CN104789957A - Microwave preparation method of flower-shaped hydroxyapatite coating layer on surface of magnesium alloy - Google Patents
Microwave preparation method of flower-shaped hydroxyapatite coating layer on surface of magnesium alloy Download PDFInfo
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Abstract
The invention relates to a microwave preparation method of a flower-shaped hydroxyapatite coating layer on the surface of magnesium alloy. The method comprises the following steps: immersing a pretreated magnesium alloy sample in a conversion coating solution, placing the conversion coating solution in a microwave chemical reactor, heating the conversion coating solution to boiling, and maintaining boiling for 2-10min; and immediately taking out the coating coated magnesium alloy sample, rinsing by using deionized water, and drying. The hydroxyapatite coating layer is a flower-shaped structure formed through clustering of hydroxyapatite nano-rods, and the length and the diameter of the nano-rods are 300-900nm and 30-90nm respectively. The thickness of the coating layer is 2-10[mu]m. The hydroxyapatite coating layer with a nanometer structure improves the bioactivity of the magnesium alloy, and also improves the corrosion resistance of the magnesium in a simulated body fluid. The preparation method of the coating layer has the advantages of simplicity, economy, environmental protection and great commercial popularization values.
Description
Technical field
The present invention relates to the microwave preparation of the flower-shaped hydroxyapatite coating layer of a kind of Mg alloy surface, belong to degradable magnesium alloy implant surface technical field of modification.
Background technology
Magnesium alloy has good biocompatibility, density and body bone tissue close, compare with materials such as cobalt-chromium alloys with the titanium alloy of wide clinical application, stainless steel, the Young's modulus (41 ~ 45GPa) of magnesium alloy more mates with osseous tissue (10 ~ 30GPa), be conducive to " stress shielding " effect reducing implant and body bone tissue interface, promote bone growth.And magnesium alloy can be completely degraded absorption in vivo, second operation is not needed to take out as implant, be considered to most and wish that becoming orthopaedics novel degradable absorbs metal implant material, can be widely used in the aspects such as bone internal fixtion, osseous tissue engineering stephanoporate support and oral cavity implantation.But, magnesium alloy is organizing degradation rate in body fluid too fast, mechanical property exhaustion run is only 6 ~ 8 weeks, and clinical bone healing time generally needs about 12 weeks, and the high magnesium ion in local that the too fast degraded of magnesium alloy causes has a strong impact on growth and the healing of wounded tissue.Just current, too fast under physiological environment of magnesium alloy is degraded into the major obstacle limiting its clinical application.Carry out hydroxyapatite coating layer surface modification to magnesium alloy to be considered to delay magnesium alloy fast degradation, one of effective way improving its biocompatibility.
Hydroxyapatite is the main inorganic composition of nature bone, in sclerotin, account for 60wt.% greatly.Hydroxyapatite has good biological activity, can be formed at short notice combine closely after implant into body with the hard and soft tissue of human body.The hydroxyapatite of nanometer or submicrometer structure is conducive to osteoblastic adhesion, propagation, differentiation, secretion collagen, engulfs degraded, promotes calcification, realize the normal reconstruct process of nature bone, be a kind of hard tissue repair equivalent material of excellent property, be successfully applied to the fields such as dentistry, plastic surgery and facies maxillaris reconstruction at present.Prepare hydroxyapatite coating layer at Mg alloy surface, not only can represent the excellent mechanical property of magnesium alloy substrate, the excellent biological activity of hydroxyapatite coating layer and physical barriers effect can also be played.
