CN108754578A - One kind takes differential arc oxidation to improve the corrosion proof method of biological medical magnesium alloy - Google Patents
One kind takes differential arc oxidation to improve the corrosion proof method of biological medical magnesium alloy Download PDFInfo
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- CN108754578A CN108754578A CN201810971007.6A CN201810971007A CN108754578A CN 108754578 A CN108754578 A CN 108754578A CN 201810971007 A CN201810971007 A CN 201810971007A CN 108754578 A CN108754578 A CN 108754578A
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- magnesium alloy
- arc oxidation
- differential arc
- alloy product
- improve
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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
- C25D11/026—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
- 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
- A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
- A61L27/56—Porous materials, e.g. foams or sponges
-
- 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
- A61L27/58—Materials at least partially resorbable by the body
-
- 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
- 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 one kind, and differential arc oxidation to be taken to improve the corrosion proof method of biological medical magnesium alloy, the specific steps are：S1, it is polished ZK60 magnesium alloy article surfaces using sand paper；S2, the magnesium alloy product polished is placed in ethanol solution be cleaned by ultrasonic after dry；S3, prepared solution is poured into electrolytic cell；S4, magnesium alloy product is fixed on holder by stainless steel wire and is immersed in electrolyte；S5, start mao power source, carrying out differential arc oxidation to magnesium alloy product than the running parameter that 30%, negative sense duty ratio 70%, positive negative sense umber of pulse are 1 using forward voltage 250V, negative voltage 20V, working frequency 600Hz, positive vacuum handles 15min；S6, using blotting paper rear natural drying is blotted after cleaning magnesium alloy product with deionized water ultrasound.The method of the present invention is convenient without noxious material, environmental protection, and prepared differential arc oxidation magnesium alloy product has good corrosion resistance.
Description
Technical field
It is modified the present invention relates to the surface of biological medical magnesium alloy more particularly to one kind takes differential arc oxidation to improve biology doctor
With the method for corrosion stability of magnesium alloy.
Background technology
In surgery bone collection and interior fixed biomaterial, titanium alloy and stainless steel are clinically mostly used, but these
Material is non-degradable in human body, needs to take out the pain for increasing patient by second operation.Meanwhile traditional bone grafting material is deposited
In " stress shielding " effect, the growth and healing of strong influence tissue.In recent years, magnesium alloy is in people's degradable in vivo, with people
Biomechanics of bone similar performance, while magnesium ion is proven to have the performance for facilitating bone, therefore widely studied by scientists.
But magnesium alloy is after human body implantation that there are corrosion rates is too fast, the hydrogen of generation and causes excessively high around tissue
PH value can all make be implanted into effect be deteriorated even fail.Immersion metal by being used as sun by micro-arc oxidation process in the solution
Pole, alternating voltage are added between anode and cathode, arc discharge are generated in magnesium alloy using high pressure on the basis of anodic oxidation, in table
Face generates dense oxidation film.By the suitable technological parameter of regulation and control, high rigidity, bond strength can be prepared, it is excellent corrosion-resistant
The quality coating of performance and abrasion resistance properties.Magnesium and magnesium alloy differential arc oxidation coating are in total by up of three layers：External porous layer,
There are many big and deep holes；The middle layer of low porosity；Very thin dense barrier layer.In addition, many micropores and micro-crack are random
It is distributed in the surface of differential arc oxidation coating, but not is penetrated into entire coating.This some holes and crackle there are both advantageous and disadvantageous：It is micro-
The helping to of hole promotes combining closely for coating and substrate, however can weaken the corrosion resistance of coating.
In order to obtain the differential arc oxidation coating with good corrosion resistance, the electricity used in the differential arc oxidation of magnesium alloy is adjusted
It solves liquid and technological parameter is most important.Meanwhile in bio-medical material, used material demand is nontoxic, to use up
It can be avoided that heavy metal and have the addition of noxious material.In order to later being capable of industrialized production, it is also necessary to reduce pair setting as far as possible
The time required to prepared by standby requirement and reduction.Magnesium alloy after preparation is needed to carry out corrosion proof characterization, is optimized with determining
The technological parameter of differential arc oxidation.
