CN103451643A - Biological magnesium alloy with surface coated with sodium magnesium fluoride film and preparation method thereof - Google Patents
Biological magnesium alloy with surface coated with sodium magnesium fluoride film and preparation method thereof Download PDFInfo
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- CN103451643A CN103451643A CN2013103911346A CN201310391134A CN103451643A CN 103451643 A CN103451643 A CN 103451643A CN 2013103911346 A CN2013103911346 A CN 2013103911346A CN 201310391134 A CN201310391134 A CN 201310391134A CN 103451643 A CN103451643 A CN 103451643A
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Abstract
The invention relates to a biological magnesium alloy with a surface coated with a sodium magnesium fluoride film and a preparation method thereof. The surface of the biological magnesium alloy is coated with the sodium magnesium fluoride film. The preparation method of the biological magnesium alloy comprises the following steps: carrying out alkaline oil removal; washing; preparing the sodium magnesium fluoride film; washing; washing by using alcohol; air-drying. The method for preparing the sodium magnesium fluoride film particularly comprises the following steps: immersing the biological magnesium alloy into a treatment solution with the temperature of 75-90 DEG C and the molar concentration of sodium fluoride and hydrofluoric acid respectively equal to 1.6 mol/L and 4.8 mol/L; performing heat preservation for 10-90 minutes, and then taking out the biological magnesium alloy. According to the biological magnesium alloy with the surface coated with the sodium magnesium fluoride film, the sodium magnesium fluoride film has the characteristics of simple preparation process, convenience for operation, suitability for industrial production, and the like, and can be used for the surface modification coating of a magnesium alloy; the biological magnesium alloy disclosed by the invention can be used for preparing a biological magnesium alloy device.
Description
Technical field
The present invention relates to technical field of biological materials, be specially adapted to the surface modification field of biological magnesium alloy device, be specifically related to a kind of surface and be coated with biological magnesium alloy of sodium magnesium fluoride film and preparation method thereof.
Background technology
Magnesium is the major element of needed by human, magnesium alloy has biodegradable, density (1.74g.cm
-3) and human body bone (1.75g.cm
-3) quite, Young's modulus (45GPa) approaches with people's bone (20GPa), specific tenacity and specific rigidity high, is the metallic substance that has broad prospect of application aspect the biological implant devices such as hone lamella, nail, intravascular stent.Yet, because the higher chemically reactive of magnesium causes corrosion stability of magnesium alloy poor, cause on the one hand the service life due with it in work-ing life of the biological implant devices of magnesium alloy not mate, too fast corrosion causes the alkalization of surrounding environment on the other hand, also is unfavorable for its application in human body.Therefore, significant by the solidity to corrosion of surface and/or bulk modified raising magnesium alloy.
Research shows, surface modification is one of important channel of improving corrosion stability of magnesium alloy.Yet different from general magnesium alloy component surface modification, the surface modified coat of medical magnesium alloy device, except requiring to have good solidity to corrosion, also must have good biocompatibility, and do not change the degradable characteristic of device.
Research both at home and abroad shows, in biological magnesium alloy hone lamella surface-coated magnesium fluoride coating, not only can obviously reduce the erosion rate of magnesium alloy hone lamella, and the fluorion in coating has the effect that promotes that area of new bone cell and freshman bone tissue form.Chinese invention patent (the patent No. 200710159202.0 for example, the applying date 2007/12/26) a kind of band medicine degradable magnesium alloy angiocarpy bracket and preparation method thereof is disclosed, the magnesium fluoride film of Mg alloy surface not only can reduce the degradation rate of magnesium alloy angiocarpy bracket, and the fluorine that forms of degraded reacts formation magnesium fluoride with magnesium ion is deposited on rack surface, there is certain self-repair function.Yet magnesium fluoride film barrier propterty and magnesium fluoride film thickness have much relations, obtaining the thick approximately magnesium fluoride film of 2 μ m at least needs the 48h left and right.
Summary of the invention
the technical problem solved:the solidity to corrosion existed in as a kind of metal material embedded application at biomedical sector for magnesium alloy is not enough and the thicker magnesium fluoride membrane process overlong time problem of preparation, the invention provides a kind of surface and is coated with biological magnesium alloy of sodium magnesium fluoride film and preparation method thereof.
technical scheme:the invention provides the biological magnesium alloy that a kind of surface is coated with the sodium magnesium fluoride film, biological Mg alloy surface is coated with one deck sodium magnesium fluoride film.
