CN104831331B - A kind of method that Mg alloy surface prepares magnetic differential arc oxidation film layer - Google Patents

A kind of method that Mg alloy surface prepares magnetic differential arc oxidation film layer Download PDF

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CN104831331B
CN104831331B CN201510182681.2A CN201510182681A CN104831331B CN 104831331 B CN104831331 B CN 104831331B CN 201510182681 A CN201510182681 A CN 201510182681A CN 104831331 B CN104831331 B CN 104831331B
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arc oxidation
alloy
film layer
differential arc
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CN104831331A (en
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王云龙
王淼
朱林中
黄积伟
陈彩燕
刘志成
林东
陆玲梅
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Jiangsu University
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Jiangsu University
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Abstract

The present invention relates to differential arc oxidization technique, a kind of method for preparing magnetic differential arc oxidation film layer in Mg alloy surface is refered in particular to.This method can directly be formed the magnetic differential arc oxidation film layer containing magnetic component in Mg alloy surface, be both the expansion to magnesium alloy substrate performance by changing the composition of electrolyte, while also providing a kind of thin magnetic film provides a kind of new attachment carrier and its method;The present invention is applied to various magnesium alloys, especially medical magnesium alloy such as AZ91 series, AZ31 series etc..

Description

A kind of method that Mg alloy surface prepares magnetic differential arc oxidation film layer
Technical field
The present invention relates to differential arc oxidization technique, a kind of side that magnetic differential arc oxidation film layer is prepared in Mg alloy surface is refered in particular to Method.
Background technology
Differential arc oxidization technique is as the surface film grown up in recent years a treatment technology, and the technology can be in material Surface is modified especially metal surface and prepares various films, can both improve the performance of metallic matrix, while can also obtain each Plant function film, the focus as investigation of materials field;Differential arc oxidization technique is especially in so-called valve metal and its alloy surface Applied in processing, such as Al, Mg, Ti and its alloy, some scholars were gradually carrying out iron-based material differential of the arc oxygen in recent years The research of change.
Differential arc oxidation obtains larger achievement in research in terms of coloured light metal, including for the wear-and corrosion-resistant of aluminium alloy Film layer, the high temperature resistance for titanium alloy, the wear-resistance film layer of wear-and corrosion-resistant film layer and magnesium alloy, in addition to for these metals Some feature film layers, such as this to application surface high emissivity film layer of the titanium alloy in aerospace field, magnesium alloy in life Bioactivity and biocompatibility film layer of thing medical field etc..
Currently for magnesium alloy differential arc oxidization surface be modified film layer be mainly wear-and corrosion-resistant oxide membranous layer such as magnesia, Aluminum oxide, titanium dioxide or calcic phosphorus(Including the film layer containing only calcium P elements, and hydroxyl apatite HA and calcium phosphate TCP crystalline phase film layer)Bioactive film;The present invention closes magnesium in Mg alloy surface magnetic differential arc oxidation film layer, expansion Gold utensil has a variety of applications including the fields such as bio-medical, power electronics are applied, in particular for bio-medical field, magnetic Property film layer can be obviously improved the blood compatibility of magnesium alloy substrate, be currently based on magnetic be modified differential arc oxidation coating improve blood Compatibility has not been reported in differential arc oxidation field.