Multiple method can be adopted at present to prepare hydroxyapatite coating layer at Mg alloy surface.Wherein, Guan Shaokang etc. (patent No. 200910065998.2) adopt pulse electrodeposition technique to prepare hydroxyapatite coating layer at pure magnesium or Mg alloy surface.Yao Zhong equality (application number 201310099462.9) first prepares differential arc oxidation layer at Mg alloy surface, then be placed in hydroxyapatite powder suspension by the magnesium alloy with differential arc oxidation layer, recycling hydrothermal method prepares hydroxyapatite coating layer at Mg alloy surface.Lu Wei etc. (application number 201310420659.8) adopt bionic artistic, pretreated magnesium alloy are placed in conversion coating liquid and soak 5 ~ 100h, then prepared hydroxyapatite coating layer through Overheating Treatment at Mg alloy surface.Cai Shu etc. (application number 201210381119.9) adopt sol-gel-dip czochralski process to prepare meso-porous nano hydroxyl phosphorite coating at Mg alloy surface.Above-mentioned various hydroxyapatite coating layer all can improve the corrosion resisting property of magnesium alloy substrate to some extent, but because being subject to the restriction of preparation technology, also there is certain deficiency, as: the density of the hydroxyapatite coating layer adopting impulse electrodeposition technology to prepare is not high, limited to the provide protection of magnesium alloy substrate; Sol-gel technique is adopted to be difficult to prepare the larger hydroxyapatite coating layer of thickness, undesirable to the protected effect of magnesium alloy substrate; Adopt hydro-thermal or bionics techniques to prepare the hydroxyapatite coating layer needs longer time, production efficiency is too low.
It is pointed out that traditional bionic coating technique is immersed in by metal implant in the bionical solution of supersaturation modification to keep certain hour in certain temperature, can in metallic implant surface in-situ deposition one deck CaP coating.Produce bubble because magnesium alloy is easily corroded in bionical solution and reduce bionic coating quality, so magnesium alloy substrate needs to carry out pre-treatment to improve its solidity to corrosion in bionical solution and to shorten the time that magnesium alloy substrate soaks in bionical solution as far as possible, to improving the quality of prepared bionic coating.As document Chen et al., 2011.A simple route towards a hydroxyapatite-Mg (OH)
2conversion coating for magnesium.Corrosion Science and Gray-Munro et al., report in 2008.Themechanism of deposition of calcium phosphate coatings from solution onto magnesium alloy AZ31.Journal of Biomedical Materials Research Part A, adopt traditional bionic coating technique mostly to be particle agglomeration structure at hydroxyapatite coating layer prepared by Mg alloy surface, usually not there is nanostructure.Current research is verified, there is the hydroxyapatite coating layer of nanometer or submicrometer structure, owing to having larger specific surface area, will significantly promote that scleroblast is in the adhesion of coatingsurface and growth, and then promote that implant implants rear and the quick bone bonding of host bone, improve and be implanted to power.
Summary of the invention
The object of the present invention is to provide the microwave preparation of the flower-shaped hydroxyapatite coating layer of a kind of Mg alloy surface.The method has multiple advantage, wherein, the most important thing is that the hydroxyapatite coating layer of the nanostructure prepared not only increases the biological activity of magnesium alloy, and significantly improves the solidity to corrosion of magnesium alloy in simulated body fluid.
At present, micro-wave energy, as a kind of novel heat resource form, has been applied in drying, sintering, sterilization more and more, has completed, the field such as chemical synthesis in liquid phase.Civilian microwave heating mainly contains two frequency: 915MHz or 2450MHz.The principle of microwave heating under the polarized action of alternating electromagnetic field, makes material-to-be-heated middle free charge again arrange and dipole rotates repeatedly, thus produce powerful vibration and friction, in this microprocess, alternating electromagnetism can be converted into energy in medium, medium temperature is caused to raise, its heating means do not need thermal conduction from outward appearance to inner essence, and therefore microwave heating belongs to volume heating.On the whole, compare with conventional electrically heated, microwave heating significantly can accelerate reaction process, and can optimize reaction process, obtains novel substance, newly pattern, new texture that conventional electric-heating technology cannot obtain.Therefore, this novel process of microwave radiation+biomimetic method is adopted to prepare hydroxyapatite coating layer at medical magnesium alloy surface, there is the advantages such as technique simple and fast, energy-conserving and environment-protective, and coat-thickness is controlled, to obtaining the Coated With Hydroxyapatite magnesium alloy materials with good corrosion resistance.
The present invention can be achieved through the following technical solutions for achieving the above object:
The microwave preparation of the flower-shaped hydroxyapatite coating layer of a kind of Mg alloy surface, pretreated magnesium alloy sample is soaked in conversion coating solution, conversion coating solution is positioned in microwave chemical reactor, conversion coating solution is heated to boiling, keep 2 ~ 10min; Then immediately magnesium alloy sample coated for coating is taken out, use deionized water rinse, dry.