Biological magnesium alloy described above is the Mg-Nd-Zn-Zr magnesium alloy.
Sodium magnesium fluoride film described above is porous-film or continuous film, its granulometric composition of sodium magnesium fluoride by cube shaped, the average rib length of sodium magnesium fluoride particle is 2 μ m, this sodium magnesium fluoride crystal grain is that magnesium alloy is in the treatment solution of Sodium Fluoride and hydrofluoric acid composition, by chemical reaction after Mg alloy surface forms the sodium magnesium fluoride core, then by the formation of growing up of the mechanism of the Step Growth after two-dimentional forming core and spiral growth mechanism.
A kind of surface described above is coated with the preparation method of the biological magnesium alloy of sodium magnesium fluoride film, comprise alkaline degreasing, wash, prepare the sodium magnesium fluoride film, washing, alcohol is washed and the step of drying, the described concrete grammar for preparing the sodium magnesium fluoride film is that biological magnesium alloy is immersed to temperature is that 75 ℃～90 ℃, Sodium Fluoride and hydrofluoric acid volumetric molar concentration are respectively in the treatment solution of 1.6mol/L and 4.8mol/L, after insulation 10min～90min, biological magnesium alloy is taken out.
In the described above step for preparing the sodium magnesium fluoride film, can, by changing Sodium Fluoride and the concentration of hydrofluoric acid and technological temperature and the time for preparing the sodium magnesium fluoride film in treatment solution, obtain sodium magnesium fluoride porous-film or the continuous film of the different porosities that meets different biological magnesium alloy device surface rete application requiring.Adopting grid method to carry out quantitative metallographic analysis shows, in the 1.6mol/L Sodium Fluoride that is 80 ℃ in temperature and 4.8mol/L hydrofluoric acid treatment liquid, when the process time is 10min, 20min and 30min, can obtain respectively porosity and be about 23%, 8% and 4% sodium magnesium fluoride porous-film, energy spectrum analysis shows, in sodium magnesium fluoride porous-film hole, is the magnesium fluoride film; When technological temperature is 80 ℃, the process time, while being 30min, the mean thickness of sodium magnesium fluoride film is 2.5 μ m approximately.When technological temperature is 90 ℃, process time while being 30min, can obtain the sodium magnesium fluoride continuous film.
In the described above step for preparing the sodium magnesium fluoride film, after temperature is to process 30min during 80 ℃, Sodium Fluoride and hydrofluoric acid volumetric molar concentration are respectively the treatment solution of 1.6mol/L and 4.8mol/L, adopt again the ultrasonic wave infusion method to prepare the poly(lactic acid) coating, the sodium magnesium fluoride film can effectively suppress the katalysis of magnesium to the polylactic acid membrane degraded, reduces the degradation rate of polylactic acid membrane.
A kind of surface of the present invention is coated with the biological magnesium alloy of sodium magnesium fluoride film, and in the interface region between simulated body fluid and magnesium alloy substrate, sodium magnesium fluoride dissolves the fluorion (NaMgF produced
3→ Na
++ Mg
2++ 3F
-) also can be by the magnesium ion (Mg+2H with magnesium alloy substrate corrosion generation
2o → H
2↑+Mg
2++ 2OH
-) or SBF in Ca
2+between chemical reaction (2F occurs
-+ Mg
2+→ MgF
2or 2F
-+ Ca
2+→ CaF
2), the magnesium fluoride or the Calcium Fluoride (Fluorspan) that form indissoluble are deposited in protective membrane, thereby the protective membrane of Mg alloy surface is produced to self-repair function.
