CN105457099A - Two-layer crystal whisker-shaped fluorine-doped hydroxyapatite coating on magnesium alloy and microwave preparation method thereof - Google Patents
Two-layer crystal whisker-shaped fluorine-doped hydroxyapatite coating on magnesium alloy and microwave preparation method thereof Download PDFInfo
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- A—HUMAN NECESSITIES
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- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/28—Materials for coating prostheses
- A61L27/30—Inorganic materials
- A61L27/32—Phosphorus-containing materials, e.g. apatite
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L2420/00—Materials or methods for coatings medical devices
- A61L2420/02—Methods for coating medical devices
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L2420/00—Materials or methods for coatings medical devices
- A61L2420/08—Coatings comprising two or more layers
Abstract
The invention discloses a two-layer crystal whisker-shaped fluorine-doped hydroxyapatite coating on magnesium alloy and a microwave preparation method thereof, and belongs to the technical field of degradable magnesium alloy implantation materials. The fluorine-doped hydroxyapatite coating is of a two-layer structure. The length and diameter of the bottom-layer fluorine-doped hydroxyapatite crystal whisker is 0.5-0.8 micrometer and 50-70 nm respectively. The length and diameter of the top-layer fluorine-doped hydroxyapatite crystal whisker is 1.0-2.0 micrometers and 30-50 nm respectively. The microwave preparation method mainly comprises the steps that a conversion coating solution containing Ca2+, PO43- and F- is prepared, and magnesium alloy subjected to alkali treatment is placed in the conversion coating solution and subjected to microwave heating for 10-30 min. The microwave preparation method is applicable to magnesium alloy of any shapes and sizes, the technology is simple, energy is remarkably saved, and the application and popularization value is huge.
Description
Technical field
The present invention relates to double-deck crystal whisker-shaped Fluorin doped hydroxyapatite coating layer and microwave preparation thereof on magnesium alloy, belong to degradable magnesium alloy implant surface technical field of modification.
Background technology
Medical 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, rustless steel, the elastic modelling quantity (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 medical 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, medical 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 practice.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.Especially nano whisker shape hydroxyapatite, owing to having great specific surface area, be conducive to osteoblastic adhesion, propagation, differentiation, secretion collagen, engulf degraded, promote calcification, realize the normal reconstruct process of nature bone, be a kind of hard tissue repair substitution material of function admirable, be successfully applied to the fields such as dentistry, plastic surgery and maxillary surface reconstruction at present
[1-4].If crystal whisker-shaped hydroxyapatite coating layer can be prepared at medical magnesium alloy surface, not only can represent the excellent mechanical property of magnesium alloy substrate, the excellent biological nature of crystal whisker-shaped hydroxyapatite coating layer and physical barriers effect can also be played.
Lot of documents shows, by F
-introduce hydroxyapatite lattice to go to replace OH
-, promote that crystal is along c-axis preferential growth
[1,2], Fluorin doped hydroxyapatite (FHA, Ca
5(PO
4)
3(OH)
1-xf
x) be extensively present in human skeleton and enamel.Compared with hydroxyapatite, Fluorin doped hydroxyapatite has good acid-resisting, antilysis, high degree of crystallinity.If Fluorin doped hydroxyapatite coating layer can be prepared at Mg alloy surface, by the degradation cycle of prolongation magnesium alloy in physiological environment, weaken the defect of corrosive liquid by coating and permeate to magnesium alloy substrate and corrode magnesium alloy.
At present, the report about crystal whisker-shaped hydroxyapatite synthetic method is mainly the synthesis and preparation of powder, as hydro-thermal method, modification biomimetic method etc.The people such as Costa
[3]first obtained CaP dry gel powder, and then hydrothermal treatment consists has prepared one dimension hydroxyapatite powder in 170 DEG C of insulation 6 to 24h.And be detected in the people such as Xia about the report of crystal whisker-shaped hydroxyapatite coating layer
[4]research, titanium oxide alloy sheet is placed in bionical solution, soaks 14 days obtained compact arranged crystal whisker-shaped Fluorin doped hydroxyapatite coating layers respectively at 37 DEG C and 60 DEG C.But said method needs loaded down with trivial details technique and longer time usually, it is not the preparation method of efficient energy-saving.