Described Mg alloy surface pre-treatment is preferably: by Mg alloy surface polishing to 1200 ~ 2000 orders, and then ultrasonic cleaning 3 ~ 10min in acetone, deionized water, ethanol successively, dries; Again magnesium alloy to be immersed in NaOH solution in 60 ~ 90 DEG C of insulations, then to use deionized water rinse, dry.
Described conversion coating solution is preferably: with Ca (NO
3)
2, CaCl
2or Ca (CH
3cOO)
2for Ca is prepared in Ca source
2+the aqueous solution, with NH
4h
2pO
4, Na
2hPO
4or NaH
2pO
4for PO is prepared in P source
4 3-the aqueous solution; Then by PO
4 3-the aqueous solution is added dropwise to Ca
2+in the aqueous solution, finally with diluted acid, the pH value of mixing solutions is transferred to 5 ~ 6, magnetic agitation 1 ~ 2h; Wherein, Ca in mixing solutions
2+concentration be 4 ~ 6mmol/L, PO
4 3-concentration be 1 ~ 2mmol/L.
Described diluted acid is preferably the one in dust technology, dilute hydrochloric acid, acetic acid, and its concentration is 1 ~ 20mol/L.
Described magnesium alloy is preferably the one of AZ31, AZ61, AZ80 or AZ91.
It is 915MHz or 2450MHz that described microwave chemical reactor produces micro-wave frequency.
The flower-shaped hydroxyapatite coating layer of Mg alloy surface prepared by the present invention, hydroxyapatite coating layer is that hydroxyapatite nano rod cluster forms flower-like structure, and the length of nanometer rod is 300 ~ 900nm, and the diameter of nanometer rod is 30 ~ 90nm.Coat-thickness is 2 ~ 10 μm.
In sum, core of the present invention is that preparation comprises Ca
2+and PO
4 3-conversion coating solution, the pH value of conversion coating solution is 5 ~ 6.Make full use of under microwave radiation, the water molecules fast rotational in conversion coating solution, vibration, accelerate the nucleation and growth of hydroxyapatite in conversion coating solution, and promote that hydroxyapatite nucleus growth is hydroxyapatite nano rod.In addition, the pH value that conversion coating solution is suitable ensure that the coating of synthesis is the hydroxyapatite of pure phase.Further, after NaOH solution process, Mg alloy surface generates one deck Mg (OH)
2, Mg (OH)
2there is adsorption to hydroxyapatite nucleus, and facilitate growing up of hydroxyapatite crystal grain.The synergy of above-mentioned three aspects makes to be synthesized rapidly at Mg alloy surface by microwave liquid phase process to have certain thickness flower-shaped hydroxyapatite coating layer.
The flower-shaped hydroxyapatite coating layer of medical magnesium alloy surface, is characterized in that: described hydroxyapatite coating layer, forms flower-like structure by great amount of hydroxy group phosphatic rock nanometer rod cluster, and the length of nanometer rod is 300 ~ 900nm, and the diameter of nanometer rod is 30 ~ 90nm.
Compared with prior art, advantage of the present invention and positively effect are:
(1) the present invention utilizes microwave liquid phase process to prepare hydroxyapatite coating layer at Mg alloy surface, and coating forms flower-like structure by great amount of hydroxy group phosphatic rock nanometer rod cluster, and the length of nanometer rod is 300 ~ 900nm, and the diameter of nanometer rod is 30 ~ 90nm.The hydroxyapatite of nanostructure, has very large specific surface area, can promote that scleroblast adheres to and growth at coatingsurface, drastically increase the biological activity of magnesium alloy.
(2) invention significantly improves the solidity to corrosion of magnesium alloy in simulated body fluid.The thickness of hydroxyapatite coating layer is controlled by changing the microwave catalysis reaction times, coat-thickness is 2 ~ 10 μm, because the thickness of hydroxyapatite coating layer is thicker, be conducive to the physical barriers effect better playing coating, reduce the contact of magnesium alloy and electrolyte solution, improve the solidity to corrosion of magnesium alloy implant in human physiological environment.
