CN109646717A - Mg alloy surface nano hydroxyapatite coating and preparation method based on ultrasound - Google Patents

Mg alloy surface nano hydroxyapatite coating and preparation method based on ultrasound Download PDF

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CN109646717A
CN109646717A CN201811620372.9A CN201811620372A CN109646717A CN 109646717 A CN109646717 A CN 109646717A CN 201811620372 A CN201811620372 A CN 201811620372A CN 109646717 A CN109646717 A CN 109646717A
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coating
hydroxyapatite coating
ultrasound
alloy
alloy surface
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CN109646717B (en
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孙金娥
蔡舒
刘杰
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Tianjin College Of University Of Science And Technology Beijing
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    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
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Abstract

The invention belongs to degradable magnesium alloy implant surface technical field of modification, disclose it is a kind of based on ultrasound Mg alloy surface nano hydroxyapatite coating and preparation method, the preparation method comprising steps of by after the exposed surface base extraction of magnesium alloy with contain Si (OH)4Hydroxyapatite coating layer solution carry out coating coating reaction under ultrasound environments after obtain Mg alloy surface nano hydroxyapatite coating；The coating is formed by the lobate hydroxyapatite of a large amount of nano bamboos is closely interlaced.Coating of the invention has biggish surface roughness, has good long-term corrosion resistance and bioactivity.

Description

Mg alloy surface nano hydroxyapatite coating and preparation method based on ultrasound
Technical field
The invention belongs to degradable magnesium alloy implant surface technical field of modification, and in particular to a kind of magnesium based on ultrasound Alloy surface nano hydroxyapatite coating and preparation method.
Background technique
Compared with conventional medical metal material stainless steel, titanium alloy, NiTi marmem and cobalt-base alloys etc., magnesium and Magnesium alloy becomes life with its unique biodegradable performance, with mechanical performance and good bio-compatible performance etc. similar in bone The important development of object field of medical materials.The density of magnesium and magnesium alloy and people's bone density are very close, and elasticity modulus is also far below Titanium alloy, stainless steel etc. are more matched with bone tissue, and generated " stress shielding " is imitated when it can be effectively relieved as implantation material It answers.In addition, the magnesium ion that magnesium alloy is generated by corrosion is the particularly important element of human body, to guarantor in human physiological environment Hold the stability of DNA and RNA, promote new bone growth and accelerate bone defect healing etc. plays an important role.But magnesium alloy exists It organizes degradation rate in body fluid too fast, the time required to mechanical property invalidation period is much smaller than clinical bone defect healing, influences bone The growth and healing of tissue, limit its clinical application.Therefore, the corrosion resisting property of magnesium and magnesium alloy is improved to extend it in human body The military service period it is most important.The modification of biological active coating layer surface is to reduce magnesium alloy degradation rate and enhance having for bioactivity One of efficacious prescriptions method, with excellent bioactivity, osteoacusis and bone regeneration capability, being expected to, which becomes novel bioactivity, to drop Solve bone renovating material.
Biologic medical magnesium and the degradation material of coating of magnesium alloy surface modification mainly include hydroxyapatite, phosphate dihydrate The bioactivity CaP coating such as hydrogen calcium, fluor-apatite, because CaP class bone apatite calcium salt have with inorganic constituents as human body bone photo, The growth that can induce bone tissue forms firm bone bonding, shows excellent biocompatibility.Currently, in bio-medical gold The common method for belonging to material surface preparation bioactivity hydroxyapatite coating layer includes that hydro-thermal method, electrochemical deposition method and colloidal sol are solidifying Glue method etc..(the A biodegradable AZ91magnesium alloy coated with a such as Mukhametkaliyev thin nanostructured hydroxyapatite for improving the corrosion Resistance.Materials Science and Engineering:C, 75 (2017) 95-103) it reports and is splashed using magnetic control It is about 500nm hydroxyapatite HA coating that shooting method, which prepares thickness in AZ91 Mg alloy surface, which does not have hole, more cause Close, discovery nanostructure HA coating sample can effectively reduce the corrosion rate of magnesium alloy after simulated body fluid SBF impregnates 7 days. (patent No. WO2014020446A2) such as Mirjam assists the growth of bionical solution hydroxyapatite using microwave radiation, can be direct Complete hydroxyapatite coating layer is obtained on surfaces such as titanium alloy, magnesia.Bo Li et al. (Formation Mechanism, Degradation Behavior,and Cytocompatibility of a Nanorod-Shaped HA and Pore- Sealed MgO Bilayer Coating on Magnesium.Applied Materials&Interfaces.2014,9) The method combined using both micro-arc oxidation and hydro-thermal method, the rodlike HA that one layer of Nano grade is prepared on magnesium alloy are applied Layer, coating is comparatively dense, and in vitro in Degrading experiment, coating sample impregnates the 5th day by Eroded in SBF, and pH value is big In 9, it is unfavorable for prolonged erosion performance study；In addition, this method is needed by differential arc oxidation in conjunction with hydro-thermal method, experimentation is more It is complicated.