CN104611699A - Preparation method of magnesium alloy surface micro-arc oxidation-electrophoresis composite coating - Google Patents

Preparation method of magnesium alloy surface micro-arc oxidation-electrophoresis composite coating Download PDF

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CN104611699A
CN104611699A CN201310536595.8A CN201310536595A CN104611699A CN 104611699 A CN104611699 A CN 104611699A CN 201310536595 A CN201310536595 A CN 201310536595A CN 104611699 A CN104611699 A CN 104611699A
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electrophoresis
magnesium alloy
arc oxidation
preparation
alloy surface
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CN104611699B (en
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常立民
田利丰
刘伟
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Harbin specification Technology Co.,Ltd.
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Jilin Normal University
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    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25DPROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02Anodisation
    • C25D11/30Anodisation of magnesium or alloys based thereon
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS 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
    • A61L27/00Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/02Inorganic materials
    • A61L27/04Metals or alloys
    • A61L27/047Other specific metals or alloys not covered by A61L27/042 - A61L27/045 or A61L27/06
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS 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
    • A61L27/00Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/28Materials for coating prostheses
    • A61L27/30Inorganic materials
    • A61L27/306Other specific inorganic materials not covered by A61L27/303 - A61L27/32
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS 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
    • A61L27/00Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/28Materials for coating prostheses
    • A61L27/30Inorganic materials
    • A61L27/32Phosphorus-containing materials, e.g. apatite
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS 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
    • A61L27/00Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/50Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
    • A61L27/54Biologically active materials, e.g. therapeutic substances
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS 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
    • A61L27/00Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/50Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
    • A61L27/56Porous materials, e.g. foams or sponges
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C28/00Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/04Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings of inorganic non-metallic material
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25DPROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D13/00Electrophoretic coating characterised by the process
    • C25D13/02Electrophoretic coating characterised by the process with inorganic material
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS 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
    • A61L2420/00Materials or methods for coatings medical devices
    • A61L2420/02Methods for coating medical devices
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS 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
    • A61L2420/00Materials or methods for coatings medical devices
    • A61L2420/06Coatings containing a mixture of two or more compounds
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS 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
    • A61L2420/00Materials or methods for coatings medical devices
    • A61L2420/08Coatings comprising two or more layers
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS 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
    • A61L2430/00Materials or treatment for tissue regeneration
    • A61L2430/02Materials or treatment for tissue regeneration for reconstruction of bones; weight-bearing implants

Abstract

The invention discloses a preparation method of a magnesium alloy surface micro-arc oxidation-electrophoresis composite coating, and belongs to the field of magnesium alloy surface treatment. The preparation method is used for solving problems of conventional magnesium alloy that biological activity is poor, and bonding force with composite membrane is low. According to the preparation method, micro-arc oxidation is adopted so as to form a micro-arc oxidized ceramic coating on magnesium alloy surface, and a composite coating with biological activity is obtained via electrophoresis treatment using a pulsed power supply; and a used electrophoretic liquid is composed of one compound selected from hydroxyapatite, acetic acid, and absolute ethyl alcohol or polyethylene glycol, and one compound selected from lanthanum nitrate or cerous nitrate. Ideal combination of micro-arc oxidation with pulse electrophoresis is realized; compounds such as hydroxyapatite are introduced onto the surface of magnesium alloy; and electrophoresis treatment is used for hole sealing of holes of the micro-arc oxidized ceramic coating so as to improve biological activity and corrosion resistance of magnesium alloy, and bonding strength is relatively high.

Description

The preparation method of a kind of magnesium alloy surface micro-arc oxidation-electrophoresis compound coating
Technical field
The present invention relates to the preparation method of alloy surface differential arc oxidization-electrophoresis compound coating, compound coating prepared thus has good corrosion-proof wear performance, is expected the biomedical material becoming a kind of novelty.