At present, magnesium alloy is prepared hydroxyapatite coating layer and there is multiple method, as (patent No.s 200910065998.2) such as Guan Shaokang adopts 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 hydro-thermal method has prepared 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.The hydroxyapatite coating layer that said method relates to is all the signal layer coating be made up of graininess hydroxyapatite.But the research preparing double-deck crystal whisker-shaped Fluorin doped hydroxyapatite coating layer at Mg alloy surface rarely has report.Compared to monolayer of particles shape hydroxyapatite coating layer, the advantage of double-deck crystal whisker-shaped Fluorin doped hydroxyapatite coating layer is: 1) crystal whisker-shaped hydroxyapatite coating layer, especially top layer crystal whisker-shaped hydroxyapatite coating layer has great specific surface area, biological activity is high, not only be conducive to osteoblastic adhesion, propagation, differentiation, also promote Ca in physiological environment
2+, PO
4 3-ion, at crystal whisker-shaped hydroxyapatite surface secondary nucleation, extends and improves the protected effect of coating; 2) F
-doping improves the antilysis of hydroxyapatite coating layer, extends the protected effect of coating; 3) double-deck crystal whisker-shaped hydroxyapatite coating layer is usually thick than monolayer hydroxyapatite coating layer, extends the protected effect of coating.Therefore, a kind of double-deck crystal whisker-shaped Fluorin doped hydroxyapatite coating layer of development is the problem that current research field needs to solve.
At present, microwave energy, as a kind of novel heat resource form, has been applied in drying, heating, sterilization field more and more, as drying of wood dehydration, food drying sterilization, tea green-keeping, plastics drying etc.The principle of microwave heating under the polarization 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 conduction of heat from outward appearance to inner essence, and therefore microwave heating belongs to volume heating.At present, microwave technology medicine, organic chemical industry, inorganic particle synthesis field had application to a certain degree, especially microwave technique application in chemical synthesis in liquid phase, not only can improve reaction system intermediate ion or molecular diffusion rate
[5,6], reaction rate heats raising tens to hundred times than traditional electrical, and can reduce the free energy of activation of reaction system
[7], obtain new material, newly pattern, new construction etc. that conventional electric-heating technology cannot obtain.Therefore, adopt microwave-assisted liquid chemical method to prepare crystal whisker-shaped Fluorin doped hydroxyapatite coating layer at medical magnesium alloy surface, have that aggregate velocity is fast, the advantage such as energy-conserving and environment-protective, technique are simple, coating structure morphology controllable.
List of references:
[1]IijimaM,OldakJM.Controlofapatitecrystalgrowthinafluoridecontainingamelogenin-richmatrix[J].Biomaterials,2005,26:1595–1603.
[2] Wang Fen, Zhang Ling. draw the impact [J] of fluorine amount on fluoridated hydroxyapatite nanocrystalline structure. material science and technique, 2008,16 (4): 559 – 561.WANGFen, ZHANGling.Influenceoffluorinecontentoncrystalstructureof nano-fluorhydroxyapatitepowders.MaterSciTechnol, 2008,16 (4): 559 – 561.
[3]CostaDO,DixonSJ,RizkallaAS.One-andthree-dimensionalgrowthofhydroxyapatitenanowiresduringsol-gel-hydrothermalsynthesis[J].ACSApplMaterInter,2012,4:1490–1499.
[4]XiaW,LausmaaJ,ThomsenP,etal.Highlypackedandalignedfluoridesubstitutehydroxyapatiteviaasurfactant-freeprocess[J].JBiomedMaterResPartB,2012,51:75–81.
