CN104789957B - A kind of microwave preparation of the flower-shaped hydroxyapatite coating layer of Mg alloy surface - Google Patents
A kind of microwave preparation of the flower-shaped hydroxyapatite coating layer of Mg alloy surface Download PDFInfo
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Abstract
The present invention relates to a kind of microwave preparation of the flower-shaped hydroxyapatite coating layer 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, 2~10min is kept；The magnesium alloy sample that coating is coated immediately after takes out, and uses deionized water rinse, dries.Hydroxyapatite coating layer is that hydroxyapatite nano rod cluster forms flower-like structure, and the length of nanometer rods is 300~900nm, a diameter of 30~90nm of nanometer rods.Coating layer thickness is 2~10 μm.The hydroxyapatite coating layer of nanostructured not only increases the bioactivity of magnesium alloy, and improves corrosion resistance of the magnesium alloy in simulated body fluid.This preparation technology of coating is simple, economical, environment-friendly, is worth with larger business promotion.
Description
Technical field
The present invention relates to a kind of microwave preparation of the flower-shaped hydroxyapatite coating layer of Mg alloy surface, belong to degradable magnesium
Alloy implants process for modifying surface field.
Background technology
Magnesium alloy has good biocompatibility, and density is approached with body bone tissue, is closed with the titanium of wide clinical application
The material such as gold, stainless steel and cobalt-chromium alloy is compared, modulus of elasticity (41~45GPa) and the bone tissue (10~30GPa) of magnesium alloy
More match, advantageously reduce " stress shielding " effect of implant and body bone tissue interface, promote bone growth.And magnesium
Alloy can be completely degraded absorption in vivo, not need second operation to take out as implant, it is considered to be most to wish to turn into
Orthopaedics novel degradable absorbs metal implant material, can be widely used for fixed, osseous tissue engineering stephanoporate support and oral cavity in bone and plants
In terms of entering.However, magnesium alloy degradation rate in tissue body fluid is too fast, mechanical property exhaustion run is only 6~8 weeks, and is faced
Bed bone healing time is generally required 12 weeks or so, and local high magnesium ion has a strong impact on injured group caused by the too fast degraded of magnesium alloy
The growth and healing knitted.For at present, too fast under physiological environment of magnesium alloy is degraded into the master for limiting its clinical practice
Want obstacle.It is considered as to delay magnesium alloy fast degradation that magnesium alloy, which is carried out hydroxyapatite coating layer surface to be modified, improves its life
One of effective way of thing compatibility.
Hydroxyapatite is the main inorganic composition of nature bone, and 60wt.% is constituted about in sclerotin.Hydroxyapatite has
Hard and soft tissue formation that can be in a short time with human body after good bioactivity, implantation human body is combined closely.Nanometer or sub-micro
The hydroxyapatite of rice structure is conducive to adhesion, propagation, differentiation, secretion collagen, phagocytosis degraded, the promotion calcification of Gegenbaur's cell,
The normal process of reconstruction of nature bone is realized, is a kind of hard tissue repair alternative materials of function admirable, has been applied successfully at present
In fields such as dentistry, plastic surgery and facies maxillaris reconstructions.Hydroxyapatite coating layer is prepared in Mg alloy surface, can not only be showed
The excellent mechanical property of magnesium alloy substrate, moreover it is possible to play the excellent bioactivity of hydroxyapatite coating layer and acted on physical barriers.
Hydroxyapatite coating layer can be prepared in Mg alloy surface using a variety of methods at present.Wherein, (the patents such as health that continue are closed
Number 200910065998.2) hydroxyapatite coating layer is prepared in pure magnesium or Mg alloy surface using pulse electrodeposition technique.Yao
Loyal equality (application number 201310099462.9) prepares differential arc oxidation layer in Mg alloy surface first, then will carry differential arc oxidation
The magnesium alloy of layer is placed in hydroxyapatite powder suspension, recycles hydro-thermal method to prepare hydroxyapatite in Mg alloy surface
Coating.Lu Wei etc. (application number 201310420659.8) uses bionic artistic, and the magnesium alloy of pretreatment is placed in into conversion coating liquid
5~100h of middle immersion, is then prepared for hydroxyapatite coating layer through Overheating Treatment in Mg alloy surface.(the application numbers such as Cai Shu
201210381119.9) use sol-gel-dip czochralski process to be prepared for meso-porous nano hydroxyl phosphorite painting in Mg alloy surface
Layer.Above-mentioned various hydroxyapatite coating layers can improve the corrosion resisting property of magnesium alloy substrate to some extent, but because being prepared
The limitation of technique, also in the presence of certain deficiency, such as：The consistency of the hydroxyapatite coating layer prepared using impulse electrodeposition technology
Not high, the protective effect to magnesium alloy substrate is limited；It is difficult to prepare the larger hydroxyapatite of thickness using sol-gel technique
Coating, it is undesirable to the protecting effect of magnesium alloy substrate；Using hydro-thermal or bionics techniques prepare hydroxyapatite coating layer need compared with
The long time, production efficiency is too low.
