wire cutting is into 50 × 50 × 10mm3Cuboid, with 180~1000# water Sand paper is from coarse to fine to polish successively, is then cleaned in distilled water, is finally cleaned and is inserted after drying in atmosphere dry with acetone It is stand-by in dry device.
Difference from Example 1 is：
Use dipulse electric current, 2000 hertz of frequency, positive electricity current density 50mA/cm2, positive dutycycle 5%, negative electricity current density 30mA/cm2, negative duty 20%, oxidization time 20 minutes, just whole voltage 300V, it is 120V to bear whole voltage.Oxidation film layer thickness For 12 μm, color is grey.
Embodiment 5
Using extruding WE43 magnesium alloys.
Sample wire cutting is into 50 × 50 × 10mm3Cuboid, beaten successively with 180~1000# waterproof abrasive paper is from coarse to fine Mill, is then cleaned in distilled water, is finally cleaned and is inserted after drying in atmosphere stand-by in drier with acetone.
Difference from Example 1 is：
Microarc oxidation solution is by 350g/L hexamethylenetetramine, 6g/L ammonium acid fluorides, 35g/L phosphoric acid, 8g/L phytic acid and 24g/L EDTAFeNa are formed, and iron-holder is very high in oxide-film, up to 8.16wt%.
Embodiment 6
Difference from Example 1 is：
Using as cast condition Mg-1.0Ca alloys.Sample wire cutting is into 50 × 50 × 10mm3Cuboid, with 180~1000#'s Waterproof abrasive paper is from coarse to fine to polish successively, is then cleaned in distilled water, is finally cleaned with acetone and is inserted after drying in atmosphere It is stand-by in drier.
, also can be in its Surface Creation containing appropriate fluorine and higher using differential arc oxidation method when matrix is Mg-1.0Ca alloys Iron coating.
Embodiment 7
Degreasing uses aqueous slkali as 5~40g/L of concentration sodium hydroxides, 5~35g/L potassium hydroxide, 10~25g/L silicic acid Sodium, 10~30g/L sodium carbonate, 10~20g/l sodium phosphates one of which or its compound, its wash temperature are controlled at 50~95 DEG C Between, the time is 5~15 points；
The pickling use solution for 5~20g/L of concentration hydrofluoric acid, 5~15g/L nitric acid, 5~25g/L sulfuric acid, 5~ A kind of sour or a variety of sour combination solutions in 40g/l phosphoric acid, for the control of its wash temperature at 20~60 DEG C, the time is 0.5~5 point.
Remaining is the same as embodiment 1.
Embodiment 8
Using as cast condition WE43 magnesium alloys.Sample wire cutting is into 50 × 50 × 10mm3Cuboid, with 180~1000# water Sand paper is from coarse to fine to polish successively, is then cleaned in distilled water, is finally cleaned and is inserted after drying in atmosphere dry with acetone It is stand-by in dry device.
Difference from Example 1 is：
The post processing is the sealing of hole in the phytic acid aqueous solution：Solution is made up of 4g/L sodium hydroxides and 12g/L sodium phytates, molten For liquid temperature control at 60 DEG C, the sealing of hole time is 10 minutes.
Embodiment 9
Using extruding WE43 magnesium alloys.
Micro-arc oxidation electrolyte is by 6g/L ammonium acid fluorides, 25g/L phosphoric acid, 12g/L phytic acid, 350g/L hexamethylenetetramine With 20g/L Fe2(SO)3Composition, can be successfully generated oxide-film.