[5]YamadaS,TakasuA,KawamuraK.Theeffectofmicrowaveirradiationonthekineticsandactivationthermodynamicsofring-openingpolymerizationofε-caprolactone[J].JPolymSciPartA:PolymChem,2013,51:3732–3739.
[6]BooskeJH,CooperRF,FreemanSA.Microwaveenhancedreactionkineticsinceramics[J].MaterResInnov.1997,1:77–84.
[7]HaqueE,KhanNA,KimCM,etal.Synthesesofmetal–organicframeworksandaluminophosphatesundermicrowaveheating:quantitativeanalysisofaccelerations[J].CrystGrowthDes,2011,11:4413–4421.
Summary of the invention
The object of the present invention is to provide the double-deck crystal whisker-shaped Fluorin doped hydroxyapatite coating layer of a kind of Mg alloy surface and microwave preparation thereof.Prepared nano whisker shape Fluorin doped hydroxyapatite coating layer is double-decker: primer coating is the Fluorin doped hydroxyapatite crystal whisker at Mg alloy surface growth in situ; Top coat is the Fluorin doped hydroxyapatite crystal whisker of separating out from solution.The length of bottom Fluorin doped hydroxyapatite crystal whisker is 0.5 ~ 0.8 μm, and diameter is 50 ~ 70nm; The length of top layer Fluorin doped hydroxyapatite crystal whisker is 1.0 ~ 2.0 μm, and diameter is 30 ~ 50nm.Double-deck crystal whisker-shaped Fluorin doped hydroxyapatite coating layer not only increases the biological activity of magnesium alloy, and improves the corrosion resistance of magnesium alloy at physiological environment.
The microwave preparation of above-mentioned Mg alloy surface double-deck crystal whisker-shaped Fluorin doped hydroxyapatite coating layer, is characterized in that carrying out according to the following steps:
1) Mg alloy surface pretreatment: by sand papering to 1200 ~ 2000 used for magnesium alloy order, then ultrasonic cleaning 3 ~ 10min in acetone, deionized water, ethanol successively, dry.
2) magnesium alloy alkali treatment: the NaOH aqueous solution of preparation 0.5 ~ 5mol/L; Magnesium alloy after polishing is immersed in NaOH solution and is incubated 0.5 ~ 2h in 60 ~ 90 DEG C, then use deionized water rinsing, 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+aqueous solution, with NH
4h
2pO
4, Na
2hPO
4or NaH
2pO
4for PO is prepared in P source
4 3-aqueous solution, with NaF or KF for F is prepared in F source
-aqueous solution; Then by PO
4 3-aqueous solution dropwise adds Ca
2+in aqueous solution, be stirred for solution A; By F
-aqueous solution dropwise adds in solution A, is stirred for B solution.Finally with diluted acid, the pH value of B solution is transferred to 5.5 ~ 7.0, stirs 0.5 ~ 1h and conversion coating solution.Wherein, Ca in conversion coating solution
2+concentration be 4 ~ 7mmol/L, PO
4 3-concentration be 1 ~ 2mmol/L, F
-concentration be 0.15 ~ 0.5mmol/L.
4) preparation of double-deck Fluorin doped hydroxyapatite coating layer: the magnesium alloy sample after alkali treatment is soaked in conversion coating solution, conversion coating solution is positioned in microwave chemical reactor, with the output of 1000 ~ 4000W, conversion coating solution is heated to boiling, keeps 10 ~ 30min.Then immediately magnesium alloy sample coated for coating is taken out, with deionized water rinsing, dry.
Described step 3) in diluted acid be one in dust technology, dilute hydrochloric acid, acetic acid, its concentration is 1 ~ 10mol/L.Described magnesium alloy is the one in AZ31, AZ61, AZ80, AZ91 medical magnesium alloy.Described step 4) in the microwave frequency of microwave chemical reactor be 915MHz or 2450MHz.
