CN109295438A - A kind of method that hydro-thermal prepares Mg alloy surface micro-nano structure hydroxyapatite coating layer - Google Patents
A kind of method that hydro-thermal prepares Mg alloy surface micro-nano structure hydroxyapatite coating layer Download PDFInfo
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- CN109295438A CN109295438A CN201811111658.4A CN201811111658A CN109295438A CN 109295438 A CN109295438 A CN 109295438A CN 201811111658 A CN201811111658 A CN 201811111658A CN 109295438 A CN109295438 A CN 109295438A
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- 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
- C23C18/02—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 by thermal decomposition
- C23C18/12—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 by thermal decomposition characterised by the deposition of inorganic material other than metallic material
- C23C18/1204—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 by thermal decomposition characterised by the deposition of inorganic material other than metallic material inorganic material, e.g. non-oxide and non-metallic such as sulfides, nitrides based compounds
- C23C18/1208—Oxides, e.g. ceramics
- C23C18/1216—Metal oxides
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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
- A61L27/28—Materials for coating prostheses
- A61L27/30—Inorganic materials
- A61L27/32—Phosphorus-containing materials, e.g. apatite
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- 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
- C23C18/02—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 by thermal decomposition
- C23C18/04—Pretreatment of the material to be coated
Abstract
The present invention relates to a kind of methods that hydro-thermal prepares Mg alloy surface micro-nano structure hydroxyapatite coating layer.Surface polishing treatment is carried out to magnesium alloy first: Mg alloy surface being polished, is then successively cleaned by ultrasonic in acetone, deionized water, ethyl alcohol, is dried；Then the magnesium alloy after polishing treatment is immersed in the NaOH solution that concentration is 1~2mol/L, keeps the temperature in 60~90 DEG C of baking oven, is then cleaned with deionized water, dried；Finally the pretreated magnesium alloy sample of NaOH is put into the autoclave for filling hydro-thermal reaction solution, reaction kettle is put into 100~140 DEG C of baking oven and is kept the temperature, taken out after cooling, cleaned and dry.The HA coating that micro-nano structure is made is divided into two layers, and the micron order flower clusters structure that upper layer is made of nano bar-shape can see by the gap between cluster, and lower layer is the nano bar-shape structure of even compact.This coating has long-term corrosion resistance, has biggish business promotion value.
Description
Technical field
The present invention relates to a kind of to prepare the hydrothermal method with the hydroxyapatite coating layer of micro-nano structure on magnesium alloy, belongs to
In degradable magnesium alloy implant surface technical field of modification.
Background technique
The density and yield strength and natural bone density of magnesium alloy are very close, and elasticity modulus is also far below titanium alloy, no
Become rusty steel etc., therefore when as implantation material, " stress shielding " effect can be effectively relieved.And magnesium alloy can drop in human body
Solution promotes symphysis and growth, is the bio-medical material of great potential.But corrosion resistance of magnesium alloy is poor, is easy hair
Raw degradation causes just to have lost intrinsic mechanical property in damaged tissues healing completely not yet.And magnesium alloy
Chemical composition and bone tissue difference are larger, cannot form synostosis with bone tissue, influence organization healing effect.And hydroxy-apatite
The chemical stability of stone (HA) is high, is the main inorganic composition of skeleton.It can be improved by the HA coating of matrix of magnesium alloy
Corrosion resistance of the magnesium alloy in physiological environment, the chemical bonding of enhancing and bone tissue, it is ensured that the early stage of implant stablizes.Cause
This, is carried out the preparation of Mg alloy surface HA coating, becomes the important way for being reduced its drawback using its advantage, can effectively improve
The corrosion resistance of implant.