Claims (9)

1. a kind of Mg alloy surface prepares the micro-arc oxidation electrolyte of iron content coating, it is characterised in that：Including：Fluoride, amine salt (or ammoniacal liquor), iron content and phosphorous electrolyte, the fluoride are hydrofluoric acid, ammonium acid fluoride, sodium fluoride or potassium fluoride, the amine salt For hexamethylenetetramine, the iron content electrolyte is ferric acetate, ferric sulfate, EDTAFeNa one or more, the phosphorous electricity It is organic phytic acid or phytate such as sodium phytate, POTASSIUM PHYTATE, phytic acid ammonium or inorganic phosphoric acid or phosphate such as sodium phosphate, phosphoric acid to solve matter Hydrogen sodium.
2. a kind of Mg alloy surface as claimed in claim 1 prepares the micro-arc oxidation electrolyte of iron content coating, it is characterised in that： Wherein fluoride concentration is 3g/L~20g/L, and amine salt (or ammoniacal liquor) concentration is 50-500g/L, and iron content electrolyte concentration is 2- 50g/L, phosphorous electrolyte concentration are 3g/L~50g/L.
3. a kind of Mg alloy surface as claimed in claim 1 prepares the micro-arc oxidation electrolyte of iron content coating, it is characterised in that： Bath composition also includes boric acid or borate, potassium fluorozirconate, carbonate one or more electrolyte；The borate is alkali gold The salt sodium tetraborate or dipotassium tetraborate of category, or the metaborate kodalk or potassium metaborate of alkali metal, or using boron Acid replaces borate；The carbonate is alkali metal salt sodium carbonate, potassium carbonate, lithium carbonate or their bicarbonate.
4. a kind of Mg alloy surface as claimed in claim 3 prepares the micro-arc oxidation electrolyte of iron content coating, it is characterised in that： The boric acid or borate concentration are 5g/L~50g/L, and potassium fluorozirconate concentration is 5-30g/L, carbonate concentration be 5g/L~ 20g/L。
5. a kind of Mg alloy surface prepares the differential arc oxidation method of iron content coating, it is characterised in that：Comprise the following steps：
1) pre-treatment：By workpiece sandblasting, grinding or degreasing, pickling；
2) differential arc oxidation：Workpiece after pre-treatment is immersed in any one of the claim 1-4 electrolyte, then differential of the arc oxygen Change；Power supply used is the pulse power, and electrolyte temperature is controlled between 10-50 DEG C, and the time is 2~30 minutes, and whole voltage is 100 ~800V；
3) post-process.
6. a kind of Mg alloy surface as claimed in claim 5 prepares the differential arc oxidation method of iron content coating, it is characterised in that：Institute State sandblasting and grinding can remove workpiece surface burr, firm oxide, extruding with lubricator, releasing agent, casting model powder, cutting oil Deng foreign matter, reduce surface roughness；Degreasing use aqueous slkali for 5~40g/L of concentration sodium hydroxides, 5~35g/L potassium hydroxide, 10~25g/L sodium metasilicate, 10~30g/L sodium carbonate, 10~20g/L sodium phosphates one of which or its compound, its wash temperature Between 50~95 DEG C, the time is 5~15 points for control；The pickling uses solution as 5~20g/L of concentration hydrofluoric acid, 5~15g/ A kind of sour or a variety of sour combination solutions in L nitric acid, 5~25g/L sulfuric acid, 5~40g/L phosphoric acid, its wash temperature are controlled 20 ~60 DEG C, the time is 0.5~5 point.
7. a kind of Mg alloy surface as claimed in claim 5 prepares the differential arc oxidation method of iron content coating, it is characterised in that：Institute It is the pulse power with power supply, it has the characteristics of positive negative pulse stuffing, frequency and pulse duty factor continuously adjustabe, and current density is 10mA/cm2~80mA/cm2, frequency range is 100Hz~2000Hz, positive and negative pulse duty factor each 5~40%, and just whole voltage is 100~800V, bear whole 50~200V of voltage.
8. a kind of Mg alloy surface as claimed in claim 5 prepares the differential arc oxidation method of iron content coating, it is characterised in that：Institute It is using running water and distilled water flushing, then with hot blast drying, or using in phytic acid (or phytate) aqueous solution to state post processing In or sodium silicate aqueous solution in sealing of hole.
9. a kind of Mg alloy surface as claimed in claim 8 prepares the differential arc oxidation method of iron content coating, it is characterised in that：Institute State the sealing of hole in phytic acid (or phytate) aqueous solution：Solution is made up of phytic acid or phytate such as sodium phytate, POTASSIUM PHYTATE or phytic acid ammonium, Sodium hydroxide or potassium hydroxide are added, solution temperature is controlled at 60-95 DEG C, and the sealing of hole time is 5-20 minutes；It is described in sodium metasilicate Sealing of hole in the aqueous solution：Sodium silicate aqueous solution concentration is 50g/L, is handled in 95 DEG C 15 minutes, then places and 30 points are cooled down in air Clock.
CN201710968066.3A 2017-10-17 2017-10-17 Micro-arc oxidation electrolyte for preparing iron-containing coating on surface of magnesium alloy and method Expired - Fee Related CN107699935B (en)