In sum, core of the present invention is that preparation comprises Ca
2+, PO
4 3-and F
-conversion coating solution, under microwave radiation, due to the dielectric loss of hydrone in conversion coating solution, solution is rapidly heated to boiling, it substantially increase the chemical driving force that Fluorin doped hydroxyapatite nucleus is separated out, accelerate the nucleation and growing of Fluorin doped hydroxyapatite at Mg alloy surface, final quick in situ synthetic coating.F
-enter hydroxyapatite lattice and replace OH
-, impel it along C axle preferential growth.In addition, the pH value that conversion coating solution is suitable ensure that the coating of synthesis is single-phase Fluorin doped hydroxyapatite.Further, after alkali treatment, generate one deck Mg (OH) at Mg alloy surface
2, Mg (OH)
2there is strong adsorption effect to Fluorin doped hydroxyapatite nucleus, facilitate Fluorin doped hydroxyapatite nucleus at Mg alloy surface growth in situ.The synergism of above-mentioned three aspects makes by microwave-assisted liquid chemical method at Mg alloy surface one step Fast back-projection algorithm double-deck crystal whisker-shaped Fluorin doped hydroxyapatite coating layer.
Compared with prior art, advantage of the present invention and good effect are:
(1) the present invention's double-deck crystal whisker-shaped Fluorin doped hydroxyapatite coating layer that utilized microwave-assisted liquid chemical method at Mg alloy surface one-step synthesis.The length of bottom Fluorin doped hydroxyapatite crystal whisker is 0.5 ~ 0.8 μm, and diameter is 50 ~ 70nm; The length of top layer Fluorin doped hydroxyapatite crystal whisker is 1.0 ~ 2.0 μm, and diameter is 30 ~ 50nm.
(2) the present invention utilizes microwave-assisted liquid chemical method by F
-introduce hydroxyapatite lattice and replace OH
-prepare double-deck crystal whisker-shaped Fluorin doped hydroxyapatite coating layer, compared with pure ha, crystal whisker-shaped Fluorin doped hydroxyapatite has higher degree of crystallinity and antilysis, reduce dissolving and the cracking of Fluorin doped hydroxyapatite coating layer after implant into body, improve the corrosion resistance of magnesium alloy in physiological environment.
(3) reliability of the present invention is high.For the magnesium alloy sample of any shape, size, all can at the double-deck crystal whisker-shaped Fluorin doped hydroxyapatite coating layer of its surface preparation.
(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 temperature.
(5) present invention process simple, fast, environmental protection, only need 10min, just can prepare double-deck crystal whisker-shaped Fluorin doped hydroxyapatite coating layer at Mg alloy surface, microwave-assisted liquid chemical method disclosed in this invention is a kind of efficient, economic, green, brand-new material preparation process.
Accompanying drawing explanation
The glancing incidence XRD figure spectrum of the coating coated magnesium alloy of Fig. 1 prepared by the embodiment of the present invention 1.
The surface topography low power SEM of the double-deck Fluorin doped hydroxyapatite coating layer of Fig. 2 prepared by the embodiment of the present invention 1 schemes.
The surface topography high power SEM of the Fluorin doped hydroxyapatite top coat of Fig. 3 prepared by the embodiment of the present invention 1 schemes.
The surface topography high power SEM of the Fluorin doped hydroxyapatite primer coating of Fig. 4 prepared by the embodiment of the present invention 1 schemes.
Detailed description of the invention
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.
Embodiment 1
(1) AZ31 magnesium alloy is processed into the block of 10mm × 10mm × 2mm, is polished to 2000 orders with SiC sand paper, 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 10 polishings is immersed in 60 DEG C of insulation 0.5h in NaOH solution, then by magnesium alloy sample deionized water rinsing, oven dry.