Invention content
In order to form with good corrosion resistance, harmless differential arc oxidation in biological medical magnesium alloy article topsheet
Coating, the present invention provide following technical scheme：
One kind takes differential arc oxidation to improve the corrosion proof method of biological medical magnesium alloy, includes the following steps：
S1, it is polished ZK60 magnesium alloy article surfaces using sand paper；
S2, the magnesium alloy product polished is placed in ethanol solution be cleaned by ultrasonic after dry；
S3, electrolyte is prepared：The electrolyte includes 0.05mol/L Na3PO4, 0.02mol/LNa2B4O7, 0.05mol/L
KOH；Prepared solution is poured into electrolytic cell, agitating device agitating solution is started；
S4, magnesium alloy product is fixed on by stainless steel wire on holder and is immersed in electrolyte；
S5, start mao power source, it is true using forward voltage 250-400V, negative voltage 20V, working frequency 600Hz, forward direction
Sky carries out at differential arc oxidation magnesium alloy product than the running parameter that 30%, negative sense duty ratio 70%, positive negative sense umber of pulse are 1
Reason, processing time 15min；The differential arc oxidation processing time only 15min of the present invention, preparation efficiency is substantially increased；
S6, using blotting paper rear natural drying is blotted after cleaning magnesium alloy product with deionized water ultrasound.
Further, sand paper described in step S1 is the fine sandpaper of 2000 mesh.
Further, forward voltage selects 250V in step S5.
The beneficial effects of the present invention are：
1. efficient：It is short that this method prepares the differential arc oxidation time needed for magnesium alloy, only 15 minutes；
2. operation difficulty is low：This method only needs mao power source and container, advantage of lower cost to be easily obtained, and equipment is grasped
It is low to make difficulty.
3. environmental protection：Micro-arc oxidation electrolyte used in rigid method does not contain heavy metal and the substance toxic to human body,
Electrolyte can direct emission, it is environment friendly and pollution-free；
4. corrosion resistance is high：Differential arc oxidation magnesium alloy prepared by this method has the advantages that oxide layer densification, is impregnated by body fluid
Its excellent corrosion resistance is demonstrated with electrochemistry experiment；
5. with further modified potentiality：The differential arc oxidation layer that this method is prepared in Mg alloy surface has uniform hole,
These holes can continue addition in the later stage can improve magnesium alloy biocompatibility or the substance of antibacterial, such as hydroxy-apatite
Stone, nano silver etc. improve the performance of magnesium alloy clinically with this.
Description of the drawings
Fig. 1, micro-arc oxidation device schematic diagram.
Magnesium alloy differential arc oxidation sample surfaces microscopic appearance under Fig. 2, embodiment 1.
Magnesium alloy differential arc oxidation sample surfaces microscopic appearance under Fig. 3, embodiment 2.
Magnesium alloy differential arc oxidation sample surfaces microscopic appearance under Fig. 4, embodiment 3.
Magnesium alloy differential arc oxidation sample surfaces microscopic appearance under Fig. 5, embodiment 4.
The Tafel curves of differential arc oxidation sample and untreated ZK60 magnesium alloys sample under Fig. 6, embodiment 1-4.
After the bionical solution of differential arc oxidation sample and untreated ZK60 magnesium alloys sample under Fig. 7, embodiment 1-4 impregnates
PH value of solution datagram.
After the bionical solution of differential arc oxidation sample and untreated ZK60 magnesium alloys sample under Fig. 8, embodiment 1-4 impregnates
Sample quality datagram.
Specific implementation mode
Embodiment 1
ZK60 magnesium alloys are cut into the coupon of 20*20*5mm using electro-spark cutting machine, are got on surface using electric drill head logical
Hole.It is polished magnesium alloy with the sand paper of 2000 mesh, obtains bright surface.The magnesium alloy for milled of fighting each other uses EtOH Sonicate
Cleaning, and it is dried.Harbin Institute of Technology's WHD20 equipment is taken, forward voltage 250V, negative voltage 20V, working frequency are used
600Hz, positive duty ratio 30%, negative sense duty ratio 70%, positive negative sense umber of pulse is 1.Electrolyte is 0.05mol/L Na3PO4,
0.02mol/L Na2B4O7,0.05mol/L KOH, reaction time 15min, prepared solution pour into electrolytic cell, start
Agitating device agitating solution makes solution be uniformly mixed, and passes through magnesium alloy using 304 stainless steel wires, magnesium alloy is immersed electrolyte
In, and stainless steel wire is fixed on holder, as shown in Figure 1.Start mao power source, by the technological parameter pair of experimental design
Sample carries out differential arc oxidation processing, after the completion of processing, closes power supply.After reaction, sample is cleaned with deionized water ultrasound,
Allow sample natural drying after being blotted using blotting paper.Coupon surface microscopic topographic is as shown in Figure 2 after processing.