Has relevant report in metal surface preparation HA coating using hydro-thermal method.Hydro-thermal method utilizes closed reactor, in height
Indissoluble or insoluble matter can be made to dissolve and recrystallize under the conditions of pressure, high temperature etc., can not influenced using the method
In the case where host material performance, comparatively dense coating is formed, and coating binding force and corrosion resistance are preferable, can also passed through
Optimize reaction condition regulation coating structure, pattern and performance.For example, Indonesia patent KR20030087664 provide it is anti-with hydro-thermal
The method that HA film should be prepared on titanium surface is dissolved in hydrochloric acid using HA powder as biocompatible materials, then closes titanium
Gold, which is put into solution, carries out hydro-thermal reaction preparation HA coating.(the Crystalline such as Katarzyna Suchanek
hydroxyapatite coatings synthesized under hydrothermal conditions on modified
51 (2015) 57-63 of titanium substrates.Materials Science and Engineering C) it reports
At Ca (EDTA)2-(NH4)2HPO4In solution, the symmetrical HA acicular crystal of six sides has been synthesized on titanium alloy substrate by hydro-thermal method
Coating.Equally, (the Characterization of hydroxyapatite coatings deposited such as Daihua He
by hydrothermal electrochemical method on NaOH immersed Ti6Al4V.Journal of
672 (2016) 336-343 of Alloys and Compounds) it reports, it is handled using hydro-thermal method in NaOH solution
HA coating is prepared on Ti6Al4V.It, being capable of rapid induction phosphorus after coating modified Ti6Al4V sample is impregnated 3 days in SBF
The formation of lime stone significantly improves the bioactivity of titanium alloy.Hydro-thermal method also has phase in the research of Mg alloy surface prepares coating
Close report.China Patent No. CN108004527A, which is reported, prepares the painting of zinc doping modified HA in Mg alloy surface using hydro-thermal method
Layer, the coating have nano flower-like structure and even compact, effectively improve biocompatibility.In addition, 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) it reports and is combined using micro-arc oxidation and hydro-thermal method, nano bar-shape HA is prepared on magnesium alloy
Coating, coating is fine and close, morphology controllable.But existing document and patent report in relation to coating modified magnesium alloy, not to institute
The long-term corrosion resistance for preparing material can be carried out research.And as degradable bone renovating material, 10 should be kept in simulated body fluid
There are preferable mechanical property and no heavy corrosion, time needed for being just able to satisfy repair of damaged tissues in week.Bo Li et al. system
After standby sample impregnates the 5th day in simulated body fluid, pH value has risen to 9 or more, is not able to satisfy long-term corrosion resistance
It is required that.
Coating surface microstructure directly affects adherency, proliferation and the differentiation of the biocompatibility and cell of implant.By
The inspiration of natural bony structure, micro-nano structure receive significant attention.Research shows that: the suitable micrometer structure of implant surfaces or nanometer
Structure goes out positive effect to the behavior expression of cell, and has both the surface of micron and nanometer hierarchical structure with the association of micro-nano structure
Same effect can advantageously promote Integrated implant.Such as (the Effects of Superimposed Micro/ such as By Teng Wang
Nano-Structured Titanium Alloy Surface on Cellular Behaviors In Vitro) it reports
The micro-nano structure of titanium alloy surface provides beneficial interface environments for the growth of MC3T3, helps to induce its differentiation, is to improve
The effective ways of titanium alloy biocompatibility.(the Boron-containing micro/nano- such as Dawen Ying
structured TiO2/bioceramics coatings with modulatory effects on SaOS-2cell
Response.Materials Letters 228 (2018) 29-32) report, it is prepared on Titanium base using micro-arc oxidation
Micron order TiO2Coating, then Hydrothermal Growth boracic nanometer rods, then it is transformed into nano particle after being heat-treated.This micro-nano structure
Coating can promote adherency, proliferation and the differentiation of SaOS-2 cell, enhance osteogenic action.But need differential arc oxidation and hydro-thermal method
It combines, and carries out Post isothermal treatment, experimentation is complicated.China Patent No. CN106792238A is reported using differential arc oxidation
Micron-sized magnesium oxide layer and the hydro-thermal process in the alkaline solution containing silicon source are constructed in Mg alloy surface, re-forms nanometer
The hydroxide layer of grade, so that surface has micro-nano structure, biocompatibility is good.But for micro-arc oxidation, one
As the coating for preparing it is not fine and close enough, it is limited to the protective effect of magnesium alloy substrate, be unfavorable for long-term corrosion-resistant.So far a step is used
Hydro-thermal method Mg alloy surface prepare micro-nano structure HA research and patent report it is very few, especially in relation to micro-nano structure HA coating
The research for coating the long-term corrosion resistance of magnesium alloy materials has not been reported.