(3) reliability of the present invention is high.For the magnesium alloy sample of any shape, size, all hydroxyapatite coating layer can be prepared on its surface.
(4) the present invention is a kind of low-temperature fabrication, and maximum heat treatment temperature is 100 DEG C (boiling points of water), can not reduce mechanics and the chemical property of magnesium alloy substrate due to higher thermal treatment temp.
(5) the present invention is simple, fast, only need 2 ~ 10min, just can prepare hydroxyapatite coating layer at Mg alloy surface, microwave liquid liquid phase method disclosed in this invention is a kind of not only economy but also environmentally friendly novel process.
The hydroxyapatite coating layer of nanostructure of the present invention not only increases the biological activity of magnesium alloy, and improves the solidity to corrosion of magnesium alloy in simulated body fluid.This preparation technology of coating is simple, economy, environmental friendliness, has larger business promotion and is worth.
Accompanying drawing explanation
The coating of Fig. 1 prepared by the embodiment of the present invention 1 and sedimental XRD figure spectrum.
The surface topography SEM photo of the hydroxyapatite coating layer of Fig. 2 prepared by the embodiment of the present invention 1.
The section S EM photo of the hydroxyapatite coating layer of Fig. 3 prepared by the embodiment of the present invention 1.
The Coated With Hydroxyapatite magnesium alloy of Fig. 4 prepared by the embodiment of the present invention 1 and the ac impedance spectroscopy of magnesium alloy nude film in simulated body fluid.
Embodiment
Below in conjunction with embodiment the present invention be further explained and illustrate, but the present invention is not constituted any limitation.The raw material used in following examples is commercially available analytical pure raw material.
Preparation method is as follows in general introduction:
1) Mg alloy surface pre-treatment: by sand papering to the 1200 ~ 2000 used for magnesium alloy order of certain size and shape, then ultrasonic cleaning 3 ~ 10min in acetone, deionized water, ethanol successively, dry.
2) magnesium alloy alkaline purification: the NaOH aqueous solution of preparation 1 ~ 3mol/L.Magnesium alloy after polishing is immersed in NaOH solution and is incubated 1h in 60 ~ 90 DEG C, then use deionized water rinse, dry.
3) preparation of conversion coating solution: with Ca (NO
3)
2, CaCl
2or Ca (CH
3cOO)
2for Ca is prepared in Ca source
2+the aqueous solution, with NH
4h
2pO
4, Na
2hPO
4or NaH
2pO
4for PO is prepared in P source
4 3-the aqueous solution.Then by PO
4 3-the aqueous solution dropwise adds Ca
2+in the aqueous solution, finally with diluted acid, the pH value of mixing solutions is transferred to 5 ~ 6, magnetic agitation 1 ~ 2h.Wherein, Ca in mixing solutions
2+concentration be 4 ~ 6mmol/L, PO
4 3-concentration be 1 ~ 2mmol/L.
4) preparation of hydroxyapatite conversion coating: the magnesium alloy sample after alkaline purification is soaked in conversion coating solution, conversion coating solution is positioned in microwave chemical reactor, with peak power output, conversion coating solution is heated to boiling, keeps 2 ~ 10min; Then immediately magnesium alloy sample coated for coating is taken out, use deionized water rinse, dry.
Embodiment 1
(1) AZ31 magnesium alloy is processed into the block of 10mm × 10mm × 2mm, uses 240 successively
#, 1200
#, 2000
#siC sand papering, then ultrasonic cleaning 10min in acetone, deionized water, ethanol successively, hot-air seasoning.
(2) the NaOH deionized water solution 150mL of 2mol/L is prepared.Magnesium alloy after polishing is immersed in NaOH solution and is incubated 1h in 60 DEG C, then magnesium alloy sample is used deionized water rinse, dry.
