CN103505763A - Surface coating for magnesium alloy intra-bony fixing products and preparation method thereof - Google Patents
Surface coating for magnesium alloy intra-bony fixing products and preparation method thereof Download PDFInfo
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- CN103505763A CN103505763A CN201310354548.1A CN201310354548A CN103505763A CN 103505763 A CN103505763 A CN 103505763A CN 201310354548 A CN201310354548 A CN 201310354548A CN 103505763 A CN103505763 A CN 103505763A
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Abstract
The invention discloses a surface coating for magnesium alloy intra-bony fixing products. The surface coating is a composite coating composed of magnesium fluoride and fluor apatite, wherein the magnesium fluoride coating is characterized by being a nano particle coating with a particle size of 5 to 50 nm, and the coating thickness is 0.1 to 15 [mu]m; and the fluor apatite coating is a flower-shaped cluster composed of numerous nano-rods whose diameter is in a range of 50 to 500 nm and length is in a range of 10 to 500 [mu]m. The preparation method of the surface coating comprises the following steps: soaking a magnesium alloy intro-bony fixing product into a hydrofluoric acid water solution so as to generate a magnesium fluoride nano particle coating, then soaking the processed product into a water solution containing Ca<2+> and PO4<2-> ions, and allowing the automatic deposition of fluor apatite so as to obtain the magnesium fluoride/fluor apatite composite coating. The surface coating has the advantages that the composite coating solves the problems of bad biding force between a single hydroxyapatite coating and a substrate body and low corrosion resistant performance, is more suitable for being used as a surface coating for intra-bony fixing materials such as magnesium alloy bone nail, magnesium alloy bone plate, and the like.
Description
Technical field
The invention belongs to technical field of material, relate to a kind of face coat for fixed product in magnesium alloy bone and preparation method thereof.
Background technology
Magnesium and magnesium alloy are extensive as the degradable absorbing material application prospect that implants, compare with other metal materials, it has the following advantages: with the near elastic modelling quantity of people's bone photo, effectively prevent magnesium ion after stress shielding effect, degraded be human essential elements, can promote plurality of enzymes synthetic with regulate body temperature and muscle contraction etc., the degradability that it is unique, can avoid second operation to bring patient's misery.Yet magnesium alloy also exists such problem in biologic applications: initial stage degradation rate is too fast, mechanical property decay is serious; Ion stripping is too fast, causes surrounding tissue inflammation and reduces the stability of area of new bone.
At Mg alloy surface, preparing coating is to improve its corrosion proof effective way.By consulting existing document, K.Y. Chiu etc. are by preparing MgF by magnesium alloy long-time immersion in HF solution
2coating, and the corrosion resisting property in simulated body fluid is studied to it.Song etc. are immersed in magnesium alloy to contain Ca
2+, PO
4 3-solution in, by controlling the conditions such as temperature, synthos are deposited on to magnesium surface.Yet prepared MgF
2coating biology activity is poor, and calcium phosphate coating and basal body binding force are low, and short texture can not effectively slow down Corrosion Behaviors of Magnesium Alloys.Song Yang, a peasant etc. is placed in magnesium alloy to contain fluorine derivant and Ca in its patent " fluorine-substituted apatite coating of biologic medical magnesium or its alloy surface and preparation method "
2+and PO
4 2-solution in spontaneous deposition, after having deposited, heat, on surface, form fluor-apatite, yet in heating process, likely cause coating fragility increase or come off with matrix.
The invention provides a kind of reliable method of simple economy, only pass through chemical immersion, and in immersion process by regulating temperature, the parameters such as pH, just can be in magnesium alloy bone fixed product surface form the composite construction of nexine Afluon (Asta) nanoparticle coating, outer fluorapatite coating, the face coat that is extremely suitable for the bone fracture internal fixation materials such as magnesium alloy nail, hone lamella uses, and increases its biocompatibility and corrosion resistance.