It is pointed out that traditional bionic coating technique is that metal implant is immersed in the modified bionical solution of supersaturation
Kept for certain time in certain temperature, you can in one layer of CaP coating of metallic implant surface in-situ deposition.Because magnesium alloy is imitative
Easily it is corroded in raw solution and produces bubble reduction bionic coating quality, so magnesium alloy substrate needs to be pre-processed to carry
Its high corrosion resistance in bionical solution and the time that shortening magnesium alloy substrate soaks in bionical solution as far as possible, to improve
The quality of prepared bionic coating.Such 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.,2008.The mechanism of deposition of calcium phosphate
coatings from solution onto magnesium alloy AZ31.Journal of Biomedical
Reported in Materials Research Part A, the hydroxyl phosphorus prepared using traditional bionic coating technique in Mg alloy surface
Lime stone coating is generally particle agglomeration structure, generally without nanostructured.Research has confirmed at present, with nanometer or sub-micron
The hydroxyapatite coating layer of structure, due to larger specific surface area, Gegenbaur's cell will be remarkably promoted in the viscous of coating surface
Attached to be bonded with growing, and then after promotion implant implantation with the quick bone of host bone, raising is implanted to power.
The content of the invention
It is an object of the invention to provide a kind of microwave preparation of the flower-shaped hydroxyapatite coating layer of Mg alloy surface.Should
Method has a variety of advantages, wherein, it is most important that the hydroxyapatite coating layer of the nanostructured of preparation not only increases magnesium conjunction
The bioactivity of gold, and significantly improve corrosion resistance of the magnesium alloy in simulated body fluid.
At present, microwave energy is as a kind of new heat resource form, be increasingly used in dry, sintering, sterilization,
The fields such as fixing, chemical synthesis in liquid phase.Civilian microwave heating mainly has two frequencies：915MHz or 2450MHz.Microwave heating
Principle is material-to-be-heated middle free charge rearrangement and dipole is rotated repeatedly under the polarization of alternating electromagnetic field,
So as to produce powerful vibration and friction, alternating electromagnetism can be converted into the interior energy of medium in this microprocess, cause medium
Temperature is raised, the heat transfer that its heating means need not be from outward appearance to inner essence, therefore microwave heating belongs to volume heating.It is overall next
Say, compared with conventional electrical heating, microwave heating can dramatically speed up reaction process, and can optimize course of reaction, obtain routine
Novel substance that electric-heating technology can not be obtained, new pattern, new construction.Therefore, existed using this new technology of microwave radiation+biomimetic method
Medical magnesium alloy surface prepares hydroxyapatite coating layer, has the advantages that technique simple and fast, energy-conserving and environment-protective, and coating layer thickness can
Control, is desirably to obtain the Coated With Hydroxyapatite magnesium alloy materials with good corrosion resistance.
The present invention can be achieved through the following technical solutions to achieve the above object：
A kind of microwave preparation of the flower-shaped hydroxyapatite coating layer of Mg alloy surface, by pretreated magnesium alloy sample
It is soaked in conversion coating solution, conversion coating solution is positioned in microwave chemical reactor, conversion coating solution is heated
To seething with excitement, 2~10min is kept；The magnesium alloy sample that coating is coated immediately after takes out, and uses deionized water rinse, dries.