beneficial effect:compared with prior art, a kind of surface provided by the invention is coated with biological magnesium alloy of sodium magnesium fluoride film and preparation method thereof, has the following advantages:
1. sodium magnesium fluoride film of the present invention is the same with the magnesium fluoride film, and the fluorine that the sodium magnesium fluoride membrane degradation produces reacts the magnesium fluoride formed the sodium magnesium fluoride film is had to certain self-repair function with magnesium ion;
2. its liberation of hydrogen speed can be significantly reduced when sodium magnesium fluoride film of the present invention is separately as biological Mg alloy surface anti-corrosion coating, the corrosion-resistant time of biological magnesium alloy can be effectively extended;
3. sodium magnesium fluoride film of the present invention also can be used as the middle supercoat of the magnesium alloy implant devices of medicine carrying and coating poly(lactic acid) organic membrane;
4. the preparation time of sodium magnesium fluoride film of the present invention is short, with obtaining the magnesium fluoride film that approximately 2 μ m are thick, need to compare by about 48h, and the present invention obtains the 2.5 thick sodium magnesium fluoride films in μ m left and right and only needs 0.5h;
5. the present invention has the characteristics such as preparation technology is simple, easy to operate, cost is low, is applicable to industrialization production, can be used for preparing biological magnesium alloy device.
The accompanying drawing explanation
The surface topography that Fig. 1 is the Mg-Nd-Zn-Zr Mg alloy surface sodium magnesium fluoride film for preparing of the embodiment of the present invention 1.
The XRD spectrum that Fig. 2 is the Mg-Nd-Zn-Zr Mg alloy surface sodium magnesium fluoride film for preparing of the embodiment of the present invention 1.
Fig. 3 is Mg-Nd-Zn-Zr magnesium alloy substrate of the present invention and sodium magnesium fluoride film liberation of hydrogen speed correlation curve in SBF liquid.
Embodiment
embodiment 1
A kind of surface is coated with the preparation method of the biological magnesium alloy of sodium magnesium fluoride film, the volumetric molar concentration that at first will immerse 80 ℃, Sodium Fluoride and hydrofluoric acid through the Mg-Nd-Zn-Zr magnesium alloy sample of oil removing and washing is respectively in the treatment solution of 1.6mol/L and 4.8mol/L, after reaction 30min, sample is taken out, dry after washing through washing, alcohol.
As shown in Figure 1, morphology observation by scanning electronic microscope to biological magnesium alloy sample surface fluorination magnesium sodium film shows, the sodium magnesium fluoride film is by approximate cubical sodium magnesium fluoride granulometric composition, the sodium magnesium fluoride particle has two-dimentional forming core Step Growth and two kinds of growth mechanisms of spiral growth, the average rib of sodium magnesium fluoride particle is about 2 μ m, the porosity of porous-film approximately 4%.
As shown in Figure 2, X-ray diffraction analysis shows, the film that reaction forms is the sodium magnesium fluoride film.
As shown in Figure 3, in SBF liquid, soak test shows, the sodium magnesium fluoride film can significantly reduce the liberation of hydrogen speed of matrix magnesium alloy.
Adopt potassium permanganate (0.5 grams per liter) and nitric acid (30 milliliters/liter) solution titration to show, the variable color time of sodium magnesium fluoride film sample is 4.4 times of magnesium alloy substrate; Electro-chemical test shows, be about-1.53V of the corrosion potential of magnesium alloy substrate, the be about-1.42V of corrosion potential of sodium magnesium fluoride film sample; The cross section film thickness measuring shows, the mean thickness of sodium magnesium fluoride film is 2.5 μ m approximately.
embodiment 2
A kind of surface is coated with the preparation method of the biological magnesium alloy of sodium magnesium fluoride film, the volumetric molar concentration that at first will immerse 80 ℃, Sodium Fluoride and hydrofluoric acid through the Mg-Nd-Zn-Zr magnesium alloy sample of oil removing and washing is respectively in the treatment solution of 1.6mol/L and 4.8mol/L, after reaction 10min, sample is taken out, dry after washing through washing, alcohol.
As shown in Figure 3, in SBF liquid, soak test shows, the sodium magnesium fluoride film can significantly reduce the liberation of hydrogen speed of matrix magnesium alloy.
Morphology observation by scanning electronic microscope to biological magnesium alloy sample surface fluorination magnesium sodium film shows, the sodium magnesium fluoride film is by approximate cubical sodium magnesium fluoride granulometric composition, and the average rib of sodium magnesium fluoride particle is about 2 μ m; To sodium magnesium fluoride, intergranular internal pore surface energy spectrum analysis shows, in hole, is the magnesium fluoride film; Adopt grid method to calculate and show, the porosity of porous-film is about 23%; Adopt potassium permanganate (0.5 grams per liter) and nitric acid (30 milliliters/liter) solution titration to show, its variable color time is 2.2 times of matrix magnesium alloy.