(patent No. CN103938246A) such as Liu Maolin mixes strontium hydroxyl phosphorus in the pure titanium surface preparation of metal using electrochemical deposition method Lime stone band spinal rod shape structure coating, the coating structure increase the specific surface area of coating, make it have better wetability；Simultaneously The doping of strontium ion changes the dissolution characteristics of coating.The biodegradable activity HA coating of above-mentioned document and patent report can be The degradation property and bioactivity of magnesium and magnesium alloy substrate are improved to a certain extent, but tests process and is limited by preparation process, are consumed Duration, production efficiency are low.Such as device configuration needed for electrochemical deposition technique is complicated, cumbersome, voltage and current is unstable, Cause coating uneven.In addition, the degradation cycle of ideal degradable implantation material should be with the healing cycle phase of bone defect Match, it usually needs 3 to 6 months, external degradation test at least needs 2.5 months, Cai Kewei bone remoulding provide early stage support and It is fixed, it is finally gradually degraded and absorbed or is excreted by metabolism.But so far, the magnesium alloy coating modified about HA is long Phase is anti-corrosion, and Journal of Sex Research report is less.
Currently, ultrasonic method has been applied to the preparation of hydroxy apatite powder: China Patent No. (CN106430138A) report Using the porous HA microsphere particles of ultrasonic wave added multi-emulsion method preparation, diameter is about 50~200nm, and size uniformity has big Bone tissue biocompatibility is presented in specific surface area.(the Ultrasonic- such as Jutharatana Klinkaewnarong assisted conversion of limestone into needle-like hydroxyapatite Nanoparticles, Ultrasonics-Sonochemistry, 46 (2018) 18-25) using ultrasonic method it is prepared for diameter about For the needle-like hydroxyapatite particle of 7.4nm, and show that ultrasonic wave is conducive to that calcium monohydrogen phosphate is induced mutually to generate hydroxyapatite phase, Accelerate the crystallization and growth of hydroxyapatite.Compared with Conventional coating techniques, ultrasonic method is to utilize ultrasonic cavitation generation office Portion's high temperature and pressure and thump etc. control chemical reaction and crystallization rate, can substantially weaken the combination between nano particle, effectively It prevents from reuniting, to obtain even-grained micro/nano level HA powder.The method has simple process, and capacity usage ratio is high, energy conservation Outstanding advantages of environmental protection, coating layer thickness and morphology controllable.But be mostly at present hydroxy apatite powder is prepared using ultrasonic method, and It is not directly to prepare hydroxyapatite coating layer, and the method for preparing hydroxyapatite coating layer compared to other is super using a step The research that sound method prepares hydroxyapatite coating layer is not reported so far, and especially ultrasonic method prepares the modified magnesium of hydroxyapatite coating layer The research of the prolonged erosion performance of alloy material also has not been reported.
Summary of the invention
In order to solve the above problems existing in the present technology, it is an object of that present invention to provide a kind of magnesium alloys based on ultrasound Nano surface hydroxyapatite coating layer and preparation method.The present invention by ultrasound and alkali process collective effect under, the short time Inherent Mg alloy surface prepares the fine and close lobate hydroxyapatite coating layer of nano bamboo, improves the external degradation of magnesium alloy Can, while further improving the bioactivity of Mg alloy surface, it is ensured that it heals as biodegradable implantation material in bone tissue Mechanical support and fixation are provided in the period.
The technical scheme adopted by the invention is as follows:
A kind of preparation method of the Mg alloy surface nano hydroxyapatite coating based on ultrasound, comprising steps of magnesium is closed After the exposed surface base extraction of gold and contain Si (OH)4Hydroxyapatite coating layer solution coating is carried out under ultrasound environments Mg alloy surface nano hydroxyapatite coating is obtained after coating reaction.
Further, described to contain Si (OH)4Hydroxyapatite coating layer solution in Ca2+Concentration be 0.01- 0.03mol/L、PO4 3-Concentration be 0.004-0.006mol/L；It is described to contain Si (OH)4Hydroxyapatite coating layer solution PH value is 4-9；It is described to contain Si (OH)4Hydroxyapatite coating layer solution in Si (OH)4Pass through Na2SiO3Hydrolysis generates, Na2SiO3Concentration be 0.002-0.006mol/L.