Background technology
Mg-based hydrogen storage base biomaterial most possibly becomes metal matrix body implanting material of future generation.The density of MAGNESIUM METAL and the Young's modulus of magnesium and people's bone close, can stress-shielding effect be avoided; Magnesium is indispensable element in human body, and content is only second to calcium, sodium and potassium, and magnesium is also the main component of composition bone simultaneously, can promote that bone, tooth and cell are formed, and play important regulating effect in the mineral metabolism of bone.Even if generate magnesium ion in human body fluid, also can be absorbed by surrounding body tissues or be excreted by metabolism, there is biodegradability.Therefore, magnesium and alloy thereof have considerable application prospect as biomaterial.The differential arc oxidization technique grown up on anodic oxidation basis in recent years can be used for the surface modification treatment of magnesium alloy, and its generated in-situ porous oxide coatings has the features such as nontoxic, anti-corrosion, wear-resisting, is a kind of up-and-coming magnesium alloy surface treatment.Differential arc oxidization technique has following outstanding feature: can avoid adopting conventional high-temperature coating and the matrix phase transformation that causes and embrittlement; Realize forming uniform ceramic deposit in metallic substrate surface that is complex-shaped or porous surface; Zone of oxidation and matrix set are firm, zone of oxidation composition easy to control, thickness; Equipment is simple, easy to operate; Film preparation cost is low; Technique environmental protection.Hydroxyapatite molecular formula is Ca 10(PO 4) 6(OH) 2, be the main inorganic composition in osseous tissue and tooth.In human body dentine, hydroxyapatite accounts for 70%, accounts for 90% in enamel, and enamel surface accounts for more than 95%.Hydroxyapatite has excellent biocompatibility, biological activity and osteoconductive, from the physical structure of hydroxyapatite, can think that bone is the toughness reinforcing hydroxyapatite based composites of a kind of elastopolymer.The inanimate matter constituent structure of the composition of artificial-synthetic hydroxyapatite, structure and body bone tissue is similar, it has nontoxic, nonirritant, without sensitization, without mutagenicity and carinogenicity, a kind of biocompatible materials, can with ostosis chemical action, there is good osteoconductive.Electrochemical deposition has the advantages such as equipment is simple, cost is low, easy to operate, depositing operation is easy to control.But in electrochemical deposition process, the conditions such as electrolyte temperature, substrate and electrolytic solution composition all can have an impact to the composition of electrochemical deposition calcium phosphorus product, structure and surface topography etc., therefore also can there is hydroxyapatite coating layer and the problem such as metallic surface bonding strength is low.
Summary of the invention
The object of the invention is to the shortcoming overcoming above-mentioned prior art, the method utilizing the pulse power to carry out electrophoretic process forms differential arc oxidation-electrophoresis (MgO/HA) compound coating of high-quality at magnesium alloy differential arc oxidation sample surfaces.
The concrete steps of the preparation method of magnesium alloy surface micro-arc oxidation of the present invention/electrophoresis compound coating are:
One, the preparation of magnesium alloy surface micro-arc oxidation rete: be placed in electrolytic solution as anode using carrying out pretreated magnesium alloy, stainless steel plate is as negative electrode, and carry out differential arc oxidation process 3-20min, the magnesium alloy obtaining having differential arc oxidation film layer is for subsequent use;
(1) preparation method of wherein said electrolytic solution is as follows: take raw material sodium aluminate or potassium aluminate 15-50g/l, sodium hydroxide or potassium hydroxide highly basic 1-10g/l, hydrogen peroxide or potassium permanganate or Potassium monofluoride 1-10g/l, glycerol 1-10ml/l, Sodium.alpha.-hydroxypropionate 5-30ml/l, dissolve in successively in deionized water, obtain electrolytic solution described in step one;
(2) treatment process condition of wherein differential arc oxidation: take magnesium alloy product as anode, the insoluble inert metal of stainless steel is that negative electrode is in above-mentioned electrolytic solution, apply the pulse power between anode and cathode and carry out differential arc oxidation process, processing parameter is: voltage: 300-500V, temperature: 5-50 DEG C, time: 3-20min, pH value: 8-14;
In described step one, preprocessing process refers to after raw material magnesium alloy employing 400,1200,2000 order sand paper successively sanding and polishing, completes with at least one ultrasonic cleaning process in deionized water, acetone or alcohol etc.