The content of the invention
It is one it is an object of the invention to provide a kind of method for directly generating magnetic differential arc oxidation film layer in Mg alloy surface Magnetic-film layer new method is grown in metal surface, this method can be direct in Mg alloy surface by changing the composition of electrolyte The magnetic differential arc oxidation film layer containing magnetic component is formed, is both the expansion to magnesium alloy substrate performance, while also providing one kind Thin magnetic film provides a kind of new attachment carrier and its method;The present invention is applied to various magnesium alloys, especially medical magnesium alloy Such as AZ91 series, AZ31 series.
The present invention is carried out as steps described below:
The technical solution adopted for the present invention to solve the technical problems is:
(1)First to magnesium alloy article surfaces carry out deoiling cleaning, can be polished as needed or polishing at Reason.
(2)Magnesium alloy product is placed in electrolyte solution as anode, carries out differential arc oxidation processing.
(3)The magnesium alloy product of surface by micro-arc oxidation film is carried out simply to clean and dry.
Micro-arc oxidation process of the present invention can be using the bi-directionally or uni-directionally pulse power, and voltage is 300-600v, current density In 2-15A/dm2Between, the component of following concentration is contained in the electrolyte solution of use:0.1-5 mol/LCa(OH)2、0.1-5 mol/L Ca(H2PO2)2、0.5-4mol/LCa(NO3)2、0.1-5 mol/L NH4H2PO4、0.1-10 mol/L Ca (CH3COO)2、0.1-5 mol/L Ca3(PO4)2、0.1-5 mol/L Na3PO4With 0.05-0.2 mol/L NaH2PO4In appoint Anticipate three kinds, 0.05-10mol/L Sr (NO3)2And/or 0.05-10mol/L Ba (NO3)2 With 0.05-20mol/L Fe (NO3)3
The mechanism of each component and effect:
In above-mentioned calcium phosphorus system micro-arc oxidation electrolyte, under conditions of ensureing that differential arc oxidation can be carried out, and do suitable Work as adjustment, introduce magnetic source component electrolyte such as Fe (NO3)3(0.05-20mol/L)With Sr (NO3)2(0.05-10mol/L)Or Person Fe (NO3)3(0.05-20mol/L)With Ba (NO3)2 (0.05-10mol/L)Or Fe (NO3)3(0.05-20mol/L)、Sr (NO3)2(0.05-10mol/L)With Ba (NO3)2 (0.05-10mol/L)Mutually originated for magnetic component thing.
The present invention uses steel scope:
The present invention is applied to various magnesium alloys, and its principle is that above-mentioned magnetic is introduced in magnesium alloy differential arc oxidation electrolyte system Property component source, realizes the preparation of magnetic-film layer, it is adaptable to various magnesium alloys.
The specific preparation method of electrolyte:
In the case where being stirred continuously, calcium phosphorus system differential arc oxidation basic electrolyte liquid is first configured, loads suitable in beaker Deionized water is measured, appropriate Ca (OH) is sequentially added2、Na3PO4、NH4H2PO4Etc. component and it is stirred continuously, then is separately added into Fe (NO3)3With Sr (NO3)2Or Fe (NO3)3With Ba (NO3)2 Or Fe (NO3)3、Sr(NO3)2With Ba (NO3)2
The present invention distinctive feature and beneficial effect be:
(1)The preparation of Mg alloy surface magnetic micro-arc oxidation films is realized, report is had no in differential arc oxidation field.
(2)Magnesium alloy with ceramic film has than having better performance without film layer, such as significantly improves blood phase Capacitive, while having more preferable decay resistance.
