CN104800888A - Magnesium and magnesium alloy surface modification zinc tin composite film and preparing method thereof - Google Patents
Magnesium and magnesium alloy surface modification zinc tin composite film and preparing method thereof Download PDFInfo
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- CN104800888A CN104800888A CN201510237459.8A CN201510237459A CN104800888A CN 104800888 A CN104800888 A CN 104800888A CN 201510237459 A CN201510237459 A CN 201510237459A CN 104800888 A CN104800888 A CN 104800888A
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Abstract
The invention discloses a magnesium and magnesium alloy surface modification zinc tin composite film and a preparing method thereof, and belongs to the technical field of surface treatment. The zinc tin composite film is prepared on the surfaces of magnesium and magnesium alloy by an electrochemical deposition method, the film layer is formed by compounding MgO, ZnO and SnO2, and the thickness of the film layer is 2 to 5 mu m. Through the film layer preparation, the anti-corrosion performance of the magnesium and the magnesium alloy is improved.
Description
Technical field
The invention belongs to the process for treating surface of a kind of Magnesium and magnesium alloys Mg-X (in the biocompatibility element such as X=Zn, Ca, Sr, Zr one or more), adopt electrochemical deposition method to prepare zinc-tin composite membrane on Magnesium and magnesium alloys surface.
Background technology
At present, be widely used in clinical metal implant material and mainly comprise rustless steel, cochrome and titanium alloy, they all have good corrosion resistance, can stablize by long-term holding structure in vivo, but these materials produce abrasive dust because of body internal friction and produce poisonous ion because of corrosion, cause local anaphylaxis or inflammation, reduce its biocompatibility.In addition, these materials are inert material, non-degradable in fluid environment.They may cause the situation such as tissue inflammation and vascular restenosis in implant site long-term existence, therefore need to carry out second operation, and this not only increases patient suffering, and considerably increases surgery cost.Magnesium is one of macroelement of needed by human, is mainly distributed in skeleton, muscle, extracellular fluid and blood plasma, can activates multiple enzyme, participates in the metabolic processes of human body, and promoting the deposition of calcium, is the indispensable element of osteogenesis.Magnesium excessive in this ectosome excretes by urine, can not cause the obvious rising of serum magnesium content or is deposited in body and causes toxic reaction.Magnesium and magnesium alloys is important orthopaedics fixture and cardiovascular implant degradable metal material.
The MgO thin film that under dry environment, Magnesium and magnesium alloys surface meeting self-assembling formation one deck is loose, becomes Mg (OH) in wet environment
2thin film, this thin film can improve Magnesium and magnesium alloys decay resistance to a certain extent.But the protectiveness rete of self-assembling formation is very thin and uneven, will soon be destroyed in body fluid, and then there is violent corrosion in matrix material.In general, desirable degradable orthopaedics fixture and cardiovascular implant material require kept its mechanical property not worsen in six months, but the degradation rate of Magnesium and magnesium alloys too fast (being no more than four months), can not meet clinical needs, so need to reduce its degradation rate further.
Surface modification means are a kind of methods of effectively suppression Magnesium and magnesium alloys Initial Corrosion speed.Electrochemical deposition method is simple, is easy to realize, and the even film layer of deposition is fine and close, effectively can improve the decay resistance of matrix.Zinc is one of trace element of needed by human, plays an important role in the important physiological process such as growth in humans's growth, reproduction heredity, immunity, endocrine.Stannum can promote the synthesis of protein and nucleic acid, is conducive to the growth promoter of health; And form multiple enzyme and participate in the biological respinse of flavo-enzyme, can the stability etc. of reinforcement environment.If the too fast problem of magnesium alloy degradation rate just can be solved at the zinc-tin composite membrane that preparation a kind of thickness in Magnesium and magnesium alloys surface is moderate, ensure the good biocompatibility of material simultaneously.