The preparation of two, magnesium alloy differential arc oxidation-electrophoresis compound coating: the magnesium alloy with differential arc oxidation film layer that step one is obtained is placed in electrophoresis suspensioning liquid as negative electrode, the insoluble inert metal of stainless steel is anode, two interpole gap 1cm, in electrophoresis suspensioning liquid, the pulse power is utilized to carry out constant voltage electrophoretic process 100-500s, after reaction terminates, magnesium alloy is taken out at 80 ~ 100 DEG C dry, obtain the magnesium alloy with differential arc oxidation-electrophoresis compound coating;
(1) preparation method of wherein said electrophoresis suspensioning liquid is as follows: take hydroxyapatite (HA) 5-50g/l first respectively, dehydrated alcohol 10-200ml/l or polyoxyethylene glycol 5-50ml/l, lanthanum nitrate or cerous nitrate rare-earth cation 1-10g/l, be dissolved in successively in deionized water, and by acetic acid adjust ph to 2 ~ 6, then carry out supersound process 1 ~ 3h, finally stir 12 ~ 24h, obtain electrophoresis suspensioning liquid described in step 2;
(2) processing condition of ability cathode electrophoresis process are: with the magnesium alloy sample through differential arc oxidation process for negative electrode, stereotype or the insoluble inert metal of stainless steel are anode, and two interpole gap 1cm, in above-mentioned electrophoresis suspensioning liquid, the pulse power is utilized to carry out constant voltage electrophoretic process, processing parameter is: voltage: 50-300V, forward dutycycle: 20-60%, negative sense dutycycle: 10-40%, frequency: 50-500Hz, temperature: 5-50 DEG C, time: 100-500s, pH value: 2-6.
Advantage of the present invention and beneficial effect are:
Can arc discharge be suppressed after adding glycerol or Sodium.alpha.-hydroxypropionate in the electrolytic solution of 1, the inventive method step one, reduce the aperture of ceramic membrane surface, improve the solidity to corrosion of rete; The electrophoretic process of step 2 can process the differential arc oxidation sample surfaces obtained and obtain the thin layer containing hydroxyapatite and calcium and phosphoric in step one, makes sample have certain biological activity; After adding cerium ion in the electrophoresis suspensioning liquid of step 2, improve the ratio of calcium and phosphorus of the composite film after process, further increase the biological activity of composite film; The Mg alloy surface of the electrophoretic process of step 2 has vesicular structure, and adopts the pulse power to carry out electrophoretic process, improves the bonding strength of the rear compound layer of process.Therefore, have certain biological activity by the compound coating obtained after differential arc oxidation and electrophoretic process, solidity to corrosion is good, and high with substrate combinating strength.
2, method of the present invention obtains at Mg alloy surface and has solidity to corrosion and certain bioactive compound layer, and thickness can reach 10-40 μm.After differential arc oxidation process obtains porous ceramic film, utilize electrophoretic process to add the calcium phosphorous compounds such as hydroxyapatite in ceramic membrane, make sample have certain biological activity.
3, the present invention adopts the electrophoretic process processing condition of optimization, and obtain the compound coating with inside and outside double-layer structure, its inner compact layer is complete, is the composite oxides of Mg, Al, and combines closely with matrix metal; Its skin is smooth, is hydroxyapatite and the composite oxides containing Ca, P, has biological activity.
Accompanying drawing explanation
The electron scanning micrograph of Fig. 1 differential arc oxidation film layer that to be the present invention obtain at Mg alloy surface;
Fig. 2 is the electron scanning micrograph of differential arc oxidation of the present invention-electrophoresis compound coating;
Fig. 3 is the elementary composition energy spectrum analysis of differential arc oxidation of the present invention-electrophoresis compound coating;
Fig. 4 is the XRD crystal species analysis of differential arc oxidation of the present invention-electrophoresis compound coating, and X-coordinate is 2 θ, and ordinate zou is intensity.