Further, described to contain Si (OH)4Hydroxyapatite coating layer solution in generate Ca2+Raw material be Ca (NO3)2 Or CaCl2One of or it is a variety of；Contain Si (OH)4Hydroxyapatite coating layer solution in generate PO4 3-Raw material be Na2HPO4、NH4H2PO4、(NH4)2HPO4Or NaH2PO4One of or it is a variety of.
Further, the ultrasonic frequency of the ultrasound environments is 40kHZ or 45kHZ.
Further, the temperature of the coating cladding is 50 DEG C -70 DEG C；The time of coating cladding is 10min-2h.
Further, the sodium hydroxide solution that the lye that the base extraction uses is 1mol/L-2mol/L for concentration；Alkali The time of liquid processing is 0.5h-2h；The temperature of base extraction is 60 DEG C -90 DEG C.
Further, the exposed surface of the magnesium alloy is made using following steps: Mg alloy surface pre-processes: magnesium is closed The exposed surface of magnesium alloy is obtained after gold surface polishing, cleaning, drying.
Further, the cleaning step includes: that the surface of the magnesium alloy after polishing is successively used third in ultrasound environments Ketone, deionized water and ethyl alcohol cleaning, drying are spare；It further include washing step after the coating cladding: what the washing step used Detergent is deionized water or ethyl alcohol；The number of the ASTM of the magnesium alloy is AZ31, AZ61, AZ80 or AZ91.
A kind of Mg alloy surface nano hydroxyapatite coating, the coating are tight by the lobate hydroxyapatite of a large amount of nano bamboos It is close interlaced to form.
Further, the leaf of bamboo shape hydroxyapatite width be 45-55nm, a length of 0.5-3 μm.
The invention has the benefit that a kind of Mg alloy surface nano hydroxyapatite coating based on ultrasound of the invention And preparation method is by forming Mg (OH) with Alkaline pretreatment on the not oxidized surface of magnesium alloy2Protective layer passes through coating Na in solution2SiO3The Si (OH) hydrolyzed to form4, in ultrasound environments, make full use of the part of ultrasonic cavitation effect and generation High temperature and pressure, thump and hydroxyl (OH) assist out-phase forming core, and orientation in situ attracts Ca2+And PO43-, induce hydroxyapatite A large amount of nucleation in a short time, along specific direction oriented growth.These synergistic effects ensure that be quickly generated in Mg alloy surface Mg alloy surface nanometer hydroxyapatite (HA) coating with compact nanometer structure, while can inhibit the generation of hydrogen, make to apply Not the defects of layer does not generate stomata and crackle during the preparation process.
Preparation method of the invention compared with prior art, is also equipped with following advantage:
(1) ultrasonic method used in the present invention is novel, equipment is simple, process is time-consuming short and high-efficient, it is only necessary to 10min-2h, and And for the magnesium alloy sample of any shape, size, the lobate hydroxyapatite coating layer of nano bamboo can be prepared on its surface.
(2) hydroxyapatite coating layer that the present invention is prepared using ultrasonic method in Mg alloy surface, coating is by a large amount of nano bamboos Lobate hydroxyapatite it is close it is interlaced forms, the leaf of bamboo wide about 50nm, a length of 1-2 μm, coating flawless, structure uniformly and It is fine and close.This nano bamboo foliation structure has biggish surface roughness, adheres to for osteoblast in coating surface and growth mentions For advantage, good bioactivity is embodied.
(3) the lobate HA coating of nano bamboo prepared by the present invention, electro-chemical test: AC impedance 11kohmcm2, electric current Density is 5.562 μ A/cm2, 96.8% is reduced compared with magnesium alloy current density, embodies the coating with good short-term Corrosion resisting property.
(4) in vitro in the test of simulated body fluid long-term degradation, coating sample soaking solution pH value was maintained at 8.5 in 60 days Hereinafter, specimen surface has no obvious corrosion, and pH value just rises to 8.5 or more, 14 days and is corroded completely naked magnesium alloy on day 4 Degradation.And most of coatings only embody preferable protective effect in 28 days.Therefore the lobate HA coating of nano bamboo of the invention It is played an important role in magnesium alloy prolonged erosion aspect of performance.
(5) the preparation method is that a kind of high, environmentally friendly technique at low cost, repeatable, preparation have The hydroxyapatite coating layer of nanostructure improves the corrosion resistance and bioactivity of magnesium alloy, has biggish business promotion Value.
Detailed description of the invention
Fig. 1 is the XRD diagram of coating prepared by the embodiment of the present invention 1.
Fig. 2 is the surface topography SEM figure of hydroxyapatite coating layer prepared by the embodiment of the present invention 1.
Fig. 3 is that the lobate hydroxyapatite coating layer of nano bamboo prepared by the embodiment of the present invention 1 coats magnesium alloy and magnesium alloy AC impedance figure of the bare die in simulated body fluid.