(3)The process stabilizing of the present invention is reliable, and the equipment of use is simple, and reaction is carried out at normal temperatures, easy to operate, it is easy to Grasp.
Brief description of the drawings
Fig. 1 is the hysteresis curve figure of the magnetic-film layer of embodiment 1.
Fig. 2 is the decay resistance schematic diagram of embodiment.
Embodiment
Embodiment 1
1. a pair AZ91 Mg alloy surfaces are mechanically polished, deoiling cleaning is then carried out.
2. the electrolyte of the following weight concentration of configuration:0.1-5 mol/L Ca(OH)2, 0.05-0.2 mol/L biphosphates Sodium, 0.1-5 mol/L NH4H2PO4, ferric nitrate 0.05-20mol/L Fe (NO3)3, 0.05-10mol/L strontium nitrate Sr (NO3)2
3. carry out differential arc oxidation processing, voltage 400-600v, current density 5-8 A/ using AZ91 magnesium alloys as anode dm2, handle 15-50 minutes.
4. the magnesium alloy of micro-arc oxidation films is cleaned, dried by Surface Creation.
Fig. 1 is hysteresis curve figure, and the magnetic behavior of film layer is characterized with hysteresis curve, shows that differential arc oxidation film layer has magnetic Property, saturation magnetization is up to 73Am2/kg。
Fig. 2 is decay resistance schematic diagram, in 3.5%NaCl solution, and corrosion resistance is measured with Tafel polarization curves, Compare corrosion resisting property quality with corrosion electric current density density and corrosion potential, the corrosion current of film layer is 8.54 × 10-7 A/cm2 Than matrix 9.09 × 10-5A/cm2Reduction, film layer corrosion potential is that -1.64V improves 0.18V, larger raising than matrix -1.82 Corrosion resisting property.
Embodiment 2
1. a pair ZK60 magnesium alloy article surfaces are mechanically polished, deoiling cleaning is then carried out.
2. the electrolyte of the following weight concentration of configuration:1-2 mol/LCa(NO3)2, 0.1-5 mol/L Ca (OH)2, 0.1-5 mol/L Na3PO4, 0.05-20mol/L ferric nitrate Fe ((NO3)3, 0.05-10mol/L barium nitrate Br (NO3)2
3. carry out differential arc oxidation processing, 400-600V, current density 6-15 A/dm using ZK601 magnesium alloys as anode2, Processing 15-50 minutes.
4. the magnesium alloy of micro-arc oxidation films is cleaned, dried by Surface Creation.
Enter magnetic behavior and corrosion resisting property test to film layer.Saturation magnetization is up to 72Am2/ kg, in 3.5%NaCl In solution, corrosion resistance is measured with Tafel polarization curves, compares corrosion resisting property with corrosion electric current density density and corrosion potential good Bad, the corrosion current of film layer is 3.324 × 10-6 A/cm2Than matrix 4.36 × 10-5A/cm2Reduction, film layer corrosion potential for- 1.352V is improved than matrix -1.694, and larger improves corrosion resisting property.
Embodiment 3
1. a pair AM60B magnesium alloy article surfaces are mechanically polished, deoiling cleaning is then carried out.
2. the electrolyte of the following weight concentration of configuration:0.1-5 mol/L Ca(CH3COO)2, 0.1-5 mol/L NH4H2PO4,0.1-5 mol/L Ca3(PO4)2,0.05-20mol/L ferric nitrate Fe ((NO3)3, 0.05-10mol/L strontium nitrates Sr (NO3)2, 0.05-10mol/L barium nitrate Br (NO3)2
3. carry out differential arc oxidation processing, 300-600v, current density 3-10A/dm using AM60B magnesium alloys as anode2, place Reason 15-50 minutes.
4. the magnesium alloy of micro-arc oxidation films is cleaned, dried by Surface Creation.
Enter magnetic behavior and corrosion resisting property test to film layer;Saturation magnetization is up to 72Am2/kg.In 3.5%NaCl In solution, corrosion resistance is measured with Tafel polarization curves, compares corrosion resisting property with corrosion electric current density density and corrosion potential good Bad, the corrosion current of film layer is 1.23 × 10-6 A/cm2Than matrix 8.36 × 10-5A/cm2Reduction, film layer corrosion potential for- 1.503V is improved than matrix -1.596, and larger improves corrosion resisting property.