Embodiment
Embodiment one:
One, the preparation of electrolytic solution: take raw material sodium aluminate or potassium aluminate 20g/l, sodium hydroxide or potassium hydroxide 3g/l, hydrogen peroxide 2ml/l, glycerol 3ml/l, Sodium.alpha.-hydroxypropionate 5ml/l, dissolves in successively in deionized water, obtains electrolytic solution for subsequent use.
Two, the preparation of electrophoresis suspensioning liquid: take hydroxyapatite (HA) 10g/l first respectively, polyoxyethylene glycol 10ml/l, cerous nitrate 2g/l, be dissolved in deionized water successively, and by acetic acid adjust ph to 4, then carry out supersound process 2h, finally stir 24h, obtain electrophoresis suspensioning liquid for subsequent use.
Three, the preparation of magnesium alloy surface micro-arc oxidation rete: (described preprocessing process refers to after raw material magnesium alloy employing 400,1200,2000 order sand paper successively sanding and polishing will to carry out pre-treatment, complete with at least one ultrasonic cleaning process in deionized water, acetone or alcohol etc.) magnesium alloy be placed in electrolytic solution as anode, stainless steel plate is as negative electrode, carry out differential arc oxidation 3 ~ 20min, obtain the magnesium alloy sample with differential arc oxidation film layer; Controlling electrolyte temperature is 5 ~ 20 DEG C, and micro-arc oxidation process parameter is: current density is 200mA/cm 2, frequency is 100Hz, forward dutycycle 35%, negative sense dutycycle 35%, final voltage 450V; As shown in Figure 1, the present invention is typical differential arc oxidation pattern at the rete that Mg alloy surface obtains.
Four, the magnesium alloy sample of step 3 process is placed in electrophoresis suspensioning liquid as negative electrode, the insoluble inert metal such as stainless steel is anode, two interpole gap 1cm, in electrophoresis suspensioning liquid, the pulse power is utilized to carry out constant voltage electrophoretic process 200s, taken out by magnesium alloy at 90 DEG C dry after reaction terminates, complete the preparation method of magnesium alloy surface micro-arc oxidation-electrophoresis compound coating, the processing parameter of electrophoretic process is: voltage density is 40V/cm 2, frequency 100Hz, forward dutycycle 45%, negative sense dutycycle 30%.
The electron scanning micrograph of the differential arc oxidation that Fig. 2 the present invention obtains-electrophoresis compound coating, as shown in Figure 2, magnesium alloy differential arc oxidation of the present invention-electrophoresis compound coating surface arrangement is even, after electrophoretic process, typical differential arc oxidation pattern disappears, and presents the comparatively uniform electrophoresis film shape of distribution.
Fig. 3 is the elementary composition energy spectrum analysis of differential arc oxidation-electrophoresis compound coating that the present invention obtains, and following table is mass percent and the atomic ratio of wherein calcium, phosphorus and oxygen element:
The elementary composition EDAX results of the differential arc oxidation that table 1 obtains for the present invention-electrophoresis compound coating
Element Wt% At%
O 43.40 63.31
P 21.88 16.48
Ca 34.71 20.21
Ca/P 1.59 1.23
From Fig. 3 and table 1, introduce calcium and phosphoric at the Mg alloy surface after electrophoretic process, its ratio of calcium and phosphorus is close to the ratio of calcium and phosphorus 1.67 of hydroxyapatite.Visible, the differential arc oxidation prepared by the present invention-electrophoresis compound coating has certain biological activity.
Fig. 4 is the XRD crystal species analysis of differential arc oxidation-electrophoresis compound coating that the present invention obtains, and X-coordinate is 2 θ, and ordinate zou is intensity.As shown in Figure 4, the Mg alloy surface after electrophoresis introduces has bioactive hydroxyapatite.
Table 2 for directly carrying out electrophoresis (HA/Mg) at Mg alloy surface, the bonding strength of differential arc oxidation-electrophoresis compound coating (PC-HA-MAO/Mg) of utilizing D.C. regulated power supply to obtain at magnesium alloy differential arc oxidation sample surfaces electrophoresis (AC-HA-MAO/Mg) and the present invention contrasts:
HA/Mg AC-HA-MAO/Mg PC-HA-MAO/Mg
σ 6.32MPa 10.35MPa 13.56MPa
Wherein σ is the resisting binding strength between coating and matrix.