Fig. 4 is the pH value figure of coating and naked magnesium alloy during long period of soaking prepared by the embodiment of the present invention 1.
Specific embodiment
With reference to the accompanying drawing and specific embodiment does further explaination to the present invention.
Raw material used in following embodiment is commercially available analysis pure raw material.
A kind of preparation method of Mg alloy surface nano hydroxyapatite coating based on ultrasound of the invention is specific to prepare Steps are as follows:
1) Mg alloy surface pre-processes: by certain size and the Mg alloy surface of shape with multiple between 800-2000 mesh Sand paper successively polishes according to the sequence of mesh number from small to large, is then successively cleaned by ultrasonic 5- in acetone, deionized water, ethyl alcohol 10min, drying；
2) pretreated magnesium alloy Mg alloy surface alkali process: is immersed in the NaOH solution that concentration is 1-2mol/L In, it keeps the temperature in 60 DEG C -90 DEG C of digital display constant water bath box, is then cleaned with deionized water, dried；
3) preparation of calcium phosphor coating solution: with Ca (NO3)2Or CaCl2The source Ca is provided, with Na2HPO4、(NH4)2HPO4Or NaH2PO4The source P is provided；Na2SiO3By hydrolyzing to form Si (OH)4, OH is provided-, it is water-soluble that the source P aqueous solution is then added dropwise to the source Ca After liquid mixing, then it is added dropwise to Na2SiO3In solution, the pH value of mixed solution is finally transferred to 4-9, magnetic agitation 1-2h with diluted acid； Wherein, Ca in mixed solution2+Concentration be 0.01-0.03mol/L, PO43-Concentration be 0.004-0.006mol/L.
4) preparation of hydroxyapatite coating layer: the magnesium alloy sample after alkali process is soaked in coating solution, by coating Solution is placed in ultrasonic reactor, and coating solution is heated 50 DEG C -70 DEG C, keeps 10min-2h；Then by coating cladding Magnesium alloy sample takes out, and is cleaned and is dried with detergent.
Embodiment 1
A kind of preparation method of the Mg alloy surface nano hydroxyapatite coating based on ultrasound, comprising steps of
(1) AZ31 magnesium alloy is processed into 10mm × 10mm × 2mm block, successively with 800#、1200#、2000#SiC Sand paper polishing, is then successively cleaned by ultrasonic 10min, hot-air seasoning in acetone, deionized water, ethyl alcohol.
(2) compound concentration is the NaOH solution 50mL of 1.5mol/L.Magnesium alloy after polishing is impregnated in the solution in 80 1h is kept the temperature at DEG C, then cleans magnesium alloy sample with deionized water, is dried.
(3) with Ca (NO3)2The source Ca is provided, with NaH2PO4·12H2O provides the source P.Na2SiO3By hydrolyzing to form Si (OH)4, OH is provided-, Na2SiO3Concentration be 0.0038mol/L；Then the source P aqueous solution the source Ca aqueous solution is added dropwise to mix Afterwards, then it is added dropwise to Na2SiO3In solution, the pH value of mixed solution is finally transferred to 6.3 with the dust technology of 1M, magnetic agitation 1h.Its In, Ca in mixed solution2+Concentration be 0.0215mol/L, PO4 3-Concentration be 0.0046mol/L.Weigh 100mL mixed solution As coating solution.
(4) by NaOH, treated that magnesium alloy sample is soaked in coating solution, then is placed in ultrasonic reactor, exports Frequency is 40kHz ultrasonic wave, and coating solution is heated to 70 DEG C with peak power output, keeps 1h.Coating sample is taken out immediately, With deionized water rinse, drying.
Prepared coating is with the XRD spectrum of deposit as shown in Figure 1, the object of the coating of synthesis is mutually hydroxyapatite. For the surface topography of coating as shown in Fig. 2, coating is formed by the lobate hydroxyapatite close-packed arrays of nano bamboo, the leaf of bamboo is wide about 50nm, a length of 1-2 μm, coating flawless, structure is uniformly and fine and close.This nano bamboo foliation structure has biggish rough surface Degree adheres in coating surface for osteoblast and growth provides advantage, embodies good bioactivity.Fig. 3 is HA painting The ac impedance spectroscopy of layer magnesium alloy sample and naked magnesium alloy sample in simulated body fluid, AC impedance 11kohmcm2, electricity Current density is 5.562 μ A/cm2, 96.8% is reduced compared with magnesium alloy current density, improves corrosion stability of magnesium alloy energy.Fig. 4 Change for pH value in coating sample and naked magnesium alloy in vitro Degrading experiment, coating sample soaking solution (SBF) pH value was at 60 days 8.5 are inside maintained at hereinafter, specimen surface has no obvious corrosion, and pH value just rises to 8.5 or more, 14 to naked magnesium alloy on day 4 It shows that coating has good long-term corrosion resistance by complete corrosion degradation.