Summary of the invention
The object of the invention is for above-mentioned existing problems, a kind of face coat for fixed product in magnesium alloy bone and preparation method thereof is provided, this composite coating good biocompatibility, corrosion resisting property is good in vivo, slow degradation and being easily absorbed in human body, is more suitable for the face coat as fixed product in the fracture such as magnesium alloy nail, hone lamella; Its preparation method is simple, easy to operate, is easy to realize suitability for industrialized production.
Technical scheme of the present invention:
For a face coat for fixed product in magnesium alloy bone, be Afluon (Asta)/fluor-apatite composite coating, nexine is Afluon (Asta) coating (MgF
2), skin be fluorapatite coating [(Ca)
10(PO4)
6f
2], wherein the shape characteristic of Afluon (Asta) coating is that grain size is the Nanoparticulate coating of 5-50nm, coating layer thickness is 0.1-15 μ m; Fluorapatite coating crystal form is that diameter 50-500nm, length are the flower-shaped cluster of numerous nanometer rods compositions of 10-500 μ m, and coating layer thickness is 10-500 μ m.
For a preparation method for the face coat of fixed product in magnesium alloy bone, its face coat is Afluon (Asta)/fluor-apatite composite coating, and step is as follows:
1) preparation of Afluon (Asta) coating
To be soaked in the Fluohydric acid. that concentration is 10-40wt% (HF) aqueous solution and be placed in shaking bath through fixed product in the dried magnesium alloy bone of ethanol ultrasonic cleaning, temperature be to soak 0.5-72h at 10-70 ℃, and product surface generates MgF
2nanoparticle coating;
2) preparation of Afluon (Asta)/fluor-apatite composite coating
By the above-mentioned MgF that contains
2in the magnesium alloy bone of coating, fixed product is immersed in containing Ca
2+and PO
4 2-in the deposit fluid of deionized water solution, the ammonia regulator solution pH that is 25-28wt% by concentration is 3.5-8.0, in temperature, be spontaneous deposition fluor-apatite at 60-100 ℃, sedimentation time is 5-180min, can in magnesium alloy bone, make Afluon (Asta)/fluor-apatite composite coating in the surface of fixed product.
Described containing Ca
2+compound be the mixture of one or more arbitrary proportions in lime nitrate, calcium chloride, calcium acetate, containing PO
4 2-the compound of ion is the mixture of one or more arbitrary proportions in sodium hydrogen phosphate, diammonium phosphate, dipotassium hydrogen phosphate, sodium dihydrogen phosphate, Ammonium biphosphate, potassium dihydrogen phosphate, tertiary sodium phosphate, potassium phosphate and ammonium phosphate, Ca in deposit fluid
2+and PO
4 2-ion concentration is 0.05-1mol/L.
A kind of application of the described face coat for fixed product in magnesium alloy bone, for fixed product surface in Mg-Zn-Zr alloy bone, prepare Afluon (Asta)/fluor-apatite composite coating, in Mg-Zn-Zr alloy bone, fixed product comprises Mg-Zn-Zr alloy hone lamella, Mg-Zn-Zr alloy screw and Mg-Zn-Zr alloy sheet.
The present invention has following beneficial effect:
The fluor-apatite layer of this composite coating is on Afluon (Asta) coating basis, by oh group in fluorion stripping in Afluon (Asta) substituted hydroxy apatite, form, this composite coating is compared with independent Afluon (Asta) coating or hydroxyapatite coating layer, biocompatibility is better, corrosion resisting property is more excellent in vivo, slow degradation and being easily absorbed in human body, independent coating and basal body binding force have been solved poor, the problem that corrosion resisting property is low, is more suitable for the face coat as fixed product in the fracture such as magnesium alloy nail, hone lamella; Its preparation method is simple, easy to operate, is easy to realize suitability for industrialized production.
Accompanying drawing explanation
fig. 1 is the Mg-Zn-Zr alloy hone lamella cross section SEM picture of embodiment 1 preparation.
Fig. 2 is that the Mg-Zn-Zr alloy plate surface of embodiment 1 preparation is through hydrofluoric acid treatment and untreated XRD diffraction spectrogram.
Fig. 3 is embodiment 1 Mg-Zn-Zr alloy plate surface SEM photo after hydrofluoric acid treatment.