(3) with Ca (NO
3)
2for Ca is prepared in Ca source
2+aqueous solution, with Na
2hPO
4for PO is prepared in P source
4 3-aqueous solution is that F is prepared in F source with NaF
-aqueous solution.Then by PO
4 3-aqueous solution dropwise adds Ca
2+in aqueous solution, be stirred for solution A; By F
-aqueous solution dropwise adds in solution A, is stirred for B solution; Finally with the dust technology of 10M, the pH value of B solution is transferred to 6.0, magnetic agitation 1h is conversion coating solution.Wherein, Ca in conversion coating solution
2+concentration be 6mmol/L, PO
4 3-concentration be 2mmol/L, F
-concentration be 0.3mmol/L.Take 100mL conversion coating solution.
(4) magnesium alloy sample after 5 alkali treatments is soaked in conversion coating solution, conversion coating solution is positioned in microwave chemical reactor, micro-wave frequency is 2450MHz, with the output of 1000W, conversion coating solution is heated to boiling, keeps 10min.Then immediately magnesium alloy sample coated for coating is taken out, with deionized water rinsing, dry.
As shown in Figure 1, collection of illustrative plates mates intact with the diffraction spectra (JCPDS73-1727) of fluorine hydroxyapatite the glancing incidence XRD figure spectrum of the prepared coated magnesium alloy of coating, illustrates that the coating of synthesis is single-phase Fluorin doped hydroxyapatite.As shown in Figure 2, the Fluorin doped hydroxyapatite coating layer of synthesis is double-decker.Fig. 3 is that the surface topography high power SEM of Fluorin doped hydroxyapatite top coat schemes.Fig. 4 is that the surface topography high power SEM of Fluorin doped hydroxyapatite primer coating schemes.The length of bottom Fluorin doped hydroxyapatite crystal whisker is ~ 0.6 μm, and diameter is ~ 50nm; The length of top layer Fluorin doped hydroxyapatite crystal whisker is ~ 1.3 μm, and diameter is ~ 30nm.
Embodiment 2
(1) AZ91 magnesium alloy is processed into the block of 10mm × 10mm × 2mm, is polished to 1200 orders with SiC sand paper, then ultrasonic cleaning 6min in acetone, deionized water, ethanol successively, hot-air seasoning.
(2) the NaOH deionized water solution 150mL of 0.5mol/L is prepared.Magnesium alloy after polishing 5 is immersed in 70 DEG C of insulation 1h in NaOH solution, then by magnesium alloy sample deionized water rinsing, and oven dry.
(3) with CaCl
2for Ca is prepared in Ca source
2+aqueous solution, with NaH
2pO
4for PO is prepared in P source
4 3-aqueous solution.Be that F is prepared in F source with KF
-aqueous solution.Then by PO
4 3-aqueous solution dropwise adds Ca
2+in aqueous solution, be stirred for solution A, by F
-aqueous solution dropwise adds in solution A, is stirred for B solution.Finally with the dilute hydrochloric acid of 7M, the pH value of B solution is transferred to 5.5, magnetic agitation 0.5h is conversion coating solution.Wherein, Ca in conversion coating solution
2+concentration be 4mmol/L, PO
4 3-concentration be 1mmol/L, F
-concentration be 0.15mmol/L.Take 100mL conversion coating solution.
(4) be soaked in conversion coating solution by the magnesium alloy after 3 alkali treatments, be positioned over by conversion coating solution in microwave chemical reactor, micro-wave frequency is 2450MHz, with 2000Wization output, coating solution is heated to boiling, keeps 20min.Then immediately magnesium alloy coated for coating is taken out, with deionized water rinsing, dry.
Through X-ray diffraction analysis, prepared coating is single-phase Fluorin doped hydroxyapatite.Coating is double-deck crystal whisker-shaped Fluorin doped hydroxyapatite.The length of bottom Fluorin doped hydroxyapatite crystal whisker is ~ 0.7 μm, and diameter is ~ 60nm; The length of top layer Fluorin doped hydroxyapatite crystal whisker is ~ 1.6 μm, and diameter is ~ 40nm.