Described Mg alloy surface is pre-processed：Mg alloy surface is polishing to 1200~2000 mesh, then successively
It is cleaned by ultrasonic 3~10min, drying in acetone, deionized water, ethanol；Magnesium alloy is immersed in NaOH solution in 60 again~
90 DEG C of insulations, then use deionized water rinse, dry.
Described conversion coating solution is preferably：With Ca (NO3)2、CaCl2Or Ca (CH3COO)2Ca is prepared for Ca sources2+Water
Solution, with NH4H2PO4、Na2HPO4Or NaH2PO4PO is prepared for P sources4 3-The aqueous solution；Then by PO4 3-The aqueous solution is added dropwise to Ca2+Water
In solution, the pH value of mixed solution is finally transferred to 5~6,1~2h of magnetic agitation with diluted acid；Wherein, Ca in mixed solution2+'s
Concentration is 4~6mmol/L, PO4 3-Concentration be 1~2mmol/L.
Described diluted acid is preferably one kind in dust technology, watery hydrochloric acid, acetic acid, and its concentration is 1~20mol/L.
Described magnesium alloy is preferably AZ31, AZ61, AZ80 or AZ91 one kind.
The frequency that described microwave chemical reactor produces microwave is 915MHz or 2450MHz.
The flower-shaped hydroxyapatite coating layer of Mg alloy surface prepared by the present invention, hydroxyapatite coating layer is received for hydroxyapatite
Rice rod cluster forms flower-like structure, and the length of nanometer rods is 300~900nm, a diameter of 30~90nm of nanometer rods.Coating layer thickness
For 2~10 μm.
In summary, core of the invention, which is to prepare, includes Ca2+And PO4 3-Conversion coating solution, conversion coating solution
PH value be 5~6.Make full use of under microwave radiation, the hydrone in conversion coating solution quickly rotates, vibrated, and accelerates
Nucleation of the hydroxyapatite in conversion coating solution and grow up, and promote hydroxyapatite nucleus growth to be received for hydroxyapatite
Rice rod.In addition, the suitable pH value of conversion coating solution ensure that the coating of synthesis is the hydroxyapatite of pure phase.Further, NaOH
After solution processing, Mg alloy surface generates one layer of Mg (OH)2,Mg(OH)2There is suction-operated to hydroxyapatite nucleus, and promote
Growing up for hydroxyapatite crystal grain is entered.The synergy of above-mentioned three aspect causes fast in Mg alloy surface by microwave liquid phase process
Speed synthesis has certain thickness flower-shaped hydroxyapatite coating layer.
The flower-shaped hydroxyapatite coating layer of medical magnesium alloy surface, it is characterised in that：Described hydroxyapatite coating layer, by big
Measure hydroxyapatite nano rod cluster and form flower-like structure, the length of nanometer rods is 300~900nm, a diameter of the 30 of nanometer rods
~90nm.
Compared with prior art, advantages and positive effects of the present invention are：
(1) present invention is prepared for hydroxyapatite coating layer using microwave liquid phase process in Mg alloy surface, and coating is by a large amount of hydroxyls
Base apatite nanometer rods cluster forms flower-like structure, and the length of nanometer rods is 300~900nm, nanometer rods a diameter of 30~
90nm.The hydroxyapatite of nanostructured, with very big specific surface area, can promote Gegenbaur's cell coating surface adhesion and
Growth, drastically increases the bioactivity of magnesium alloy.
(2) corrosion resistance invention significantly improves magnesium alloy in simulated body fluid.When being reacted by changing microwave catalysis
Between control hydroxyapatite coating layer thickness, coating layer thickness be 2~10 μm, because the thickness of hydroxyapatite coating layer is thicker, have
Beneficial to the more preferable physical barriers effect for playing coating, contact of the magnesium alloy with electrolyte solution is reduced, magnesium alloy plant is improved
Enter corrosion resistance of the thing in human physiological environment.
(3) reliability of the present invention is high.For the magnesium alloy sample of any shape, size, hydroxyl can be prepared on its surface
Base apatite coating.
(4) present invention is a kind of low-temperature fabrication, and maximum heat treatment temperature is 100 DEG C (boiling point of water), will not be due to
Higher thermal treatment temperature and reduce the mechanics and chemical property of magnesium alloy substrate.
(5) present invention is simple, quick, it is only necessary to 2~10min, it is possible to prepare hydroxyapatite coating layer in Mg alloy surface,
Microwave liquid liquid phase method disclosed in this invention is a kind of not only economic but also environmentally friendly new technology.