Summary of the invention
The invention provides a kind of Magnesium and magnesium alloys surface modification zinc-tin composite membrane and preparation method thereof, utilize electrochemical deposition, prepare zinc-tin composite membrane on Magnesium and magnesium alloys surface, rete is by MgO, ZnO and SnO
2compound is formed.Under fluid environment, surperficial zinc-tin composite membrane is first corroded, and after zinc-tin composite membrane corrodes completely, Magnesium and magnesium alloys matrix just starts corrosion, and therefore the existence of rete improves the corrosion potential of material, reduces corrosion current.
The object of the invention is to propose one utilizes electrochemical deposition to carry out the method for surface modification to Magnesium and magnesium alloys Mg-X (in the biocompatibility element such as X=Zn, Ca, Sr, Zr one or more).Form by being electrochemically-deposited in Magnesium and magnesium alloys surface the composite membrane containing zinc-tin, this rete is by MgO, ZnO and SnO
2compound is formed, and thickness is at 2-5um, and the existence of this rete improves matrix decay resistance.In addition, zinc-tin has good biocompatibility, and the Magnesium and magnesium alloys of the zinc-tin composite membrane therefore prepared is a kind of good biocompatibility, the material that decay resistance is high, and its combination property is obviously better than Magnesium and magnesium alloys.The zinc-tin composite membrane Main Function adopting electrochemical deposition means to prepare in the present invention is to improve the decay resistance of Magnesium and magnesium alloys.
One provided by the invention utilizes electrochemical deposition to carry out the method for surface modification to Magnesium and magnesium alloys Mg-X (in the biocompatibility element such as X=Zn, Ca, Sr, Zr one or more), comprises the steps:
The first step: substrate pretreatment:
Magnesium and magnesium alloys matrix, after polishing, polishing, obtains matrix sample with after dehydrated alcohol ultrasonic cleaning 10min;
Second step: the solution of configuration needed for electrochemical deposition;
With the solution needed for deionized water configuration electrochemical deposition, solution concentration is: 0.3M ~ 1.0MZnSO
47H
2o+0.05M ~ 0.3MSnSO
4.
3rd step: electrochemical deposition prepares zinc-tin composite membrane.
(A) electrochemistry sample preparation;
(B) sample working surface carries out electrochemical deposition, the obtained sample with zinc-tin composite membrane; Electrochemical deposition process desired parameters: voltage-1 ~-5V, time 10 ~ 180min.
The Magnesium and magnesium alloys that said method prepares, surface is the composite film of zinc-tin, and rete is by MgO, ZnO and SnO
2compound is formed, and described thicknesses of layers is at 2-5um.Modified Magnesium and magnesium alloys good biocompatibility, meets the corrosion resistance of clinical practice requirement.
The invention has the advantages that:
The existence of coating improves Magnesium and magnesium alloys decay resistance, can meet clinical practice requirement.Magnesium and magnesium alloys through electrochemical deposition surface modification improves 100 ~ 350mV than the corrosion potential of unmodified Magnesium and magnesium alloys, corrosion current reduces an order of magnitude, reaches 10
- 5a/cm
2.
Accompanying drawing explanation
Fig. 1: the polarization curve of magnesium alloy before and after surface modification in embodiment 1.
Fig. 2: the surface topography of untreated pure magnesium.
Fig. 3: the surface topography of the magnesium matrix of the surface modification of preparation in embodiment 1.
Detailed description of the invention
Below in conjunction with drawings and Examples, the present invention is described in further detail.
The electrochemical deposition that utilizes provided by the invention carries out the method for surface modification to Magnesium and magnesium alloys Mg-X (in the biocompatibility element such as X=Zn, Ca, Sr, Zr one or more), comprises the steps:
The first step: substrate pretreatment:
Magnesium and magnesium alloys matrix, after polishing, polishing, obtains matrix sample with after dehydrated alcohol ultrasonic cleaning 10min;
Second step: the solution of configuration needed for electrochemical deposition;
With the solution needed for deionized water configuration electrochemical deposition, solution concentration is: 0.3M ~ 1.0MZnSO
47H
2o+0.05M ~ 0.3MSnSO
4, preferred 0.5MZnSO
47H
2o+0.1MSnSO
4.