Embodiment 2
A kind of preparation method of the Mg alloy surface nano hydroxyapatite coating based on ultrasound, comprising steps of
(1) AZ31 magnesium alloy is processed into 10mm × 10mm × 2mm block, successively with 800#、1200#、2000#SiC Sand paper polishing, is then successively cleaned by ultrasonic 10min, hot-air seasoning in acetone, deionized water, ethyl alcohol.
(2) compound concentration is the NaOH solution 50mL of 1.5mol/L.Magnesium alloy after polishing is impregnated in the solution in 80 1h is kept the temperature at DEG C, then cleans magnesium alloy sample with deionized water, is dried.
(3) with Ca (NO3)2The source Ca is provided, with Na2HPO4、(NH4)2HPO4Or NaH2PO4·12H2O provides the source P.Na2SiO3 By hydrolyzing to form Si (OH)4, OH is provided-, Na2SiO3Concentration be 0.0042mol/L；Then the source P aqueous solution is added dropwise to Ca After the mixing of source aqueous solution, then it is added dropwise to Na2SiO3In solution, the pH value of mixed solution is finally transferred to 6.3 with the dust technology of 1M, Magnetic agitation 1h.Wherein, Ca in mixed solution2+Concentration be 0.0215mol/L, PO4 3-Concentration be 0.0046mol/L.It weighs 100mL mixed solution is as coating solution.
(4) by NaOH, treated that magnesium alloy sample is soaked in coating solution, then is placed in ultrasonic reactor, exports Frequency is 40kHz ultrasonic wave, and coating solution is heated to 60 DEG C with peak power output, keeps 30min.Coating examination is taken out immediately Sample, with deionized water rinse, drying.
It is formed by coating prepared by such method by the lobate HA of a large amount of nano bamboos is interlaced, magnesium alloy coating sample exists AC impedance in simulated body fluid is 1.9kohmcm2, the AC impedance compared with magnesium alloy substrate improves nearly 3 times, corrosion electricity Current density is 16.31 μ A/cm2。
Embodiment 3
A kind of preparation method of the Mg alloy surface nano hydroxyapatite coating based on ultrasound, comprising steps of
(1) AZ80 magnesium alloy is processed into 10mm × 10mm × 2mm block, successively with 800#、1200#、2000#SiC Sand paper polishing, is then successively cleaned by ultrasonic 5min, hot-air seasoning in acetone, deionized water, ethyl alcohol.
(2) compound concentration is the NaOH solution 50mL of 1.5mol/L.Magnesium alloy after polishing is impregnated in the solution in 80 1h is kept the temperature at DEG C, then cleans magnesium alloy sample with deionized water, is dried.
(3) with Ca (NO3)2The source Ca is provided, with Na2HPO4、(NH4)2HPO4Or NaH2PO4·12H2O provides the source P.Na2SiO3 By hydrolyzing to form Si (OH)4, OH is provided-, Na2SiO3Concentration be 0.0052mol/L；Then the source P aqueous solution is added dropwise to Ca After the mixing of source aqueous solution, then it is added dropwise to Na2SiO3In solution, the pH value of mixed solution is finally transferred to 4.3 with the dust technology of 1M, Magnetic agitation 1h.Wherein, Ca in mixed solution2+Concentration be 0.0215mol/L, PO4 3-Concentration be 0.0046mol/L.It weighs 100mL mixed solution is as coating solution.
(4) by NaOH, treated that magnesium alloy sample is soaked in coating solution, then is placed in ultrasonic reactor, exports Frequency is 40kHz ultrasonic wave, and coating solution is heated to 50 DEG C with peak power output, keeps 30min.Coating examination is taken out immediately Sample, with deionized water rinse, drying.
Prepared HA coating is formed by the lobate HA of nano bamboo is closely interlaced in this way, and coating coats at this time Magnesium alloy AC impedance be 6.7 × 103ohm·cm2, corrosion electric current density is 3.795 × 10-6A/cm2, the corrosion resistant of coating It loses functional.
Embodiment 4
A kind of preparation method of the Mg alloy surface nano hydroxyapatite coating based on ultrasound, comprising steps of
(1) AZ80 magnesium alloy is processed into 10mm × 10mm × 2mm block, successively with 800#、1200#、2000#SiC Sand paper polishing, is then successively cleaned by ultrasonic 5min, hot-air seasoning in acetone, deionized water, ethyl alcohol.