Summary of the invention
In order to solve the problems, such as that existing preparation method exists, the present invention provides a kind of hydro-thermal and prepares Mg alloy surface micro-nano knot
The method of structure hydroxyapatite coating layer.By applying chelating agent in hydrothermal solution, induction HA crystal takes the invention along C axis direction
It to growth, and then realizes the micro-nano structure of HA coating, improves the bioactivity of Mg alloy surface, provided for a long time for Biological magnesium alloy
Protective effect.
It can be achieved through the following technical solutions to achieve the above object:
A kind of hydrothermal preparing process of Mg alloy surface micro-nano structure HA coating, includes the following steps:
1) magnesium alloy surface polishing processing: being polishing to 1200~2000 mesh for Mg alloy surface, then successively in acetone, go
It is cleaned by ultrasonic 5~10min, drying in ionized water, ethyl alcohol；
2) Mg alloy surface pre-processes: it is molten that the magnesium alloy after polishing treatment is immersed in the NaOH that concentration is 1~2mol/L
It in liquid, keeps the temperature in 60~90 DEG C of baking oven, is then cleaned with deionized water, dry；
3) the pretreated magnesium alloy sample of NaOH is put into the autoclave for filling hydro-thermal reaction solution, will be reacted
Kettle is put into 100~140 DEG C of baking oven and keeps the temperature, and takes out after cooling, and detergent is cleaned and dried.
0.5~2h is preferably kept the temperature in the step 2).
Preferred hydro-thermal reaction solution is in the step 3): with EDTA2NaCa for the source Ca, with KH2PO4、(NH4)2HPO4Or
NaH2PO4For the source P, the source Ca and the source P are added in distilled water and prepare solution；Then with alkaline solution by the pH value tune of mixed solution
To 6~11,1~2h of magnetic agitation；Wherein, Ca in mixed solution2+Concentration be 0.1~0.25mol/L, PO4 3-Concentration be
0.1~0.25mol/L.
One of the preferred NaOH of alkaline solution for adjusting pH value, ammonium hydroxide, concentration are 1~10mol/L.
12~48h is kept the temperature in the step 3) preferably in 100~140 DEG C of baking oven.
The preferred deionized water of detergent or alcohol in the step 3).
In conclusion core of the invention is that magnesium alloy forms Mg (OH) by NaOH pretreatment rear surface2Protective layer,
The generation for inhibiting hydrogen during carrying out hydro-thermal method and preparing HA coating, makes coating not generate stomata during the preparation process and split
The defects of line.On the one hand EDTA2NaCa in hydrothermal solution discharges Ca as calcium source2+It is crystal in specimen surface into solution
Growth provides enough driving forces；On the other hand constantly by Ca2+Be sequestered in EDTA, this chelating agent and metal ion it is strong
Strong effect, by induced crystal along specific direction oriented growth.It ensure that the densification for generating in water-heat process and there is micro-nano structure
HA coating, and long-term protective effect can be provided for magnesium alloy.
Compared with existing technology of preparing, the present invention has the advantages that
(1) present invention is prepared for the HA coating of Mg alloy surface micro-nano structure, and coating is divided into upper layer and lower layer, and lower layer is fine and close
Nano bar-shape structure (rod-like section is about 50~200nm, and length is about 1~2 μm), upper layer is by the rodlike micron formed
Grade flower clusters structure (flower-shaped diameter is about 2~4 μm)；This micro-nano structure HA cluster has biggish specific surface area, favorably
It adheres to and grows in coating surface in osteoblast, therefore there is good bioactivity.
(2) HA coating prepared by the present invention, electro-chemical test show that its AC impedance is about 110kohmcm2, corrosion electricity
Current density is 3.9 × 10-7A/cm2, short-term corrosion resistance is good.
(3) effect for passing through EDTA2NaCa chelating agent, can induce HA crystal to grow along C axis oriented, it is microcosmic to influence coating
Structure.