Embodiment 3
(1) AZ61 magnesium alloy is processed into the block of 10mm × 10mm × 2mm, is polished to 1500 orders with SiC sand paper, then ultrasonic cleaning 8min 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 15 is immersed in 80 DEG C of insulation 1.5h in NaOH solution, then by magnesium alloy sample deionized water rinsing, and oven dry.
(3) with Ca (CH
3cOO)
2for Ca is prepared in Ca source
2+aqueous solution, with NaH
2pO
4for PO is prepared in P source
4 3-aqueous solution is that F is prepared in F source with NaF
-aqueous solution.Then by PO
4 3-aqueous solution dropwise adds Ca
2+in aqueous solution, be stirred for solution A, by F
-aqueous solution dropwise adds in solution A, is stirred for B solution, and finally with the acetic acid of 4M, the pH value of B solution is transferred to 7.0, magnetic agitation 0.8h is conversion coating solution.Wherein, Ca in conversion coating solution
2+concentration be 7mmol/L, PO
4 3-concentration be 1.5mmol/L, F
-concentration be 0.5mmol/L.Take 200mL conversion coating solution.
(4) magnesium alloy after 10 alkali treatments is soaked in conversion coating solution, conversion coating solution is positioned in microwave chemical reactor, micro-wave frequency is 915MHz, with the output of 3000W, conversion coating solution is heated to boiling, keeps 10min.Then immediately magnesium alloy coated for coating is taken out, with deionized water rinsing, dry.
Through X-ray diffraction analysis, prepared coating is single-phase Fluorin doped hydroxyapatite.Coating is double-deck crystal whisker-shaped Fluorin doped hydroxyapatite.The length of bottom Fluorin doped hydroxyapatite crystal whisker is ~ 0.5 μm, and diameter is ~ 50nm; The length of top layer Fluorin doped hydroxyapatite crystal whisker is ~ 1.0 μm, and diameter is ~ 30nm.
Embodiment 4
(1) AZ80 magnesium alloy is processed into the block of 10mm × 10mm × 2mm, is polished to 1200 orders with SiC sand paper, then ultrasonic cleaning 3min in acetone, deionized water, ethanol successively, hot-air seasoning.
(2) the NaOH deionized water solution 150mL of 5mol/L is prepared.Magnesium alloy after polishing 8 is immersed in 90 DEG C of insulation 2h in NaOH solution, then by magnesium alloy sample deionized water rinsing, and oven dry.
(3) with Ca (CH
3cOO)
2for Ca is prepared in Ca source
2+aqueous solution, with NH
4h
2pO
4for PO is prepared in P source
4 3-aqueous solution is that F is prepared in F source with NaF
-aqueous solution.Then by PO
4 3-aqueous solution dropwise adds Ca
2+in aqueous solution, be stirred for solution A, by F
-aqueous solution dropwise adds in solution A, is stirred for B solution, and finally with the dust technology of 1M, the pH value of B solution is transferred to 6.3, magnetic agitation 0.6h is conversion coating solution.Wherein, Ca in conversion coating solution
2+concentration be 5mmol/L, PO
4 3-concentration be 2mmol/L, F
-concentration be 0.4mmol/L.Taking 300mL is conversion coating solution.
(4) be soaked in conversion coating solution by the magnesium alloy after 10 alkali treatments, be placed in by conversion coating solution in microwave chemical reactor, micro-wave frequency is 915MHz, with the output of 4000W, conversion coating solution is heated to boiling, keeps 30min.Then immediately magnesium alloy coated for coating is taken out, with deionized water rinsing, dry.
Through X-ray diffraction analysis, prepared coating is single-phase Fluorin doped hydroxyapatite.Coating is double-deck crystal whisker-shaped Fluorin doped hydroxyapatite.The length of bottom Fluorin doped hydroxyapatite crystal whisker is ~ 0.8 μm, and diameter is ~ 70nm; The length of top layer Fluorin doped hydroxyapatite crystal whisker is ~ 2.0 μm, and diameter is ~ 50nm.