(2) compound concentration is the NaOH solution 50mL of 1.5mol/L.Magnesium alloy after polishing is impregnated in the solution in 80 1h is kept the temperature at DEG C, then cleans magnesium alloy sample with deionized water, is dried.
(3) with Ca (NO3)2The source Ca is provided, with Na2HPO4、(NH4)2HPO4Or NaH2PO4·12H2O provides the source P.Na2SiO3 By hydrolyzing to form Si (OH)4, OH is provided-, after the source P aqueous solution is then added dropwise to the mixing of the source Ca aqueous solution, then it is added dropwise to Na2SiO3In solution, the pH value of mixed solution is finally transferred to 7.3 with the dust technology of 1M, magnetic agitation 1h.Wherein, mixed solution Middle Ca2+Concentration be 0.0215mol/L, PO4 3-Concentration be 0.0046mol/L.It is molten as coating to weigh 100mL mixed solution Liquid.
(4) by NaOH, treated that magnesium alloy sample is soaked in coating solution, then is placed in ultrasonic reactor, exports Frequency is 40kHz ultrasonic wave, and coating solution is heated to 50 DEG C with peak power output, keeps 2h.Coating sample is taken out immediately, With deionized water rinse, drying.
Prepared coating is formed by the lobate HA of nano bamboo is interlaced in this way, by coating sample and naked magnesium alloy External degradation test is carried out, coating sample soaking solution (SBF) pH value is maintained at 8.5 hereinafter, specimen surface has no in 60 days Obvious corrosion, and pH value just rises to 8.5 or more, 14 days by complete corrosion degradation to naked magnesium alloy on day 4.
Embodiment 5
A kind of preparation method of the Mg alloy surface nano hydroxyapatite coating based on ultrasound, comprising steps of magnesium is closed After the exposed surface base extraction of gold and contain Si (OH)4Hydroxyapatite coating layer solution coating is carried out under ultrasound environments Mg alloy surface nano hydroxyapatite coating is obtained after coating reaction.
It is described to contain Si (OH)4Hydroxyapatite coating layer solution in Ca2+Concentration be 0.01-0.03mol/L, PO4 3-'s Concentration is 0.004mol/L；It is described to contain Si (OH)4Hydroxyapatite coating layer solution pH value be 4；It is described to contain Si (OH)4 Hydroxyapatite coating layer solution in Si (OH)4Pass through Na2SiO3Hydrolysis generates, Na2SiO3Concentration be 0.002mol/L.
It is described to contain Si (OH)4Hydroxyapatite coating layer solution in generate Ca2+Raw material be Ca (NO3)2；Contain Si (OH)4Hydroxyapatite coating layer solution in generate PO4 3-Raw material be Na2HPO4。
The ultrasonic frequency of the ultrasound environments is 40kHZ.
The temperature of the coating cladding is 50 DEG C；The time of coating cladding is 10min.
The sodium hydroxide solution that the lye that the base extraction uses is 1mol/L for concentration；The time of base extraction is 0.5h；The temperature of base extraction is 60 DEG C.
The exposed surface of magnesium alloy is made using following steps: Mg alloy surface pre-processes: by Mg alloy surface polishing, clearly Wash, dry after obtain the exposed surface of magnesium alloy.
The cleaning step includes: that acetone, deionization are successively used in the surface of the magnesium alloy after polishing in ultrasound environments Water and ethyl alcohol cleaning, drying are spare；Further include washing step after coating cladding: the detergent that the washing step uses for Deionized water or ethyl alcohol；The number of the ASTM of the magnesium alloy is AZ31.
Embodiment 6
A kind of preparation method of the Mg alloy surface nano hydroxyapatite coating based on ultrasound, comprising steps of magnesium is closed After the exposed surface base extraction of gold and contain Si (OH)4Hydroxyapatite coating layer solution coating is carried out under ultrasound environments Mg alloy surface nano hydroxyapatite coating is obtained after coating reaction.
Contain Si (OH)4Hydroxyapatite coating layer solution in Ca2+Concentration be 0.03mol/L, PO4 3-Concentration be 0.006mol/L；It is described to contain Si (OH)4Hydroxyapatite coating layer solution pH value be 9；It is described to contain Si (OH)4Hydroxyl Si (OH) in apatite coating solution4Pass through Na2SiO3Hydrolysis generates, Na2SiO3Concentration be 0.006mol/L.
Contain Si (OH)4Hydroxyapatite coating layer solution in generate Ca2+Raw material be CaCl2；Contain Si (OH)4Hydroxyl PO is generated in base apatite coating solution4 3-Raw material be NaH2PO4。
The ultrasonic frequency of ultrasound environments is 45kHZ.
The temperature of the coating cladding is 70 DEG C；The time of coating cladding is 2h.