(4) when carrying out long period of soaking in simulated body fluid, the pH value of solution can be held in 7.2~7.4 within 10 weeks
Between, specimen surface does not also obviously corrode.And pH value just reaches interior meeting in 8 or more, 1 week by serious rotten to naked magnesium alloy on day 3
Erosion, and most of coatings also only have preferable protective effect within 4 weeks.So the HA coating in the invention is long-term corrosion-resistant
Effect aspect has great advantage.
(5) present invention repeatability is high, and experimentation equipment is simple, for the magnesium alloy sample of any shape, size,
HA coating can be prepared on its surface.
Hydro-thermal method disclosed in this invention is a kind of very economical, the high technique of repeatability.Prepared has micro-nano
The HA coating of structure has big promotion at long-term corrosion-resistant aspect, has biggish business promotion value.
Detailed description of the invention
The magnesium alloy and naked magnesium alloy that Fig. 1 is the cladding of HA coating prepared by the embodiment of the present invention 1 are in simulated body fluid
Ac impedance spectroscopy.
Fig. 2 is coating morphology SEM photograph prepared by the embodiment of the present invention 1:
Wherein Fig. 2 (a) figure is the whole pattern of coating, and Fig. 2 (b) and Fig. 2 (c) figure are respectively the partial enlargement of Fig. 2 (a) figure
Figure；Fig. 2 (b) figure is upper layer coating, and the micron order flower clusters structure with rodlike composition, Fig. 2 (c) figure is lower layer's coating, tool
There is fine and close nano bar-shape structure.
Fig. 3 is the XRD spectrum of coating prepared by the embodiment of the present invention 1.
Fig. 4 is the pH value result figure of coating and naked magnesium alloy during long period of soaking prepared by the embodiment of the present invention 1.
Specific embodiment
The present invention is further explained and is illustrated below 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.
It is as follows to summarize preparation step:
1) sand paper used for magnesium alloy of certain size and shape magnesium alloy surface polishing processing: is polishing to 1200~2000
Then mesh is successively cleaned by ultrasonic 10min in acetone, deionized water, ethyl alcohol, drying.
2) Mg alloy surface pre-processes: compound concentration is the NaOH solution of 1~2mol/L, and the magnesium alloy after polishing is impregnated
It in the above solution in 60~90 DEG C of 0.5~2h of heat preservation, is then cleaned, is dried with deionized water.
3) preparation of calcium phosphorus reagent: with EDTA2NaCa for the source Ca, with KH2PO4、(NH4)2HPO4Or NaH2PO4For the source P according to
Secondary be added in a certain amount of distilled water prepares solution；Then the pH value of mixed solution is transferred to 6~11 with alkaline solution, magnetic force stirs
Mix 1h；Wherein, Ca in mixed solution2+Concentration be 0.1~0.25mol/L, PO4 3-Concentration be 0.1~0.25mol/L.
4) preparation of HA coating: pretreated magnesium alloy sample is put into the autoclave for filling calcium phosphorus solution,
Reaction kettle is put into 12~48h of heat preservation in 100~140 DEG C of baking oven, is taken out after cooling, is cleaned and dried with deionized water.
Embodiment 1
(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 25mL 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 EDTA2NaCa for the source Ca, with KH2PO4It is sequentially added for the source P and prepares solution in distilled water；Then 2mol/ is used
The pH value of mixed solution is transferred to 9 by the NaOH solution of L, magnetic agitation 1h；Wherein, Ca in mixed solution2+Concentration and PO4 3-'s
Concentration is 0.20mol/L, measures 75ml solution and pours into autoclave.
(4) by NaOH, treated that magnesium alloy sample is put into the autoclave for filling reagent, and reaction kettle is put into 120
DEG C baking oven in keep the temperature for 24 hours, taken out after cooling, cleaned and dried with deionized water.