Embodiment 2
ZK60 magnesium alloys are cut into the coupon of 20*20*5mm using electro-spark cutting machine, are got on surface using electric drill head logical
Hole.It is polished magnesium alloy with the sand paper of 2000 mesh, obtains bright surface.The magnesium alloy for milled of fighting each other uses EtOH Sonicate
Cleaning, and it is dried.Harbin Institute of Technology's WHD20 equipment is taken, forward voltage 300V, negative voltage 20V, working frequency are used
600Hz, positive duty ratio 30%, negative sense duty ratio 70%, positive negative sense umber of pulse is 1.Electrolyte is 0.05mol/L Na3PO4,
0.02mol/L Na2B4O7,0.05mol/L KOH, reaction time 15min, prepared solution pour into electrolytic cell, start
Agitating device agitating solution makes solution be uniformly mixed, and passes through magnesium alloy using 304 stainless steel wires, magnesium alloy is immersed electrolyte
In, and stainless steel wire is fixed on holder.Start mao power source, sample is carried out by the technological parameter of experimental design micro-
Arc oxidation processes after the completion of processing, close power supply.After reaction, sample is cleaned with deionized water ultrasound, uses blotting paper
Allow sample natural drying after being blotted.Coupon surface microscopic topographic is as shown in Figure 3 after processing.
Embodiment 3
ZK60 magnesium alloys are cut into the coupon of 20*20*5mm using electro-spark cutting machine, are got on surface using electric drill head logical
Hole.It is polished magnesium alloy with the sand paper of 2000 mesh, obtains bright surface.The magnesium alloy for milled of fighting each other uses EtOH Sonicate
Cleaning, and it is dried.Harbin Institute of Technology's WHD20 equipment is taken, forward voltage 350V, negative voltage 20V, working frequency are used
600Hz, positive duty ratio 30%, negative sense duty ratio 70%, positive negative sense umber of pulse is 1.Electrolyte is 0.05mol/L Na3PO4,
0.02mol/L Na2B4O7,0.05mol/L KOH, reaction time 15min, prepared solution pour into electrolytic cell, start
Agitating device agitating solution makes solution be uniformly mixed, and passes through magnesium alloy using 304 stainless steel wires, magnesium alloy is immersed electrolyte
In, and stainless steel wire is fixed on holder.Start mao power source, sample is carried out by the technological parameter of experimental design micro-
Arc oxidation processes after the completion of processing, close power supply.After reaction, sample is cleaned with deionized water ultrasound, uses blotting paper
Allow sample natural drying after being blotted.Coupon surface microscopic topographic is as shown in Figure 4 after processing.
Embodiment 4
ZK60 magnesium alloys are cut into the coupon of 20*20*5mm using electro-spark cutting machine, are got on surface using electric drill head logical
Hole.It is polished magnesium alloy with the sand paper of 2000 mesh, obtains bright surface.The magnesium alloy for milled of fighting each other uses EtOH Sonicate
Cleaning, and it is dried.Harbin Institute of Technology's WHD20 equipment is taken, forward voltage 400V, negative voltage 20V, working frequency are used
600Hz, positive duty ratio 30%, negative sense duty ratio 70%, positive negative sense umber of pulse is 1.Electrolyte is 0.05mol/L Na3PO4,
0.02mol/L Na2B4O7,0.05mol/L KOH, reaction time 15min, prepared solution pour into electrolytic cell, start
Agitating device agitating solution makes solution be uniformly mixed, and passes through magnesium alloy using 304 stainless steel wires, magnesium alloy is immersed electrolyte
In, and stainless steel wire is fixed on holder.Start mao power source, sample is carried out by the technological parameter of experimental design micro-
Arc oxidation processes after the completion of processing, close power supply.After reaction, sample is cleaned with deionized water ultrasound, uses blotting paper
Allow sample natural drying after being blotted.Coupon surface microscopic topographic is as shown in Figure 5 after processing.