The sodium hydroxide solution that the lye that the base extraction uses is 2mol/L for concentration；The time of base extraction is 2h；The temperature of base extraction is 90 DEG C.
The exposed surface of magnesium alloy is made using following steps: Mg alloy surface pre-processes: by Mg alloy surface polishing, clearly Wash, dry after obtain the exposed surface of magnesium alloy.
Cleaning step include: in ultrasound environments by the surface of the magnesium alloy after polishing successively use acetone, deionized water and Ethyl alcohol cleaning, drying is spare；Further include washing step after coating cladding: the detergent that the washing step uses for go from Sub- water or ethyl alcohol；The number of the ASTM of the magnesium alloy is AZ91.
Embodiment 7
A kind of preparation method of the Mg alloy surface nano hydroxyapatite coating based on ultrasound, comprising steps of magnesium is closed After the exposed surface base extraction of gold and contain Si (OH)4Hydroxyapatite coating layer solution coating is carried out under ultrasound environments Mg alloy surface nano hydroxyapatite coating is obtained after coating reaction.
Contain Si (OH)4Hydroxyapatite coating layer solution in Ca2+Concentration be 0.02mol/L, PO4 3-Concentration be 0.005mol/L；It is described to contain Si (OH)4Hydroxyapatite coating layer solution pH value be 6；It is described to contain Si (OH)4Hydroxyl Si (OH) in apatite coating solution4Pass through Na2SiO3Hydrolysis generates, Na2SiO3Concentration be 0.004mol/L.
It is described to contain Si (OH)4Hydroxyapatite coating layer solution in generate Ca2+Raw material be Ca (NO3)2；Contain Si (OH)4Hydroxyapatite coating layer solution in generate PO4 3-Raw material be NH4H2PO4。
The ultrasonic frequency of the ultrasound environments is 40kHZ.
The temperature of the coating cladding is 60 DEG C；The time of coating cladding is 30min.
The sodium hydroxide solution that the lye that the base extraction uses is 1.5mol/L for concentration；The time of base extraction is 1h；The temperature of base extraction is 70 DEG C.
The exposed surface of the magnesium alloy is made using following steps: Mg alloy surface pre-processes: Mg alloy surface is beaten The exposed surface of magnesium alloy is obtained after mill, cleaning, drying.
The cleaning step includes: that acetone, deionization are successively used in the surface of the magnesium alloy after polishing in ultrasound environments Water and ethyl alcohol cleaning, drying are spare；Further include washing step after coating cladding: the detergent that the washing step uses for Deionized water or ethyl alcohol；The number of the ASTM of the magnesium alloy is AZ61.
Embodiment 8
A kind of preparation method of the Mg alloy surface nano hydroxyapatite coating based on ultrasound, comprising steps of magnesium is closed After the exposed surface base extraction of gold and contain Si (OH)4Hydroxyapatite coating layer solution coating is carried out under ultrasound environments Mg alloy surface nano hydroxyapatite coating is obtained after coating reaction.
It is described to contain Si (OH)4Hydroxyapatite coating layer solution in Ca2+Concentration be 0.025mol/L, PO4 3-Concentration For 0.0055mol/L；It is described to contain Si (OH)4Hydroxyapatite coating layer solution pH value be 7；It is described to contain Si (OH)4Hydroxyl Si (OH) in base apatite coating solution4Pass through Na2SiO3Hydrolysis generates, Na2SiO3Concentration be 0.005mol/L.
Contain Si (OH)4Hydroxyapatite coating layer solution in generate Ca2+Raw material be CaCl2；Contain Si (OH)4Hydroxyl PO is generated in base apatite coating solution4 3-Raw material be (NH4)2HPO4。
The ultrasonic frequency of the ultrasound environments is 45kHZ.
The temperature of the coating cladding is 65 DEG C；The time of coating cladding is 1.5h.
The sodium hydroxide solution that the lye that the base extraction uses is 1.8mol/L for concentration；The time of base extraction is 1.2h；The temperature of base extraction is 80 DEG C.
The exposed surface of the magnesium alloy is made using following steps: Mg alloy surface pre-processes: Mg alloy surface is beaten The exposed surface of magnesium alloy is obtained after mill, cleaning, drying.
The cleaning step includes: that acetone, deionization are successively used in the surface of the magnesium alloy after polishing in ultrasound environments Water and ethyl alcohol cleaning, drying are spare；Further include washing step after coating cladding: the detergent that the washing step uses for Deionized water or ethyl alcohol；The number of the ASTM of the magnesium alloy is AZ80.
Embodiment 9
A kind of Mg alloy surface nano hydroxyapatite coating, the coating are tight by the lobate hydroxyapatite of a large amount of nano bamboos It is close interlaced to form.