Claims (5)

1. magnesium alloy article surfaces are carried out oil removing by a kind of method for preparing magnetic differential arc oxidation film layer in Mg alloy surface first Decontamination is cleaned, and can be polished as needed or polishing;Magnesium alloy product is placed in as anode in electrolyte solution, Carry out differential arc oxidation processing;The magnesium alloy product of surface by micro-arc oxidation film is carried out simply to clean and dry, it is characterised in that adopt Contain the component of following concentration in electrolyte solution:0.1-5 mol/LCa(OH)2、0.1-5 mol/L Ca(H2PO2)2、 0.5-4mol/LCa(NO3)2、0.1-5 mol/L NH4H2PO4、0.1-10 mol/L Ca(CH3COO)2、0.1-5 mol/L Ca3 (PO4)2、0.1-5 mol/L Na3PO4With 0.05-0.2 mol/L NaH2PO4In any three kinds, 0.05-10mol/L Sr (NO3)2And/or 0.05-10mol/L Ba (NO3)2 With 0.05-20mol/L Fe (NO3)3
2. a kind of method for preparing magnetic differential arc oxidation film layer in Mg alloy surface as claimed in claim 1, it is characterised in that: Differential arc oxidation processing is using the bi-directionally or uni-directionally pulse power, and voltage is 300-600v, and current density is in 2-15A/dm2Between.
3. a kind of method for preparing magnetic differential arc oxidation film layer in Mg alloy surface as claimed in claim 1, it is characterised in that Electrolyte contains the component of following concentration:0.1-5 mol/L Ca(OH)2, 0.05-0.2 mol/L sodium dihydrogen phosphates, 0.1-5 mol/L NH4H2PO4, ferric nitrate 0.05-20mol/L Fe (NO3)3, 0.05-10mol/L strontium nitrate Sr (NO3)2
4. a kind of method for preparing magnetic differential arc oxidation film layer in Mg alloy surface as claimed in claim 1, it is characterised in that Electrolyte contains the component of following concentration:1-2 mol/LCa(NO3)2, 0.1-5 mol/L Ca (OH)2, 0.1-5 mol/L Na3PO4, 0.05-20mol/L ferric nitrate Fe ((NO3)3, 0.05-10mol/L barium nitrate Br (NO3)2
5. a kind of method for preparing magnetic differential arc oxidation film layer in Mg alloy surface as claimed in claim 1, it is characterised in that Electrolyte contains the component of following concentration:0.1-5 mol/L Ca(CH3COO)2, 0.1-5 mol/L NH4H2PO4,0.1-5 mol/L Ca3(PO4)2,0.05-20mol/L ferric nitrate Fe ((NO3)3, 0.05-10mol/L strontium nitrate Sr (NO3)2、0.05- 10mol/L barium nitrate Br (NO3)2
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CN106637346B (en) * 2016-09-08 2018-07-17 西安交通大学 A kind of preparation method with the electroactive planting body of multistage composite structure-biological
CN106637348B (en) * 2016-09-23 2019-02-05 西安交通大学 Titanium surface ferrotitanium stone-type oxide/titanium dioxide biological coating preparation method
CN107119304B (en) * 2017-04-20 2019-05-03 西安交通大学 A kind of magnetism TiO2The differential arc oxidation preparation method of bioactivity coatings
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

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CN1927410A (en) * 2006-09-25 2007-03-14 华南理工大学 Strontium containing hydroxyapatite biologically active film and preparation method thereof
CN103120805A (en) * 2013-02-04 2013-05-29 中国科学院金属研究所 Bioactive surface coating of biomedical degradable magnesium alloy and preparation method thereof
CN103741188A (en) * 2014-01-24 2014-04-23 长安大学 Method for preparing steady-persistence luminous ceramic membrane through aluminum or aluminum alloy surface micro-arc oxidation

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1927410A (en) * 2006-09-25 2007-03-14 华南理工大学 Strontium containing hydroxyapatite biologically active film and preparation method thereof
CN103120805A (en) * 2013-02-04 2013-05-29 中国科学院金属研究所 Bioactive surface coating of biomedical degradable magnesium alloy and preparation method thereof
CN103741188A (en) * 2014-01-24 2014-04-23 长安大学 Method for preparing steady-persistence luminous ceramic membrane through aluminum or aluminum alloy surface micro-arc oxidation

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