Ac impedance spectroscopy such as Fig. 1 institute of the magnesium alloy and naked magnesium alloy of prepared HA coating cladding in simulated body fluid
Show, AC impedance is about 110kohmcm2, it is known that its short-term corrosion resistance is good.The coating morphology SEM photograph of preparation
As shown in Fig. 2, wherein Fig. 2 (a) is the whole pattern of coating, it is divided into upper layer and lower layer.Upper layer is as the nanometer as shown in Fig. 2 (b)
The micron order flower clusters structure of rodlike composition, passes through the gap between flower clusters, it can be seen that lower layer shown in Fig. 2 (c),
For the nano bar-shape structure that arrangement is fine and close.The XRD spectrum of prepared coating such as Fig. 3, the object of synthesis are mutually Mg (OH)2And HA.Fig. 4
For the pH value result figure of prepared sample and naked magnesium alloy during long period of soaking, it can be seen that prepared sample is in analogue body
When impregnating 10 weeks in liquid, pH value is maintained essentially between 7.2~7.4, and naked magnesium alloy pH value after impregnating 1 week has risen to
11.5 or more, illustrate that the long-term corrosion resistance of coating is good.
Embodiment 2
(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 25mL of 1.5mol/L.Magnesium alloy impregnates in the solution in 80 DEG C after polishing
1h is kept the temperature, then cleans magnesium alloy sample with deionized water, is dried.
(3) with EDTA2NaCa for the source Ca, with NaH2PO4It is sequentially added for the source P and prepares solution in distilled water；Then it uses
The pH value of mixed solution is transferred to 9 by the NaOH solution of 2mol/L, magnetic agitation 1h；Wherein, Ca in mixed solution2+Concentration and
PO4 3-Concentration be 0.2mol/L.
(4) by NaOH, treated that magnesium alloy sample is put into the autoclave for filling reagent, and reaction kettle is put into 100
DEG C baking oven in keep the temperature 48h, taken out after cooling, cleaned and dried with deionized water.
According to said method prepared duplex coating, upper layer flower clusters integral diameter is about 2~3 μm, lower layer's nano bar-shape
Length is about 1~2 μm.Corrosion electric current density of the magnesium alloy of this coating cladding in simulated body fluid is 5.66 × 10-7A/cm2,
Corrosion electric current density compared with magnesium alloy substrate has dropped 5 orders of magnitude, it is seen that figure layer has good protective effect for magnesium alloy.
Embodiment 3
(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 25mL of 1.5mol/L.Magnesium alloy impregnates in the solution in 80 DEG C after polishing
1h is kept the temperature, then cleans magnesium alloy sample with deionized water, is dried.
(3) with EDTA2NaCa for the source Ca, with (NH4)2HPO4It is sequentially added for the source P and prepares solution in distilled water；Then it uses
The pH value of mixed solution is transferred to 9 by the NaOH solution of 2mol/L, magnetic agitation 1h；Wherein, Ca in mixed solution2+Concentration be
0.25mol/L, PO4 3-Concentration be 0.1mol/L, measure 75ml solution pour into autoclave.
(4) by NaOH, treated that magnesium alloy sample is put into the autoclave for filling reagent, and reaction kettle is put into 120
DEG C baking oven in keep the temperature for 24 hours, taken out after cooling, cleaned and dried with deionized water.
Prepared HA micro-nano structure coating in this way, lower layer's rod-like section is about 100~200nm, and length is about
It is 1~2 μm, about 2~4 μm of upper layer flower clusters diameter.The AC impedance of the magnesium alloy of coating cladding is at this time
90.2kohm·cm2, corrosion electric current density is 7.36 × 10-7A/cm2, the corrosion resistance of coating is good.
Embodiment 4
(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 25mL of 1.5mol/L.Magnesium alloy impregnates in the solution in 80 DEG C after polishing
1h is kept the temperature, then cleans magnesium alloy sample with deionized water, is dried.
(3) with EDTA2NaCa for the source Ca, with KH2PO4It is sequentially added for the source P and prepares solution in distilled water；Then 2mol/ is used
The pH value of mixed solution is transferred to 9 by the NaOH solution of L, magnetic agitation 1h；Wherein, Ca in mixed solution2+Concentration and PO4 3-'s
Concentration is 0.2mol/L, measures 75ml solution and pours into autoclave.