3rd step: electrochemical deposition prepares zinc-tin composite membrane.
(A) electrochemistry sample preparation;
(B) sample working surface carries out electrochemical deposition, the obtained sample with zinc-tin composite membrane; Electrochemical deposition process desired parameters: voltage-1 ~-5V, preferably-3V; Time 10 ~ 180min, preferably 60 ~ 180min.
Describe in detail below by specific embodiment.
embodiment 1:
The electrochemical deposition that utilizes provided by the invention carries out the method for surface modification to Magnesium and magnesium alloys Mg-X (in the biocompatibility element such as X=Zn, Ca, Sr, Zr one or more), comprises the steps:
The first step: substrate pretreatment:
Magnesium and magnesium alloys matrix, after polishing, polishing, obtains matrix sample with after dehydrated alcohol ultrasonic cleaning 10min;
Second step: the solution of configuration needed for electrochemical deposition;
With the solution needed for deionized water configuration electrochemical deposition, solution concentration is: 0.5MZnSO
47H
2o+0.1MSnSO
4.
3rd step: electrochemical deposition prepares zinc-tin composite membrane.
(A) electrochemistry sample preparation;
(B) sample working surface carries out electrochemical deposition, the obtained sample with zinc-tin composite membrane; Electrochemical deposition process desired parameters: voltage-3V, time 60min.
Decay resistance detection is carried out to alloy obtained in embodiment 1:
By composite membrane alloy obtained for embodiment 1 at 37 ± 1 DEG C, carry out electro-chemical test in simulated body fluid solution, adopt three-electrode system, platinum electrode is as auxiliary electrode, and saturated calomel electrode is as reference electrode, and potential scanning speed is 0.001v/s.From accompanying drawing 1, composite membrane corrosion potential prepared by embodiment 1 improves 100-200mV with matrix phase ratio, and the more unmodified alloy of corrosion current reduces an order of magnitude, reaches 5.54 × 10
-5a/cm
2.
embodiment 2:
The first step: substrate pretreatment:
Magnesium and magnesium alloys matrix, after polishing, polishing, obtains matrix sample with after dehydrated alcohol ultrasonic cleaning 10min;
Second step: the solution of configuration needed for electrochemical deposition;
With the solution needed for deionized water configuration electrochemical deposition, solution concentration is: 0.5MZnSO
47H
2o+0.1MSnSO
4.
3rd step: electrochemical deposition prepares zinc-tin composite membrane.
(A) electrochemistry sample preparation;
(B) sample working surface carries out electrochemical deposition, the obtained sample with zinc-tin composite membrane; Electrochemical deposition process desired parameters: voltage-3V, time 120min.
Through Performance Detection, the zinc-tin composite membrane that the method is prepared, due to the prolongation of electrochemical deposition time, causes the increase of thicknesses of layers.In corrosion resistance test, corrosion potential improves 120-250mV compared to matrix.Illustrate that increasing sedimentation time is conducive to improving its corrosive nature.
embodiment 3:
The first step: substrate pretreatment:
Magnesium and magnesium alloys matrix, after polishing, polishing, obtains matrix sample with after dehydrated alcohol ultrasonic cleaning 10min;
Second step: the solution of configuration needed for electrochemical deposition;
With the solution needed for deionized water configuration electrochemical deposition, solution concentration is: 0.5MZnSO
47H
2o+0.1MSnSO
4.
3rd step: electrochemical deposition prepares zinc-tin composite membrane.
(A) electrochemistry sample preparation;
(B) sample working surface carries out electrochemical deposition, the obtained sample with zinc-tin composite membrane; Electrochemical deposition process desired parameters: voltage-3V, time 180min.