Claims (5)
1. double-deck crystal whisker-shaped Fluorin doped hydroxyapatite coating layer on magnesium alloy, is characterized in that: described coating is double-decker: the length of bottom Fluorin doped hydroxyapatite crystal whisker is 0.5 ~ 0.8 μm, and diameter is 50 ~ 70nm; The length of top layer Fluorin doped hydroxyapatite crystal whisker is 1.0 ~ 2.0 μm, and diameter is 30 ~ 50nm.
2. the microwave preparation of double-deck crystal whisker-shaped Fluorin doped hydroxyapatite coating layer on magnesium alloy, is characterized in that comprising the following steps:
1) Mg alloy surface pretreatment: by sand papering to 1200 ~ 2000 used for magnesium alloy order, then ultrasonic cleaning 3 ~ 10min in acetone, deionized water, ethanol successively, dry;
2) magnesium alloy alkali treatment: the NaOH aqueous solution of preparation 0.5 ~ 5mol/L; Magnesium alloy after polishing is immersed in 60 ~ 90 DEG C of insulation 0.5 ~ 2h in NaOH solution, then by deionized water rinsing used for magnesium alloy, oven 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+aqueous solution, with NH
4h
2pO
4, Na
2hPO
4or NaH
2pO
4for PO is prepared in P source
4 3-aqueous solution, with NaF or KF for F is prepared in F source
-aqueous solution; Then by PO
4 3-aqueous solution is added dropwise to Ca
2+in aqueous solution, be stirred for solution A; By F
-aqueous solution is added dropwise in solution A, is stirred for B solution; Finally with diluted acid, the pH value of B solution is transferred to 5.5 ~ 7.0, stirring 0.5 ~ 1h is conversion coating solution; Wherein, Ca in conversion coating solution
2+concentration be 4 ~ 7mmol/L, PO
4 3-concentration be 1 ~ 2mmol/L, F
-concentration be 0.15 ~ 0.5mmol/L.
4) preparation of double-deck crystal whisker-shaped Fluorin doped hydroxyapatite coating layer on magnesium alloy: the magnesium alloy after alkali treatment is soaked in conversion coating solution, conversion coating solution is placed in microwave chemical reactor, with the output of 1000 ~ 4000W, conversion coating solution is heated to boiling, keeps 10 ~ 30min; Then immediately magnesium alloy coated for coating is taken out, with deionized water rinsing, dry.
3. method according to claim 2, is characterized in that, described step 3) in diluted acid be one in dust technology, dilute hydrochloric acid or acetic acid, its concentration is 1 ~ 10mol/L.
4. method according to claim 2, is characterized in that, described magnesium alloy is the one in AZ31, AZ61, AZ91, AZ80 medical magnesium alloy.
5. method according to claim 2, is characterized in that, the microwave frequency of described microwave chemical reactor is 915MHz or 2450MHz.
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|---|---|---|---|
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| CN106011815A (en) * | 2016-06-07 | 2016-10-12 | 西南交通大学 | Preparation method for hybrid composite coating used for magnesium-based biological material surface medication |
| CN107789664A (en) * | 2017-10-26 | 2018-03-13 | 陕西师范大学 | Mg alloy surface growth in situ NaMgF3The method of nanometer rods |
| 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 |
| 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 |
| CN114404652A (en) * | 2022-01-19 | 2022-04-29 | 河北科技师范学院 | Method for preparing chitosan intermediate layer on surface of medical magnesium alloy |
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| CN106011815A (en) * | 2016-06-07 | 2016-10-12 | 西南交通大学 | Preparation method for hybrid composite coating used for magnesium-based biological material surface medication |
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| 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 |
| 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 |
| CN114404652A (en) * | 2022-01-19 | 2022-04-29 | 河北科技师范学院 | Method for preparing chitosan intermediate layer on surface of medical magnesium alloy |
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