Fig. 4 is the Mg-Zn-Zr alloy plate surface SEM photo with composite coating of embodiment 1 preparation.
Fig. 5 is the Mg-Zn-Zr alloy bone nail photo with composite coating of embodiment 2 preparations.
Fig. 6 is the Mg-Zn-Zr alloy bone nail with composite coating of embodiment 2 preparations and the variation comparison diagram of pure alloy bone nail pH in simulated body fluid.
The specific embodiment
The invention will be further described in connection with accompanying drawing for following instance, and the present embodiment is implemented take technical solution of the present invention under prerequisite, provided detailed embodiment and process, but protection scope of the present invention is not limited to following embodiment.The experimental technique of unreceipted actual conditions in the following example, conventionally according to normal condition, or the condition of advising according to manufacturer.
Embodiment 1:
A preparation method for the face coat of Mg-Zn-Zr alloy hone lamella, its face coat is Afluon (Asta)/fluor-apatite composite coating, step is as follows:
1) after length and width, the thick Mg-Zn-Zr alloy hone lamella that is of a size of 20mm, 8mm, 1.5 mm are also dried with ethanol ultrasonic cleaning, being immersed in concentration is in the HF aqueous solution of 20 wt %, in 37 ℃ of shaking baths, keep 6h, after taking-up, dry up, obtain surface for flavous Afluon (Asta) coating.
2) get 11.68g Ca (NO
3)
24H
20 and 3.45g NH
4h
2pO
4be dissolved in 500ml deionized water, the ammonia that is 28wt% by concentration regulates pH to 5.0, after stirring, pour there-necked flask into and be placed in water-bath, be heated to 80 ℃, the Mg-Zn-Zr alloy hone lamella of step 1 preparation is hung and immersed in solution, after deposition 30min, take out and dry up, obtain Afluon (Asta)/fluor-apatite composite coating.
Fig. 1, for the Mg-Zn-Zr alloy hone lamella cross section SEM picture of preparation, shows in figure: the thickness of Mg-Zn-Zr alloy plate surface Afluon (Asta)/fluor-apatite composite coating is 112.5 μ m.The Mg-Zn-Zr alloy plate surface that Fig. 2 is preparation is through hydrofluoric acid treatment and untreated XRD diffraction spectrogram, in figure, show: the surface in Ca-P solution of the hone lamella after HF acid treatment can form fluor-apatite, and can only form hydroxyapatite without HF is acid-treated.Fig. 3 is Mg-Zn-Zr alloy plate surface SEM photo after hydrofluoric acid treatment, shows: the Afluon (Asta) nano-particle that coating is about 20nm by diameter forms in figure, and thickness is about 0.7 μ m; Fig. 4 is the Mg-Zn-Zr alloy plate surface SEM photo with composite coating of embodiment 1 preparation, shows: plate surface forms by the integrated flower of numerous nanometer corynebacterium fluor-apatite cluster of particle, and chemical formula is Ca in figure
10(PO
4)
6f
2.
Embodiment 2:
A preparation method for the face coat of Mg-Zn-Zr alloy screw, its face coat is Afluon (Asta)/fluor-apatite composite coating, step is as follows:
1) Mg-Zn-Zr alloy screw is immersed at 37 ℃ to 2h in the HF of 10 wt %, after taking-up, dries up, obtain surface for copper-colored Afluon (Asta) coating.
2) get 0.1mol Ca (NO
3)
24H
20 and 0.06mol NaH
2pO
4be dissolved in 500ml deionized water, the ammonia that is 25wt% by concentration is poured there-necked flask into after regulating pH to 6.5 to stir, and is heated to 90 ℃ in water-bath, and the above-mentioned alloy screw of step is put into solution, after deposition 60min, take out and dry up, obtain Afluon (Asta)/fluor-apatite composite coating.
Fig. 5 is the Mg-Zn-Zr alloy bone nail photo with composite coating of embodiment 2 preparations.Fig. 6 is the Mg-Zn-Zr alloy bone nail with composite coating of embodiment 2 preparations and the variation comparison diagram of pure alloy bone nail pH in simulated body fluid, in figure, shows: after coating applies, the early stage corrosion rate of magnesium alloy significantly reduces.