A kind of surface is coated with the preparation method of the biological magnesium alloy of sodium magnesium fluoride film, the volumetric molar concentration that at first will immerse 80 ℃, Sodium Fluoride and hydrofluoric acid through the Mg-Nd-Zn-Zr magnesium alloy sample of oil removing and washing is respectively in the treatment solution of 1.6mol/L and 4.8mol/L, after reaction 60min, sample is taken out, dry after washing through washing, alcohol.
Morphology observation by scanning electronic microscope to biological magnesium alloy sample surface fluorination magnesium sodium film shows, the sodium magnesium fluoride film is by approximate cubical sodium magnesium fluoride granulometric composition, adopt potassium permanganate (0.5 grams per liter) and nitric acid (30 milliliters/liter) solution titration to show, its variable color time is 5.3 times of matrix magnesium alloy.
embodiment 4
A kind of surface is coated with the preparation method of the biological magnesium alloy of sodium magnesium fluoride film, the volumetric molar concentration that at first will immerse 80 ℃, Sodium Fluoride and hydrofluoric acid through the Mg-Nd-Zn-Zr magnesium alloy sample of oil removing and washing is respectively in the treatment solution of 1.6mol/L and 4.8mol/L, after reaction 90min, sample is taken out, dry after washing through washing, alcohol.
Morphology observation by scanning electronic microscope to biological magnesium alloy sample surface fluorination magnesium sodium film shows, the sodium magnesium fluoride film is by approximate cubical sodium magnesium fluoride granulometric composition, adopt potassium permanganate (0.5 grams per liter) and nitric acid (30 milliliters/liter) solution titration to show, its variable color time is 6.5 times of matrix magnesium alloy.
embodiment 5
A kind of surface is coated with the preparation method of the biological magnesium alloy of sodium magnesium fluoride film, the volumetric molar concentration that at first will immerse 90 ℃, Sodium Fluoride and hydrofluoric acid through the Mg-Nd-Zn-Zr magnesium alloy sample of oil removing and washing is respectively in the treatment solution of 1.6mol/L and 4.8mol/L, after reaction 30min, sample is taken out, dry after washing through washing, alcohol.
Morphology observation by scanning electronic microscope to biological magnesium alloy sample surface fluorination magnesium sodium film shows, the sodium magnesium fluoride film is continuous film, between the sodium magnesium fluoride particle without sharp interface, the approximate average rib of cubical sodium magnesium fluoride particle of the part of convex surface is about 0.5 μ m, adopt potassium permanganate (0.5 grams per liter) and nitric acid (30 milliliters/liter) solution titration to show, its variable color time is 4.7 times of matrix magnesium alloy.
embodiment 6
A kind of surface is coated with the preparation method of the biological magnesium alloy of sodium magnesium fluoride film, the volumetric molar concentration that at first will immerse 80 ℃, Sodium Fluoride and hydrofluoric acid through the Mg-Nd-Zn-Zr magnesium alloy sample of oil removing and washing is respectively in the treatment solution of 1.6mol/L and 4.8mol/L, after reaction 30min, sample is taken out, dry after washing through washing, alcohol; Again sample ultrasonic wave in the poly(lactic acid) solution of 30g/L is dried after soaking 5min.
Sodium magnesium fluoride film obtained above and the simultaneous biological magnesium alloy sample of polylactic acid membrane are immersed in to 24h in the SBF liquid of 37 ℃, the specimen surface color does not become.And the biological magnesium alloy substrate sample that will directly apply polylactic acid membrane is immersed in 24h in the SBF liquid of 37 ℃, its surperficial polylactic acid membrane is all degraded, and biological magnesium alloy substrate is corroded, the specimen surface gray.
The present invention can also have other embodiment, and the technical scheme that the equal replacement of all employings or equivalent transformation form, within all dropping on the scope of protection of present invention.
Claims (3)
1. a surface is coated with the biological magnesium alloy of sodium magnesium fluoride film, and it is characterized in that: biological Mg alloy surface is coated with one deck sodium magnesium fluoride film.