The hydroxyapatite coating layer of the nanostructured of the present invention not only increases the bioactivity of magnesium alloy, and improves
Corrosion resistance of the magnesium alloy in simulated body fluid.This preparation technology of coating is simple, economical, environment-friendly, is pushed away with larger business
Wide value.
Brief description of the drawings
The XRD spectrum of coatings and deposit of the Fig. 1 prepared by the embodiment of the present invention 1.
Fig. 2 is the surface topography SEM photograph of the hydroxyapatite coating layer prepared by the embodiment of the present invention 1.
Fig. 3 is the section SEM photograph of the hydroxyapatite coating layer prepared by the embodiment of the present invention 1.
Coated With Hydroxyapatite magnesium alloys and magnesium alloy nude film of the Fig. 4 prepared by the embodiment of the present invention 1 are in simulated body fluid
In ac impedance spectroscopy.
Embodiment
The present invention is further explained and illustrated with reference to embodiment, but the present invention is not limited in any way.With
Raw material used in lower embodiment is commercially available analysis pure raw material.
Summarize preparation method as follows：
1) Mg alloy surface is pre-processed：The sand paper used for magnesium alloy of certain size and shape is polishing to 1200~2000 mesh,
Then it is cleaned by ultrasonic 3~10min, drying in acetone, deionized water, ethanol successively.
2) magnesium alloy alkali process：Prepare the 1~3mol/L NaOH aqueous solution.Magnesium alloy after polishing is immersed in NaOH solution
In in 60~90 DEG C be incubated 1h, then use deionized water rinse, dry.
3) preparation of conversion coating solution：With Ca (NO3)2、CaCl2Or Ca (CH3COO)2Ca is prepared for Ca sources2+The aqueous solution,
With NH4H2PO4、Na2HPO4Or NaH2PO4PO is prepared for P sources4 3-The aqueous solution.Then by PO4 3-Ca is added dropwise in the aqueous solution2+It is water-soluble
In liquid, the pH value of mixed solution is finally transferred to 5~6,1~2h of magnetic agitation with diluted acid.Wherein, Ca in mixed solution2+It is dense
Spend for 4~6mmol/L, PO4 3-Concentration be 1~2mmol/L.
4) preparation of hydroxyapatite conversion coating：Magnesium alloy sample after alkali process is soaked in conversion coating solution
In, conversion coating solution is positioned in microwave chemical reactor, conversion coating solution is heated to by boiling with peak power output
Rise, keep 2~10min；The magnesium alloy sample that coating is coated immediately after takes out, and uses deionized water rinse, dries.
Embodiment 1
(1) AZ31 magnesium alloys are processed into 10mm × 10mm × 2mm block, successively with 240#、1200#、2000#SiC
Sand paper is polished, and is then cleaned by ultrasonic 10min, hot-air seasoning in acetone, deionized water, ethanol successively.
(2) 2mol/L NaOH deionized water solutions 150mL is prepared.By magnesium alloy after polishing be immersed in NaOH solution in
60 DEG C of insulation 1h, then by magnesium alloy sample deionized water rinse, drying.
(3) with Ca (NO3)2Ca is prepared for Ca sources2+The aqueous solution, with Na2HPO4PO is prepared for P sources4 3-The aqueous solution.Then will
PO4 3-Ca is added dropwise in the aqueous solution2+In the aqueous solution, the pH value of mixed solution is finally transferred to 6, magnetic agitation with 20M dust technology
1h.Wherein, Ca in mixed solution2+Concentration be 6mmol/L, PO4 3-Concentration be 2mmol/L.Weigh 100mL mixed solutions work
For conversion coating solution.
(4) magnesium alloy sample after alkali process is soaked in conversion coating solution, conversion coating solution be positioned over micro-
In ripple chemical reactor, output frequency is 2450MHz microwaves, and conversion coating solution is heated into boiling with peak power output,
Keep 10min.The magnesium alloy sample that coating is coated immediately after takes out, and uses deionized water rinse, dries.