Embodiment 3:
A preparation method for the face coat of Mg-Zn-Zr alloy sheet, its face coat is Afluon (Asta)/fluor-apatite composite coating, step is as follows:
1) magnesium alloy plate of length and width, the thick 5mm of being of a size of, 5mm, 1mm is used successively after 500 orders, 700 orders, 1200 object SiC sand paperings, with ethanol, clean and dry up, then be immersed in 4h in the HF that concentration is 40 wt %, after taking-up, dry up, obtain surface for copper-colored Afluon (Asta) coating.
2) get 0.5mol CaCl
2with 0.3mol NH
4h
2pO
4be dissolved in 500ml deionized water, the ammonia that is 26wt% by concentration regulates pH to 4.5, after stirring, pours there-necked flask into, in water-bath, be heated to 85 ℃, above-mentioned Mg-Zn-Zr alloy sheet is put into solution, after deposition 100min, take out and dry up, obtain Afluon (Asta)/fluor-apatite composite coating.
The implementation result of this embodiment is identical with embodiment 1.
Claims (4)
1. the face coat for fixed product in magnesium alloy bone, it is characterized in that: be Afluon (Asta)/fluor-apatite composite coating, nexine is Afluon (Asta) coating, skin is fluorapatite coating, wherein the shape characteristic of Afluon (Asta) coating is that grain size is the Nanoparticulate coating of 5-50nm, and coating layer thickness is 0.1-15 μ m; Fluorapatite coating crystal form is that diameter 50-500nm, length are the flower-shaped cluster of numerous nanometer rods compositions of 10-500 μ m, and coating layer thickness is 10-500 μ m.
2. as claimed in claim 1 for a preparation method for the face coat of fixed product in magnesium alloy bone, it is characterized in that: face coat is Afluon (Asta)/fluor-apatite composite coating, and step is as follows:
1) preparation of Afluon (Asta) coating
To be soaked in the hydrofluoric acid aqueous solution that concentration is 10-40wt% and be placed in shaking bath through fixed product in the dried magnesium alloy bone of ethanol ultrasonic cleaning, temperature be to soak 0.5-72h at 10-70 ℃, and product surface generates MgF
2nanoparticle coating;
2) preparation of Afluon (Asta)/fluor-apatite composite coating
By the above-mentioned MgF that contains
2in the magnesium alloy bone of coating, fixed product is immersed in containing Ca
2+and PO
4 2-in the deposit fluid of deionized water solution, the ammonia regulator solution pH that is 25-28wt% by concentration is 3.5-8.0, in temperature, be spontaneous deposition fluor-apatite at 60-100 ℃, sedimentation time is 5-180min, can in magnesium alloy bone, make Afluon (Asta)/fluor-apatite composite coating in the surface of fixed product.
3. according to claim 2 for the preparation method of the face coat of fixed product in magnesium alloy bone, it is characterized in that: described containing Ca
2+compound be the mixture of one or more arbitrary proportions in lime nitrate, calcium chloride, calcium acetate, containing PO
4 2-the compound of ion is the mixture of one or more arbitrary proportions in sodium hydrogen phosphate, diammonium phosphate, dipotassium hydrogen phosphate, sodium dihydrogen phosphate, Ammonium biphosphate, potassium dihydrogen phosphate, tertiary sodium phosphate, potassium phosphate and ammonium phosphate, Ca in deposit fluid
2+and PO
4 2-ion concentration is 0.05-1mol/L.