The leaf of bamboo shape hydroxyapatite width be 45nm, a length of 0.5 μm.
Embodiment 10
A kind of Mg alloy surface nano hydroxyapatite coating, the coating are tight by the lobate hydroxyapatite of a large amount of nano bamboos It is close interlaced to form.
The leaf of bamboo shape hydroxyapatite width be 55nm, a length of 3 μm.
Embodiment 11
A kind of Mg alloy surface nano hydroxyapatite coating, the coating are tight by the lobate hydroxyapatite of a large amount of nano bamboos It is close interlaced to form.
The leaf of bamboo shape hydroxyapatite width be 52nm, a length of 2.5 μm.
The present invention is not limited to above-mentioned optional embodiment, anyone can show that other are each under the inspiration of the present invention The product of kind form.Above-mentioned specific embodiment should not be understood the limitation of pairs of protection scope of the present invention, protection of the invention Range should be subject to be defined in claims, and specification can be used for interpreting the claims.

Claims (10)

1. a kind of preparation method of the Mg alloy surface nano hydroxyapatite coating based on ultrasound, it is characterised in that: including step It is rapid: by after the exposed surface base extraction of magnesium alloy with contain Si (OH)4Hydroxyapatite coating layer solution in ultrasound environments Mg alloy surface nano hydroxyapatite coating is obtained after lower progress coating coating reaction.
2. a kind of preparation side of Mg alloy surface nano hydroxyapatite coating based on ultrasound according to claim 1 Method, it is characterised in that: described to contain Si (OH)4Hydroxyapatite coating layer solution in Ca2+Concentration be 0.01-0.03mol/L, PO4 3-Concentration be 0.004-0.006mol/L；It is described to contain Si (OH)4Hydroxyapatite coating layer solution pH value be 4-9； It is described to contain Si (OH)4Hydroxyapatite coating layer solution in Si (OH)4Pass through Na2SiO3Hydrolysis generates, Na2SiO3Concentration For 0.002-0.006mol/L.
3. a kind of preparation side of Mg alloy surface nano hydroxyapatite coating based on ultrasound according to claim 2 Method, it is characterised in that: described to contain Si (OH)4Hydroxyapatite coating layer solution in generate Ca2+Raw material be Ca (NO3)2Or CaCl2One of or it is a variety of；Contain Si (OH)4Hydroxyapatite coating layer solution in generate PO4 3-Raw material be Na2HPO4、 NH4H2PO4、(NH4)2HPO4Or NaH2PO4One of or it is a variety of.
4. a kind of preparation side of Mg alloy surface nano hydroxyapatite coating based on ultrasound according to claim 1 Method, it is characterised in that: the ultrasonic frequency of the ultrasound environments is 40kHZ or 45kHZ.
5. a kind of preparation side of Mg alloy surface nano hydroxyapatite coating based on ultrasound according to claim 2 Method, it is characterised in that: the temperature of the coating cladding is 50 DEG C -70 DEG C；The time of coating cladding is 10min-2h.
6. a kind of preparation side of Mg alloy surface nano hydroxyapatite coating based on ultrasound according to claim 5 Method, it is characterised in that: the sodium hydroxide solution that the lye that the base extraction uses is 1mol/L-2mol/L for concentration；Lye The time of processing is 0.5h-2h；The temperature of base extraction is 60 DEG C -90 DEG C.
7. a kind of Mg alloy surface nano hydroxyapatite coating based on ultrasound described in -6 any one according to claim 1 Preparation method, it is characterised in that: the exposed surface of the magnesium alloy using following steps be made: Mg alloy surface pre-process: The exposed surface of magnesium alloy will be obtained after Mg alloy surface polishing, cleaning, drying.
8. a kind of preparation side of Mg alloy surface nano hydroxyapatite coating based on ultrasound according to claim 7 Method, it is characterised in that: the cleaning step include: in ultrasound environments by the surface of the magnesium alloy after polishing successively use acetone, Deionized water and ethyl alcohol cleaning, drying are spare；Further include washing step after the coating cladding: what the washing step used washes Washing agent is deionized water or ethyl alcohol；The number of the ASTM of the magnesium alloy is AZ31, AZ61, AZ80 or AZ91.
9. a kind of Mg alloy surface nano hydroxyapatite coating, it is characterised in that: the coating is by the lobate hydroxyl of a large amount of nano bamboos Base apatite is closely interlaced to be formed.
10. a kind of ultrasound according to claim 9 prepares Mg alloy surface nano hydroxyapatite coating, feature exists In: the leaf of bamboo shape hydroxyapatite width be 45-55nm, a length of 0.5-3 μm.
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