Using Tafel lines extrapolation respectively to carrying out corrosion rate measurement by the sample of embodiment 1-4, result curve is such as
Shown in Fig. 6, and by under embodiment 1-4 differential arc oxidation sample and untreated ZK60 magnesium alloys sample carry out bionical solution leaching
Bubble, test data are as shown in Figure 7.The above-mentioned microscopic appearance of comparative analysis and test curve figure it is found that embodiment 1 be the present invention most
Good embodiment.
The above description of the embodiments is intended to facilitate ordinary skill in the art to understand and use the invention.
Person skilled in the art obviously easily can make various modifications to these embodiments, and described herein general
Principle is applied in other embodiment without having to go through creative labor.Therefore, the present invention is not limited to the above embodiments, ability
Field technique personnel announcement according to the present invention, improvement and modification made without departing from the scope of the present invention all should be the present invention's
Within protection domain.
Claims (3)
1. one kind takes differential arc oxidation to improve the corrosion proof method of biological medical magnesium alloy, which is characterized in that include the following steps：
S1, it is polished ZK60 magnesium alloy article surfaces using sand paper；
S2, the magnesium alloy product polished is placed in ethanol solution be cleaned by ultrasonic after dry；
S3, electrolyte is prepared：The electrolyte includes 0.05mol/L Na3PO4, 0.02mol/LNa2B4O7, 0.05mol/L
KOH；Prepared solution is poured into electrolytic cell, agitating device agitating solution is started；
S4, magnesium alloy product is fixed on by stainless steel wire on holder and is immersed in electrolyte；
S5, start mao power source, it is true using forward voltage 250-400V, negative voltage 20V, working frequency 600Hz, forward direction
Sky carries out at differential arc oxidation magnesium alloy product than the running parameter that 30%, negative sense duty ratio 70%, positive negative sense umber of pulse are 1
Reason, processing time 15min；
S6, using blotting paper rear natural drying is blotted after cleaning magnesium alloy product with deionized water ultrasound.
2. one kind as described in claim 1 takes differential arc oxidation to improve the corrosion proof method of biological medical magnesium alloy, feature
It is：Sand paper described in step S1 is the fine sandpaper of 2000 mesh.
3. one kind as described in claim 1 takes differential arc oxidation to improve the corrosion proof method of biological medical magnesium alloy, feature
It is：Forward voltage selects 250V in step S5.
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| CN201810971007.6A CN108754578A (en) | 2018-08-24 | 2018-08-24 | One kind takes differential arc oxidation to improve the corrosion proof method of biological medical magnesium alloy |
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| CN201810971007.6A CN108754578A (en) | 2018-08-24 | 2018-08-24 | One kind takes differential arc oxidation to improve the corrosion proof method of biological medical magnesium alloy |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101476143A (en) * | 2007-12-31 | 2009-07-08 | 比亚迪股份有限公司 | Differential arc oxidation electrolytic solution and differential arc oxidation method |
| US20090250351A1 (en) * | 2004-07-23 | 2009-10-08 | Ilya Ostrovsky | Method for producing a hard coating with high corrosion resistance on articles made of anodizable metals or alloys |
| CN107059094A (en) * | 2017-03-09 | 2017-08-18 | 山东大学 | A kind of differential arc oxidation coating and preparation method thereof |
-
2018
- 2018-08-24 CN CN201810971007.6A patent/CN108754578A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20090250351A1 (en) * | 2004-07-23 | 2009-10-08 | Ilya Ostrovsky | Method for producing a hard coating with high corrosion resistance on articles made of anodizable metals or alloys |
| CN101476143A (en) * | 2007-12-31 | 2009-07-08 | 比亚迪股份有限公司 | Differential arc oxidation electrolytic solution and differential arc oxidation method |
| CN107059094A (en) * | 2017-03-09 | 2017-08-18 | 山东大学 | A kind of differential arc oxidation coating and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 崔学军等: ""几种添加剂作用的微弧氧化膜表面结构及防腐性能"", 《中国表面工程》 * |
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Application publication date: 20181106 |