4. one kind as claimed in claim 1 for the application of the face coat of fixed product in magnesium alloy bone, it is characterized in that: for fixed product surface in Mg-Zn-Zr alloy bone, prepare Afluon (Asta)/fluor-apatite composite coating, in Mg-Zn-Zr alloy bone, fixed product comprises Mg-Zn-Zr alloy hone lamella, Mg-Zn-Zr alloy screw and Mg-Zn-Zr alloy sheet.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104623739A (en) * | 2015-02-28 | 2015-05-20 | 天津理工大学 | Coated magnesium alloy bone nails, bone plates and cancellous bone screws and preparation method thereof |
| CN105457099A (en) * | 2015-12-16 | 2016-04-06 | 天津大学 | Two-layer crystal whisker-shaped fluorine-doped hydroxyapatite coating on magnesium alloy and microwave preparation method thereof |
| CN107385419A (en) * | 2017-06-28 | 2017-11-24 | 河南工业大学 | Medical magnesium alloy surface is corrosion-resistant and the coating of hydrophilicity and preparation method thereof for a kind of raising |
| CN107858675A (en) * | 2017-11-08 | 2018-03-30 | 吉林大学 | A kind of preparation technology of magnesium alloy surface chemical conversion coating |
| CN108166036A (en) * | 2018-01-12 | 2018-06-15 | 郑州大学 | A kind of new method that fluorine-containing nano hydroxyapatite coating is prepared on biological medical magnesium alloy surface |
| CN109267054A (en) * | 2018-08-22 | 2019-01-25 | 泰山医学院 | The method for improving corrosion resistance of magnesium alloy using ultrasonic fluorinated coating method |
| CN115181879A (en) * | 2019-01-30 | 2022-10-14 | 四川镁合医疗器械有限责任公司 | Degradable magnesium alloy in-situ composite anastomosis nail and preparation method thereof |
| CN115677368A (en) * | 2022-11-11 | 2023-02-03 | 广东欧文莱陶瓷有限公司 | Method for preparing high-strength ceramic tile by taking recycled waste as raw material |
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104623739A (en) * | 2015-02-28 | 2015-05-20 | 天津理工大学 | Coated magnesium alloy bone nails, bone plates and cancellous bone screws and preparation method thereof |
| CN105457099A (en) * | 2015-12-16 | 2016-04-06 | 天津大学 | Two-layer crystal whisker-shaped fluorine-doped hydroxyapatite coating on magnesium alloy and microwave preparation method thereof |
| CN105457099B (en) * | 2015-12-16 | 2018-12-14 | 天津大学 | The double-deck crystal whisker-shaped Fluorin doped hydroxyapatite coating layer and its microwave preparation on magnesium alloy |
| CN107385419A (en) * | 2017-06-28 | 2017-11-24 | 河南工业大学 | Medical magnesium alloy surface is corrosion-resistant and the coating of hydrophilicity and preparation method thereof for a kind of raising |
| CN107385419B (en) * | 2017-06-28 | 2019-02-15 | 河南工业大学 | A kind of raising medical magnesium alloy surface is corrosion-resistant and the coating of hydrophilicity and preparation method thereof |
| CN107858675A (en) * | 2017-11-08 | 2018-03-30 | 吉林大学 | A kind of preparation technology of magnesium alloy surface chemical conversion coating |
| CN108166036A (en) * | 2018-01-12 | 2018-06-15 | 郑州大学 | A kind of new method that fluorine-containing nano hydroxyapatite coating is prepared on biological medical magnesium alloy surface |
| CN109267054A (en) * | 2018-08-22 | 2019-01-25 | 泰山医学院 | The method for improving corrosion resistance of magnesium alloy using ultrasonic fluorinated coating method |
| CN109267054B (en) * | 2018-08-22 | 2020-12-01 | 山东第一医科大学(山东省医学科学院) | Method for improving corrosion resistance of magnesium alloy by using ultrasonic fluorination coating method |
| CN115181879A (en) * | 2019-01-30 | 2022-10-14 | 四川镁合医疗器械有限责任公司 | Degradable magnesium alloy in-situ composite anastomosis nail and preparation method thereof |
| CN115677368A (en) * | 2022-11-11 | 2023-02-03 | 广东欧文莱陶瓷有限公司 | Method for preparing high-strength ceramic tile by taking recycled waste as raw material |
| CN115677368B (en) * | 2022-11-11 | 2023-04-25 | 广东欧文莱陶瓷有限公司 | Method for preparing high-strength ceramic tile by taking recycled waste as raw material |
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Application publication date: 20140115 |