As shown in Table 2, the bonding force of the compound coating that electrophoresis obtains is carried out apparently higher than the direct sample at Mg alloy surface electrophoresis on magnesium alloy differential arc oxidation film layer surface, and electrophoretic process is carried out on the differential arc oxidation film layer surface that coexists, the bonding force utilizing the pulse power to carry out the sample of electrophoresis comparatively utilizes D.C. regulated power supply to be significantly increased.
Embodiment two:
Present embodiment and embodiment one unlike electrolytic solution in step one by concentration be the potassium hydroxide of 3g/l, the sodium aluminate of the hydrogen peroxide of 2ml/l, the glycerol of 3ml/l, the Sodium.alpha.-hydroxypropionate of 8ml/l and 20g/l makes.Other steps and processing parameter identical with embodiment one.
Embodiment three:
Present embodiment and embodiment one unlike electrolytic solution in step one by concentration be the potassium hydroxide of 3g/l, the sodium aluminate of the hydrogen peroxide of 2ml/l, the glycerol of 2ml/l, the Sodium.alpha.-hydroxypropionate of 4.5ml/l and 25g/l makes.Other steps and processing parameter identical with embodiment one.
Embodiment four:
Present embodiment and embodiment one, two or three unlike micro-arc oxidation process parameter in step 3 are: current density is 200mA/cm 2, frequency is 100Hz, forward dutycycle 35%, negative sense dutycycle 35%, final voltage 400V.Other steps and processing parameter identical with embodiment one.
Embodiment five:
One of present embodiment and embodiment one to four unlike electrophoresis suspensioning liquid in step 2 by concentration be the hydroxyapatite of 5g/l, the polyoxyethylene glycol of the cerous nitrate of 2g/l and 10ml/l makes.Other steps and processing parameter identical with embodiment one.
Embodiment six:
One of present embodiment and embodiment one to five unlike electrophoresis suspensioning liquid by concentration be the hydroxyapatite of 10g/l, the polyoxyethylene glycol of the cerous nitrate of 5g/l and 10ml/l makes.Other steps and processing parameter identical with embodiment one.
Embodiment seven:
One of present embodiment and embodiment one to six unlike electrophoresis suspensioning liquid in step 2 by the hydroxyapatite of 10g/, the cerous nitrate of 2g/l and 50% dehydrated alcohol form, solvent is water.Other steps and processing parameter identical with embodiment one.
Embodiment eight:
One of present embodiment and embodiment one to seven are voltage density unlike the processing parameter of electrophoretic process in step 4 is 35V/cm 2, frequency 100Hz, forward dutycycle 45%, negative sense dutycycle 30%.Other steps and processing parameter identical with embodiment one.
Embodiment nine:
One of present embodiment and embodiment one to eight are 250s unlike the time of electrophoretic process in step 4.Other steps and processing parameter identical with embodiment one.
Embodiment ten:
One of present embodiment and embodiment one to eight are 300s unlike the time of electrophoretic process in step 4.Other steps and processing parameter identical with embodiment one.

Claims (8)

1. magnesium alloy surface micro-arc oxidation-electrophoresis compound coating, is characterized in that: for general Mg-Al alloy, described compound coating is made up of inside and outside two membranes, and its inner layer film is the composite oxides of Mg, Al, compact and complete, and combines closely with matrix metal; Its outer membrane is hydroxyapatite and containing the composite oxides of Ca, P, smooth, and surface arrangement evenly and spatially Gradient distribution, ectonexine is bonded compound coating.
2. according to Mg alloy surface compound coating according to claim 1, it is characterized in that: adopt the pulse power to carry out electrophoretic process, described compound coating thickness is generally between 10-40 μm, and the thickness of compound coating increases gradually with the prolongation of electrophoretic process time, can prepare the compound coating of suitable thickness according to actual needs on magnesium alloy product.