(3) with Ca (NO
3)
2for Ca is prepared in Ca source
2+the aqueous solution, with Na
2hPO
4for PO is prepared in P source
4 3-the aqueous solution.Then by PO
4 3-the aqueous solution dropwise adds Ca
2+in the aqueous solution, finally the pH value of mixing solutions is transferred to 6, magnetic agitation 1h with the dust technology of 20M.Wherein, Ca in mixing solutions
2+concentration be 6mmol/L, PO
4 3-concentration be 2mmol/L.Take 100mL mixing solutions as conversion coating solution.
(4) magnesium alloy sample after alkaline purification is soaked in conversion coating solution, conversion coating solution is positioned in microwave chemical reactor, output frequency is 2450MHz microwave, with peak power output, conversion coating solution is heated to boiling, keeps 10min.Then immediately magnesium alloy sample coated for coating is taken out, use deionized water rinse, dry.
As shown in Figure 1, the coating of synthesis is the hydroxyapatite of pure phase for prepared conversion coating and sedimental XRD figure spectrum.As shown in Figure 2, coating forms flower-like structure by great amount of hydroxy group phosphatic rock nanometer rod cluster to the surface topography of coating, and the length of nanometer rod is 600 ~ 900nm, and the diameter of nanometer rod is 60 ~ 90nm.As shown in Figure 3, the thickness of hydroxyapatite coating layer is ~ 10 μm to the Cross Section Morphology of coating.As shown in Figure 4, the alternating-current impedance of magnesium alloy nude film is ~ 1350ohmcm for the coated magnesium alloy sample of hydroxyapatite coating layer and the ac impedance spectroscopy of magnesium alloy nude film in simulated body fluid
2, the alternating-current impedance of Coated With Hydroxyapatite magnesium alloy is ~ 43000ohmcm
2.
Embodiment 2
(1) AZ91 magnesium alloy is processed into the block of 10mm × 10mm × 2mm, uses 240 successively
#, 1200
#siC sand papering, then ultrasonic cleaning 6min in acetone, deionized water, ethanol successively, hot-air seasoning.
(2) the NaOH deionized water solution 150mL of 3mol/L is prepared.Magnesium alloy after polishing is immersed in NaOH solution and is incubated 1h in 70 DEG C, then magnesium alloy sample is used deionized water rinse, dry.
(3) with CaCl
2for Ca is prepared in Ca source
2+the aqueous solution, with NaH
2pO
4for PO is prepared in P source
4 3-the aqueous solution.Then by PO
4 3-the aqueous solution dropwise adds Ca
2+in the aqueous solution, finally the pH value of mixing solutions is transferred to 5, magnetic agitation 1.5h with the dilute hydrochloric acid of 15M.Wherein, Ca in mixing solutions
2+concentration be 4mmol/L, PO
4 3-concentration be 2mmol/L.Take 100mL mixing solutions as conversion coating solution.
(4) magnesium alloy sample after alkaline purification is soaked in conversion coating solution, conversion coating solution is positioned in microwave chemical reactor, output frequency is 2450MHz microwave, with peak power output, conversion coating solution is heated to boiling, keeps 7min.Then immediately magnesium alloy sample coated for coating is taken out, use deionized water rinse, dry.
Prepared hydroxyapatite coating layer forms flower-like structure by great amount of hydroxy group phosphatic rock nanometer rod cluster, and the length of nanometer rod is 500 ~ 800nm, and the diameter of nanometer rod is 50 ~ 80nm.The thickness of hydroxyapatite coating layer is ~ 6 μm.The alternating-current impedance of Coated With Hydroxyapatite magnesium alloy is ~ 30000ohmcm
2.
Embodiment 3
(1) using AZ61 as magnesium alloy substrate, use 240 successively
#, 1200
#, 1500
#siC sand papering, then ultrasonic cleaning 8min in acetone, deionized water, ethanol successively, hot-air seasoning.
(2) the NaOH deionized water solution 150mL of 1mol/L is prepared.Magnesium alloy after polishing is immersed in NaOH solution and is incubated 1h in 80 DEG C, then magnesium alloy sample is used deionized water rinse, dry.