Through Performance Detection, the zinc-tin composite membrane that the method is prepared, due to the increase of electrochemical deposition time, causes the increase of thicknesses of layers and density.In corrosion resistance test, corrosion potential improves 180-350mV compared to matrix.The Magnesium and magnesium alloys Mg-X of the electrochemical deposition surface modification obtained through preparation method of the present invention (X=Zn, Ca, Sr, Zr etc. one or both) can be used as bio-medical material, as the blade plate, nail, angiocarpy bracket etc. of different parts.Because Magnesium and magnesium alloys is after electrochemical deposition, the zinc-tin composite membrane that surface is formed greatly reduces the corrosion rate of Magnesium and magnesium alloys, and the too fast problem of biodegradation Magnesium and magnesium alloys corrosion rate can be improved greatly.
Claims (6)
1. a Magnesium and magnesium alloys surface modification zinc-tin composite membrane, is characterized in that: the method adopting electrochemical deposition, prepares the composite membrane of zinc-tin on Magnesium and magnesium alloys surface; Rete is by MgO, ZnO and SnO
2compound is formed.
2. a kind of Magnesium and magnesium alloys surface modification zinc-tin composite membrane according to claim 1, is characterized in that: described thicknesses of layers is at 2-5um.
3. Magnesium and magnesium alloys surface modification zinc-tin composite membrane and preparation method thereof, it is characterized in that, described method comprises the steps:
The first step: substrate pretreatment:
Magnesium and magnesium alloys matrix, after polishing, polishing, obtains matrix sample with after dehydrated alcohol ultrasonic cleaning 10min;
Second step: the solution of configuration needed for electrochemical deposition;
3rd step: electrochemical deposition prepares zinc-tin composite membrane.
4. method according to claim 3, is characterized in that: second step is specially: with the solution needed for deionized water configuration electrochemical deposition, solution concentration is: 0.3M ~ 1.0M ZnSO
47H
2o+0.05M ~ 0.3M SnSO
4.
5. method according to claim 3, is characterized in that: the 3rd step is specially:
(A) electrochemistry sample preparation;
(B) sample working surface carries out electrochemical deposition, the obtained sample with zinc-tin composite membrane; Electrochemical deposition process desired parameters: voltage-1 ~-5V, time 10 ~ 180min.
6. method according to claim 3, is characterized in that: described matrix is Magnesium and magnesium alloys.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109014184A (en) * | 2018-08-10 | 2018-12-18 | 中南大学 | A kind of biological medical magnesium alloy and preparation method thereof with dual corrosion drag |
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|---|---|---|---|---|
| JP2006169543A (en) * | 2004-12-10 | 2006-06-29 | Japan Carlit Co Ltd:The | Highly corrosion resistant material for electric conduction and production method therefor |
| US20070048550A1 (en) * | 2005-08-26 | 2007-03-01 | Millero Edward R | Coating compositions exhibiting corrosion resistance properties, related coated substrates, and methods |
| CN102582827A (en) * | 2012-02-11 | 2012-07-18 | 黄廷华 | Flying device capable of moving randomly |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006169543A (en) * | 2004-12-10 | 2006-06-29 | Japan Carlit Co Ltd:The | Highly corrosion resistant material for electric conduction and production method therefor |
| US20070048550A1 (en) * | 2005-08-26 | 2007-03-01 | Millero Edward R | Coating compositions exhibiting corrosion resistance properties, related coated substrates, and methods |
| CN102582827A (en) * | 2012-02-11 | 2012-07-18 | 黄廷华 | Flying device capable of moving randomly |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109014184A (en) * | 2018-08-10 | 2018-12-18 | 中南大学 | A kind of biological medical magnesium alloy and preparation method thereof with dual corrosion drag |
| CN109014184B (en) * | 2018-08-10 | 2020-03-31 | 中南大学 | Biomedical magnesium alloy with dual corrosion resistance and preparation method thereof |
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