3. a preparation method for magnesium alloy surface micro-arc oxidation-electrophoresis compound coating, is characterized in that:
(1) magnesium alloy differential arc oxidation process:
The preparation method of (a) differential arc oxidation process electrolytic solution:
Take raw material sodium aluminate or potassium aluminate 15-50g/l, sodium hydroxide, or the highly basic 1-10g/l such as potassium hydroxide, hydrogen peroxide or potassium permanganate or Potassium monofluoride 1-10g/l, glycerol 1-10ml/l, Sodium.alpha.-hydroxypropionate 5-30ml/l, dissolves in deionized water successively, obtains electrolytic solution;
B the processing condition of () differential arc oxidation process are:
Voltage: 300-500V, temperature: 5-50 DEG C, time: 3-20min, pH value: 8-14;
(2) there is the pulse electrophoresis process of the magnesium alloy of differential arc oxidation coating:
The preparation method of the electrophoresis suspensioning liquid of (a) pulse electrophoresis process:
First hydroxyapatite (HA) 5-50g/l is taken respectively, dehydrated alcohol 10-200ml/l or polyoxyethylene glycol 5-50ml/l, lanthanum nitrate, or cerous nitrate rare-earth cation 1-10g/l, be dissolved in deionized water successively, and by acetic acid adjust ph 2 ~ 6, then carry out ultrasonic 1 ~ 3h, finally stir 12 ~ 24h, obtain electrophoresis suspensioning liquid;
B the processing condition of () pulse electrophoresis process are:
Voltage: 50-300V, forward dutycycle: 20-60%, negative sense dutycycle: 10-40%, frequency: 50-500Hz, temperature: 5-50 DEG C, time: 50-500s, pH value: 2-6.
4., according to the magnesium alloy surface micro-arc oxidation described in right 3-electrophoresis preparation method of composite coating, it is characterized in that adding Sodium.alpha.-hydroxypropionate, glycerol when carrying out differential arc oxidation process, improve the solidity to corrosion of magnesium alloy sample.
5., according to the magnesium alloy surface micro-arc oxidation described in right 3-electrophoresis preparation method of composite coating, it is characterized in that described electrophoretic process power supply is the bidirectional, dc pulse power.
6. according to the magnesium alloy surface micro-arc oxidation described in right 3-electrophoresis preparation method of composite coating, it is characterized in that the electrophoretic process of carrying out is for negative electrode with magnesium alloy differential arc oxidation sample, stereotype or the insoluble inert metal of stainless steel are anode, in hydroxyapatite suspensions, apply pulse between anode and cathode and carry out electrophoretic process.
7., according to the magnesium alloy surface micro-arc oxidation described in right 3-electrophoresis preparation method of composite coating, it is characterized in that electrophoresis liquid selects rare-earth cation as electrophoresis promotor, and hydroapatite particles changes in the coating in gradient.
8. according to the magnesium alloy surface micro-arc oxidation described in right 3-electrophoresis preparation method of composite coating, it is characterized in that utilizing the pulse power to carry out electrophoresis, improve solidity to corrosion and the bonding strength of magnesium alloy surface micro-arc oxidation-electrophoresis compound coating.