Prepared conversion coating and the XRD spectrum of deposit are as shown in figure 1, the coating of synthesis is the hydroxy-apatite of pure phase
Stone.The surface topography of coating is as shown in Fig. 2 coating forms flower-like structure, nanometer rods by great amount of hydroxy group apatite nanometer rods cluster
Length be 600~900nm, a diameter of 60~90nm of nanometer rods.The Cross Section Morphology of coating is as shown in figure 3, hydroxyapatite
The thickness of coating is~10 μm.Hydroxyapatite coating layer cladding magnesium alloy sample exchanging in simulated body fluid with magnesium alloy nude film
Impedance spectrum is as shown in figure 4, the AC impedance of magnesium alloy nude film is~1350ohmcm2, the friendship of Coated With Hydroxyapatite magnesium alloy
Flow impedance is~43000ohmcm2。
Embodiment 2
(1) AZ91 magnesium alloys are processed into 10mm × 10mm × 2mm block, successively with 240#、1200#SiC sand paper beat
Mill, is then cleaned by ultrasonic 6min, hot-air seasoning in acetone, deionized water, ethanol successively.
(2) 3mol/L NaOH deionized water solutions 150mL is prepared.Magnesium alloy after polishing is immersed in NaOH solution
1h is incubated in 70 DEG C, then by magnesium alloy sample deionized water rinse, drying.
(3) with CaCl2Ca is prepared for Ca sources2+The aqueous solution, with NaH2PO4PO is prepared for P sources4 3-The aqueous solution.Then by PO4 3-
Ca is added dropwise in the aqueous solution2+In the aqueous solution, the pH value of mixed solution is finally transferred to 5, magnetic agitation with 15M watery hydrochloric acid
1.5h.Wherein, Ca in mixed solution2+Concentration be 4mmol/L, PO4 3-Concentration be 2mmol/L.Weigh 100mL mixed solutions
It is used as conversion coating solution.
(4) magnesium alloy sample after alkali process is soaked in conversion coating solution, conversion coating solution be positioned over micro-
In ripple chemical reactor, output frequency is 2450MHz microwaves, and conversion coating solution is heated into boiling with peak power output,
Keep 7min.The magnesium alloy sample that coating is coated immediately after takes out, and uses deionized water rinse, dries.
Prepared hydroxyapatite coating layer forms flower-like structure by great amount of hydroxy group apatite nanometer rods cluster, nanometer rods
Length is 500~800nm, a diameter of 50~80nm of nanometer rods.The thickness of hydroxyapatite coating layer is~6 μm.Hydroxy-apatite
The AC impedance of stone cladding magnesium alloy is~30000ohmcm2。
Embodiment 3
(1) using AZ61 as magnesium alloy substrate, successively with 240#、1200#、1500#SiC sand paper polishing, then exist successively
It is cleaned by ultrasonic 8min, hot-air seasoning in acetone, deionized water, ethanol.
(2) 1mol/L NaOH deionized water solutions 150mL is prepared.Magnesium alloy after polishing is immersed in NaOH solution
1h is incubated in 80 DEG C, then by magnesium alloy sample deionized water rinse, drying.
(3) with Ca (CH3COO)2Ca is prepared for Ca sources2+The aqueous solution, with NaH2PO4PO is prepared for P sources4 3-The aqueous solution.Then
By PO4 3-Ca is added dropwise in the aqueous solution2+In the aqueous solution, the pH value of mixed solution is finally transferred to 5.5 with 8M acetic acid, magnetic force is stirred
Mix 2h.Wherein, Ca in mixed solution2+Concentration be 5mmol/L, PO4 3-Concentration be 1.5mmol/L.Weigh 100mL mixing molten
Liquid is used as conversion coating solution.
(4) magnesium alloy sample after alkali process is soaked in conversion coating solution, conversion coating solution be positioned over micro-
In ripple chemical reactor, output frequency is 915MHz microwaves, and conversion coating solution is heated into boiling with peak power output, is protected
Hold 5min.The magnesium alloy sample that coating is coated immediately after takes out, and uses deionized water rinse, dries.
Prepared hydroxyapatite coating layer forms flower-like structure by great amount of hydroxy group apatite nanometer rods cluster, nanometer rods
Length is 300~700nm, a diameter of 30~70nm of nanometer rods.The thickness of hydroxyapatite coating layer is~4 μm.Hydroxy-apatite
The AC impedance of stone cladding magnesium alloy is~18000ohmcm2。
Embodiment 4
(1) AZ80 magnesium alloys are processed into 10mm × 10mm × 2mm block, successively with 240#、1200#SiC sand paper beat
Mill, is then cleaned by ultrasonic 3min, hot-air seasoning in acetone, deionized water, ethanol successively.