(3) with Ca (CH
3cOO)
2for Ca is prepared in Ca source
2+the aqueous solution, with NaH
2pO
4for PO is prepared in P source
4 3-the aqueous solution.Then by PO
4 3-the aqueous solution dropwise adds Ca
2+in the aqueous solution, finally the pH value of mixing solutions is transferred to 5.5, magnetic agitation 2h with the acetic acid of 8M.Wherein, Ca in mixing solutions
2+concentration be 5mmol/L, PO
4 3-concentration be 1.5mmol/L.Take 100mL mixing solutions as conversion coating solution.
(4) be soaked in conversion coating solution by the magnesium alloy sample after alkaline purification, be positioned over by conversion coating solution in microwave chemical reactor, output frequency is 915MHz microwave, with peak power output, conversion coating solution is heated to boiling, keeps 5min.Then immediately magnesium alloy sample coated for coating is taken out, use deionized water rinse, dry.
Prepared hydroxyapatite coating layer forms flower-like structure by great amount of hydroxy group phosphatic rock nanometer rod cluster, and the length of nanometer rod is 300 ~ 700nm, and the diameter of nanometer rod is 30 ~ 70nm.The thickness of hydroxyapatite coating layer is ~ 4 μm.The alternating-current impedance of Coated With Hydroxyapatite magnesium alloy is ~ 18000ohmcm
2.
Embodiment 4
(1) AZ80 magnesium alloy is processed into the block of 10mm × 10mm × 2mm, uses 240 successively
#, 1200
#siC sand papering, then ultrasonic cleaning 3min in acetone, deionized water, ethanol successively, hot-air seasoning.
(2) the NaOH deionized water solution 150mL of 1.5mol/L is prepared.Magnesium alloy after polishing is immersed in NaOH solution and is incubated 1h in 90 DEG C, then magnesium alloy sample is used deionized water rinse, dry.
(3) with Ca (CH
3cOO)
2for Ca is prepared in Ca source
2+the aqueous solution, with NH
4h
2pO
4for PO is prepared in P source
4 3-the aqueous solution.Then by PO
4 3-the aqueous solution dropwise adds Ca
2+in the aqueous solution, finally the pH value of mixing solutions is transferred to 5.5, magnetic agitation 2h with the dust technology of 1M.Wherein, Ca in mixing solutions
2+concentration be 5mmol/L, PO
4 3-concentration be 2mmol/L.Take 100mL mixing solutions as conversion coating solution.
(4) be soaked in conversion coating solution by the magnesium alloy sample after alkaline purification, be positioned over by conversion coating solution in microwave chemical reactor, output frequency is 915MHz microwave, with peak power output, conversion coating solution is heated to boiling, keeps 2min.Then immediately magnesium alloy sample coated for coating is taken out, use deionized water rinse, dry.
Prepared hydroxyapatite coating layer forms flower-like structure by great amount of hydroxy group phosphatic rock nanometer rod cluster, and the length of nanometer rod is 200 ~ 500nm, and the diameter of nanometer rod is 20 ~ 70nm.The thickness of hydroxyapatite coating layer is ~ 2 μm.The alternating-current impedance of Coated With Hydroxyapatite magnesium alloy is ~ 12500ohmcm
2.
Claims (6)
1. the microwave preparation of the flower-shaped hydroxyapatite coating layer of Mg alloy surface, it is characterized in that: pretreated magnesium alloy sample is soaked in conversion coating solution, conversion coating solution is positioned in microwave chemical reactor, conversion coating solution is heated to boiling, keep 2 ~ 10min; Then immediately magnesium alloy sample coated for coating is taken out, use deionized water rinse, dry.
2. the method for claim 1, is characterized in that described Mg alloy surface pre-treatment is: by Mg alloy surface polishing to 1200 ~ 2000 orders, and then ultrasonic cleaning 3 ~ 10min in acetone, deionized water, ethanol successively, dries; Again magnesium alloy to be immersed in NaOH solution in 60 ~ 90 DEG C of insulations, then to use deionized water rinse, dry.