2. a kind of surface according to claim 1 is coated with the biological magnesium alloy of sodium magnesium fluoride film, it is characterized in that: described biological magnesium alloy is the Mg-Nd-Zn-Zr magnesium alloy.
3. a kind of surface as claimed in claim 1 is coated with the preparation method of the biological magnesium alloy of sodium magnesium fluoride film, comprise alkaline degreasing, wash, prepare the sodium magnesium fluoride film, washing, alcohol is washed and the step of drying, it is characterized in that: the described concrete grammar for preparing the sodium magnesium fluoride film is that biological magnesium alloy is immersed to temperature is that 75 ℃～90 ℃, Sodium Fluoride and hydrofluoric acid volumetric molar concentration are respectively in the treatment solution of 1.6mol/L and 4.8mol/L, after insulation 10min～90min, biological magnesium alloy is taken out.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105126240A (en) * | 2014-06-03 | 2015-12-09 | 陈彦彪 | Degradable ultrafine needle piece |
| CN110139681A (en) * | 2016-12-27 | 2019-08-16 | Meko激光材料加工公司 | The bracket made of biodegradable magnesium alloy with magnesium fluoride coating and organic coating |
| CN110713198A (en) * | 2018-07-11 | 2020-01-21 | 中国海洋大学 | Method for preparing sodium magnesium fluoride |
| CN114381725A (en) * | 2021-12-23 | 2022-04-22 | 滨州学院 | Biodegradable magnesium alloy surface multi-layer structure NaMgF3Method for producing a coating |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1928156A (en) * | 2005-09-05 | 2007-03-14 | 李克清 | Chemical plating method for Mg and its alloy |
| CN101468216A (en) * | 2007-12-26 | 2009-07-01 | 中国科学院金属研究所 | Degradable magnesium alloy angiocarpy bracket with medicine and preparation method thereof |
| KR20130076540A (en) * | 2011-12-28 | 2013-07-08 | 재단법인 포항산업과학연구원 | Surface treatments method of magnesium alloy |
-
2013
- 2013-09-02 CN CN201310391134.6A patent/CN103451643B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1928156A (en) * | 2005-09-05 | 2007-03-14 | 李克清 | Chemical plating method for Mg and its alloy |
| CN101468216A (en) * | 2007-12-26 | 2009-07-01 | 中国科学院金属研究所 | Degradable magnesium alloy angiocarpy bracket with medicine and preparation method thereof |
| KR20130076540A (en) * | 2011-12-28 | 2013-07-08 | 재단법인 포항산업과학연구원 | Surface treatments method of magnesium alloy |
Non-Patent Citations (1)
| Title |
|---|
| A.YAMAMOTO,ET AL.: "Microstructures and Corrosion Properties on Fluoride Treated Magnesium Alloy", 《MATERIALS TRANSACTIONS》, vol. 49, no. 5, 25 April 2008 (2008-04-25) * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105126240A (en) * | 2014-06-03 | 2015-12-09 | 陈彦彪 | Degradable ultrafine needle piece |
| CN110139681A (en) * | 2016-12-27 | 2019-08-16 | Meko激光材料加工公司 | The bracket made of biodegradable magnesium alloy with magnesium fluoride coating and organic coating |
| CN110713198A (en) * | 2018-07-11 | 2020-01-21 | 中国海洋大学 | Method for preparing sodium magnesium fluoride |
| CN114381725A (en) * | 2021-12-23 | 2022-04-22 | 滨州学院 | Biodegradable magnesium alloy surface multi-layer structure NaMgF3Method for producing a coating |
| WO2023115680A1 (en) * | 2021-12-23 | 2023-06-29 | 滨州学院 | Preparation method for hierarchical structure namgf3 coating on surface of biodegradable magnesium alloy |
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Effective date of registration: 20180626 Address after: 212000 the north side of north two weft Road, Danyang Development Zone, Zhenjiang, Jiangsu. Patentee after: Jiangsu Kay Cci Capital Ltd Address before: 211167 1 Hong Kong Avenue, Jiangning Science Park, Nanjing, Jiangsu Co-patentee before: Jiangsu Konsung Medical Equipment Co., Ltd. Patentee before: Nanjing Institute of Technology |
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