(2) 1.5mol/L NaOH deionized water solutions 150mL is prepared.Magnesium alloy after polishing is immersed in NaOH solution
In in 90 DEG C be incubated 1h, then by magnesium alloy sample deionized water rinse, drying.
(3) with Ca (CH3COO)2Ca is prepared for Ca sources2+The aqueous solution, with NH4H2PO4PO is prepared for P sources4 3-The aqueous solution.Then
By PO4 3-Ca is added dropwise in the aqueous solution2+In the aqueous solution, the pH value of mixed solution is finally transferred to 5.5, magnetic force with 1M dust technology
Stir 2h.Wherein, Ca in mixed solution2+Concentration be 5mmol/L, PO4 3-Concentration be 2mmol/L.Weigh 100mL mixing molten
Liquid is used as conversion coating solution.
(4) magnesium alloy sample after alkali process is soaked in conversion coating solution, conversion coating solution be positioned over micro-
In ripple chemical reactor, output frequency is 915MHz microwaves, and conversion coating solution is heated into boiling with peak power output, is protected
Hold 2min.The magnesium alloy sample that coating is coated immediately after takes out, and uses deionized water rinse, dries.
Prepared hydroxyapatite coating layer forms flower-like structure by great amount of hydroxy group apatite nanometer rods cluster, nanometer rods
Length is 200~500nm, a diameter of 20~70nm of nanometer rods.The thickness of hydroxyapatite coating layer is~2 μm.Hydroxy-apatite
The AC impedance of stone cladding magnesium alloy is~12500ohmcm2。
Claims (5)
1. a kind of microwave preparation of the flower-shaped hydroxyapatite coating layer of Mg alloy surface, it is characterized in that：By pretreated magnesium
Alloy sample is soaked in conversion coating solution, and conversion coating solution is positioned in microwave chemical reactor, by conversion coating
Solution is heated to boiling, keeps 2~10min；The magnesium alloy sample that coating is coated immediately after takes out, and is moistened with deionized water
Wash, dry；Described conversion coating solution is：With Ca (NO3)2、CaCl2Or Ca (CH3COO)2Ca is prepared for Ca sources2+The aqueous solution,
With NH4H2PO4、Na2HPO4Or NaH2PO4PO is prepared for P sources4 3-The aqueous solution；Then by PO4 3-The aqueous solution is added dropwise to Ca2+The aqueous solution
In, the pH value of mixed solution is finally transferred to 5~6,1~2h of magnetic agitation with diluted acid；Wherein, Ca in mixed solution2+Concentration
For 4~6mmol/L, PO4 3-Concentration be 1~2mmol/L；The flower-shaped hydroxyapatite coating layer of Mg alloy surface of preparation, hydroxyl phosphorus
Lime stone coating is that hydroxyapatite nano rod cluster forms flower-like structure, and the length of nanometer rods is 300~900nm, nanometer rods
A diameter of 30~90nm；Coating layer thickness is 2~10 μm.
2. the method as described in claim 1, it is characterized in that described Mg alloy surface pretreatment is：Mg alloy surface is polished
To 1200~2000 mesh, then it is cleaned by ultrasonic 3~10min, drying in acetone, deionized water, ethanol successively；Again by magnesium alloy
It is immersed in NaOH solution in 60~90 DEG C of insulations, then uses deionized water rinse, dries.
3. the method as described in claim 1, it is characterized in that described diluted acid is one kind in dust technology, watery hydrochloric acid, acetic acid, its
Concentration is 1~20mol/L.
4. the method as described in claim 1, it is characterized in that described magnesium alloy is AZ31, AZ61, AZ80 or AZ91 one kind.
5. the method as described in claim 1, it is characterized in that the frequency that described microwave chemical reactor produces microwave is
915MHz or 2450MHz.
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| 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 |
| WO2018187752A1 (en) * | 2017-04-07 | 2018-10-11 | The Board Of Trustees Of The University Of Illinois | Nanostructured titanium-based compositions and methods to fabricate the same |
| 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 |
| CN109137009B (en) * | 2018-09-28 | 2021-02-05 | 北京工业大学 | Method for preparing porous magnesium hydroxide by pulse electrodeposition |
| 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 |
| 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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