3. the method for claim 1, is characterized in that described conversion coating solution is: with Ca (NO
3)
2, CaCl
2or Ca (CH
3cOO)
2for Ca is prepared in Ca source
2+the aqueous solution, with NH
4h
2pO
4, Na
2hPO
4or NaH
2pO
4for PO is prepared in P source
4 3-the aqueous solution; Then by PO
4 3-the aqueous solution is added dropwise to Ca
2+in the aqueous solution, finally with diluted acid, the pH value of mixing solutions is transferred to 5 ~ 6, magnetic agitation 1 ~ 2h; Wherein, Ca in mixing solutions
2+concentration be 4 ~ 6mmol/L, PO
4 3-concentration be 1 ~ 2mmol/L.
4. method as claimed in claim 3, it is characterized in that described diluted acid is the one in dust technology, dilute hydrochloric acid, acetic acid, its concentration is 1 ~ 20mol/L.
5. the method for claim 1, is characterized in that described magnesium alloy is the one of AZ31, AZ61, AZ80 or AZ91.
6. the method for claim 1, it is characterized in that described microwave chemical reactor produces micro-wave frequency is 915MHz or 2450MHz.
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| 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 |
| CN107227453A (en) * | 2017-03-27 | 2017-10-03 | 山东科技大学 | The preparation of AZ31 Mg alloy surface Zn MMT coatings and assay method |
| CN108531893A (en) * | 2018-04-04 | 2018-09-14 | 天津大学 | A kind of microwave preparation of Mg alloy surface nano whiskers calcium monohydrogen phosphate coating |
| WO2018187762A1 (en) * | 2017-04-07 | 2018-10-11 | The Board Of Trustees Of The University Of Illinois | Nanostructured Magnesium Materials, Methods and Devices |
| CN109137009A (en) * | 2018-09-28 | 2019-01-04 | 北京工业大学 | A kind of method that pulse electrodeposition prepares porous magnesium hydroxide |
| CN109646717A (en) * | 2018-12-28 | 2019-04-19 | 北京科技大学天津学院 | Mg alloy surface nano hydroxyapatite coating and preparation method based on ultrasound |
| IT201900023586A1 (en) | 2019-12-11 | 2021-06-11 | Univ Degli Studi Di Palermo | METHOD FOR SURFACE TREATMENT OF MAGNESIUM ALLOYS FOR BIOMEDICAL APPLICATIONS |
| CN114703471A (en) * | 2022-03-10 | 2022-07-05 | 重庆大学 | Preparation method of magnesium alloy surface conversion film based on ultrasonic cavitation assistance |
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| 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 |
| CN107227453A (en) * | 2017-03-27 | 2017-10-03 | 山东科技大学 | The preparation of AZ31 Mg alloy surface Zn MMT coatings and assay method |
| WO2018187762A1 (en) * | 2017-04-07 | 2018-10-11 | The Board Of Trustees Of The University Of Illinois | Nanostructured Magnesium Materials, Methods and Devices |
| CN108531893A (en) * | 2018-04-04 | 2018-09-14 | 天津大学 | A kind of microwave preparation of Mg alloy surface nano whiskers calcium monohydrogen phosphate coating |
| CN109137009A (en) * | 2018-09-28 | 2019-01-04 | 北京工业大学 | A kind of method that pulse electrodeposition prepares porous magnesium hydroxide |
| CN109646717A (en) * | 2018-12-28 | 2019-04-19 | 北京科技大学天津学院 | Mg alloy surface nano hydroxyapatite coating and preparation method based on ultrasound |
| CN109646717B (en) * | 2018-12-28 | 2021-10-15 | 北京科技大学天津学院 | Magnesium alloy surface nano hydroxyapatite coating based on ultrasound and preparation method thereof |
| IT201900023586A1 (en) | 2019-12-11 | 2021-06-11 | Univ Degli Studi Di Palermo | METHOD FOR SURFACE TREATMENT OF MAGNESIUM ALLOYS FOR BIOMEDICAL APPLICATIONS |
| WO2021115872A1 (en) | 2019-12-11 | 2021-06-17 | Universita' Degli Studi Di Palermo | Process for the surface treatment of magnesium alloys for biomedical applications |
| CN114703471A (en) * | 2022-03-10 | 2022-07-05 | 重庆大学 | Preparation method of magnesium alloy surface conversion film based on ultrasonic cavitation assistance |
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