(4) by NaOH, treated that magnesium alloy sample is put into the autoclave for filling reagent, and reaction kettle is put into 140
DEG C baking oven in keep the temperature 12h, taken out after cooling, cleaned and dried with deionized water.
Two layers prepared of micro-nano structure coating in this way, nano bar-shape section is about 50~150nm, and length is about
1.5 μm, about 3 μm of upper layer flower clusters integral diameter.The AC impedance of the magnesium alloy of coating cladding reaches 100.2kohm
cm2.After sample impregnates 10 weeks in simulated body fluid, pH value be may remain between 7.2~7.4, and magnesium alloy bare die is impregnating
The 3rd day, pH value is corroded completely after just having reached 8 or more, 2 weeks.
Claims (8)
1. a kind of method that hydro-thermal prepares Mg alloy surface micro-nano structure hydroxyapatite coating layer, it is characterized in that including following step
It is rapid:
1) magnesium alloy surface polishing processing: Mg alloy surface is polished, then successively ultrasonic in acetone, deionized water, ethyl alcohol
Clean 5~10min, drying；
2) Mg alloy surface pre-processes: the magnesium alloy after polishing treatment being immersed in the NaOH solution that concentration is 1~2mol/L
It keeps the temperature in 60~90 DEG C of baking oven, is then cleaned with deionized water, dried；
3) the pretreated magnesium alloy sample of NaOH is put into the autoclave for filling hydro-thermal reaction solution, reaction kettle is put
Enter and kept the temperature in 100~140 DEG C of baking oven, taken out after cooling, cleaned and dries.
2. the method as described in claim 1, it is characterized in that Mg alloy surface is polishing to 1200~2000 mesh in the step 1).
3. the method as described in claim 1, it is characterized in that keeping the temperature 0.5~2h in the step 2).
4. the method as described in claim 1, it is characterized in that in the step 3) in 100~140 DEG C of baking oven heat preservation 12~
48h。
5. the method as described in claim 1, it is characterized in that preferred hydro-thermal reaction solution is in the step 3): with
EDTA2NaCa is the source Ca, with KH2PO4、(NH4)2HPO4Or NaH2PO4It is molten by being prepared in the source Ca and the source P addition distilled water for the source P
Liquid；Then the pH value of mixed solution is transferred to 6~11 with alkaline solution, 1~2h of magnetic agitation；Wherein, Ca in mixed solution2+'s
Concentration is 0.1~0.25mol/L, PO4 3-Concentration be 0.1~0.25mol/L.
6. method as claimed in claim 5, it is characterized in that one of the preferred NaOH of the alkaline solution, ammonium hydroxide, dense
Degree is 1~10mol/L.
7. the method as described in claim 1, it is characterized in that magnesium alloy is one kind of AZ31, AZ80 or AZ91.
8. the method as described in claim 1, it is characterized in that detergent is deionized water or alcohol in the step 3).
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111420128A (en) * | 2020-02-28 | 2020-07-17 | 天津大学 | Preparation method of super-hydrophobic hydroxyapatite/stearic acid composite coating with antibacterial adhesion |
| CN111973812A (en) * | 2019-05-21 | 2020-11-24 | 上海交通大学 | Hydroxyapatite coating with bioactivity and hierarchical structure on surface of degradable magnesium-based endosteal implant 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 |
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| CN107789665A (en) * | 2017-10-31 | 2018-03-13 | 重庆理工大学 | A kind of preparation method of the super-hydrophobic hydroxyapatite film layer of Mg alloy surface |
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| CN111973812A (en) * | 2019-05-21 | 2020-11-24 | 上海交通大学 | Hydroxyapatite coating with bioactivity and hierarchical structure on surface of degradable magnesium-based endosteal implant and preparation method thereof |
| CN111973812B (en) * | 2019-05-21 | 2022-06-28 | 上海交通大学 | Hydroxyapatite coating with bioactivity and hierarchical structure on surface of degradable magnesium-based endosteal implant 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 |
| CN111420128A (en) * | 2020-02-28 | 2020-07-17 | 天津大学 | Preparation method of super-hydrophobic hydroxyapatite/stearic acid composite coating with antibacterial adhesion |
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