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Cited By (11)

* Cited by examiner, † Cited by third party
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CN105543926A (en) * 2015-12-08 2016-05-04 西安工业大学 Preparation method of corrosion-resistant wear-resistant synergistic coating for surfaces of light alloy and composite material
CN106191835A (en) * 2016-08-03 2016-12-07 北方工业大学 Preparation method of novel magnesium alloy hydroxyapatite composite membrane
CN106544714A (en) * 2016-10-21 2017-03-29 郑州大学 A kind of preparation method of medical magnesium alloy surface coating
CN106884192A (en) * 2017-03-07 2017-06-23 大连海事大学 A kind of preparation technology of self-lubrication ceramic based composites
CN108014368A (en) * 2017-11-21 2018-05-11 西安理工大学 A kind of Mg alloy surface graded composite piezoelectric biological coating and preparation method thereof
CN108950651A (en) * 2018-07-16 2018-12-07 江苏科技大学 A kind of preparation method of the magnesium alloy surface micro-arc electrophoresis layer of biological composite membrane containing HA
CN109537025A (en) * 2018-12-21 2019-03-29 河南省正骨研究院 Metallic composite, degradable magnesium alloy bone screw and application containing corrosion-resistant coating
CN113502473A (en) * 2021-07-17 2021-10-15 安徽通灵仿生科技有限公司 Preparation method of corrosion-resistant coating for surface of catheter pump rotor
CN114703530A (en) * 2022-04-28 2022-07-05 徐州工程学院 Method for compositely constructing samarium-doped hydroxyapatite gradient coating on surface of magnesium alloy by utilizing electrophoresis/micro-arc oxidation technology
CN114908395A (en) * 2022-03-31 2022-08-16 西安工程大学 Preparation method of aluminum metal surface composite coating
CN116197283A (en) * 2023-04-28 2023-06-02 佛山高谱机械科技有限公司 Titanium alloy pipe thermal bending method based on self-lubricating effect

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CN105543926B (en) * 2015-12-08 2017-10-20 西安工业大学 Light-alloy and composite material surface is anti-corrosion, anti-attrition synergism coat preparation method
CN105543926A (en) * 2015-12-08 2016-05-04 西安工业大学 Preparation method of corrosion-resistant wear-resistant synergistic coating for surfaces of light alloy and composite material
CN106191835A (en) * 2016-08-03 2016-12-07 北方工业大学 Preparation method of novel magnesium alloy hydroxyapatite composite membrane
CN106191835B (en) * 2016-08-03 2018-10-23 北方工业大学 Preparation method of magnesium alloy hydroxyapatite composite membrane
CN106544714A (en) * 2016-10-21 2017-03-29 郑州大学 A kind of preparation method of medical magnesium alloy surface coating
CN106884192A (en) * 2017-03-07 2017-06-23 大连海事大学 A kind of preparation technology of self-lubrication ceramic based composites
CN108014368A (en) * 2017-11-21 2018-05-11 西安理工大学 A kind of Mg alloy surface graded composite piezoelectric biological coating and preparation method thereof
CN108950651B (en) * 2018-07-16 2020-07-14 江苏科技大学 Preparation method of magnesium alloy surface micro-arc electrophoresis HA-containing biological composite film
CN108950651A (en) * 2018-07-16 2018-12-07 江苏科技大学 A kind of preparation method of the magnesium alloy surface micro-arc electrophoresis layer of biological composite membrane containing HA
CN109537025A (en) * 2018-12-21 2019-03-29 河南省正骨研究院 Metallic composite, degradable magnesium alloy bone screw and application containing corrosion-resistant coating
CN113502473A (en) * 2021-07-17 2021-10-15 安徽通灵仿生科技有限公司 Preparation method of corrosion-resistant coating for surface of catheter pump rotor
CN113502473B (en) * 2021-07-17 2023-03-07 安徽通灵仿生科技有限公司 Preparation method of corrosion-resistant coating for surface of catheter pump rotor
CN114908395A (en) * 2022-03-31 2022-08-16 西安工程大学 Preparation method of aluminum metal surface composite coating
CN114908395B (en) * 2022-03-31 2023-11-21 西安工程大学 Preparation method of aluminum metal surface composite coating
CN114703530A (en) * 2022-04-28 2022-07-05 徐州工程学院 Method for compositely constructing samarium-doped hydroxyapatite gradient coating on surface of magnesium alloy by utilizing electrophoresis/micro-arc oxidation technology
CN114703530B (en) * 2022-04-28 2023-08-25 徐州工程学院 Method for compositely constructing samarium-doped hydroxyapatite gradient coating on magnesium alloy surface by utilizing electrophoresis/micro-arc oxidation technology
CN116197283A (en) * 2023-04-28 2023-06-02 佛山高谱机械科技有限公司 Titanium alloy pipe thermal bending method based on self-lubricating effect

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