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CN110004477A (en) * 2019-04-18 2019-07-12 西安强微电气设备有限公司 A kind of electrolyte and the method for preparing Mg alloy surface black film layer with the electrolyte
CN111321332A (en) * 2018-12-17 2020-06-23 佳能株式会社 Magnesium-lithium alloy member, method for manufacturing same, optical device, and imaging device
CN111821505A (en) * 2020-06-04 2020-10-27 东南大学 Super-paramagnetic nano-coating oral implant and preparation method thereof
US11180832B2 (en) 2018-12-17 2021-11-23 Canon Kabushiki Kaisha Magnesium-lithium alloy member, manufacturing method thereof, optical apparatus, imaging apparatus, electronic apparatus and mobile object
CN114686952A (en) * 2022-05-07 2022-07-01 山西银光华盛镁业股份有限公司 Preparation method of transparent oxide film on surface of plastic deformation magnesium alloy workpiece
CN114870083A (en) * 2022-04-16 2022-08-09 上海交通大学医学院附属第九人民医院 Preparation method and application of implant with complex coating on surface

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CN109295488A (en) * 2018-09-29 2019-02-01 广东省生物工程研究所（广州甘蔗糖业研究所） A kind of magnetic coupling membrane of oxide ceramics and preparation method with self-styled pore structure
CN109295488B (en) * 2018-09-29 2020-08-11 广东省生物工程研究所（广州甘蔗糖业研究所） Magnetic composite oxide ceramic membrane with self-sealing hole structure and preparation method thereof
CN111321332A (en) * 2018-12-17 2020-06-23 佳能株式会社 Magnesium-lithium alloy member, method for manufacturing same, optical device, and imaging device
US11180832B2 (en) 2018-12-17 2021-11-23 Canon Kabushiki Kaisha Magnesium-lithium alloy member, manufacturing method thereof, optical apparatus, imaging apparatus, electronic apparatus and mobile object
CN110004477A (en) * 2019-04-18 2019-07-12 西安强微电气设备有限公司 A kind of electrolyte and the method for preparing Mg alloy surface black film layer with the electrolyte
CN110004477B (en) * 2019-04-18 2021-03-23 西安强微电气设备有限公司 Electrolyte and method for preparing black film on surface of magnesium alloy by using same
CN111821505A (en) * 2020-06-04 2020-10-27 东南大学 Super-paramagnetic nano-coating oral implant and preparation method thereof
CN114870083A (en) * 2022-04-16 2022-08-09 上海交通大学医学院附属第九人民医院 Preparation method and application of implant with complex coating on surface
CN114870083B (en) * 2022-04-16 2023-12-22 上海交通大学医学院附属第九人民医院 Preparation method and application of implant with complex coating on surface
CN114686952A (en) * 2022-05-07 2022-07-01 山西银光华盛镁业股份有限公司 Preparation method of transparent oxide film on surface of plastic deformation magnesium alloy workpiece

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