CN109758605A - Mg alloy surface fine acicular hydroxyapatite micro nano structure coating and preparation method - Google Patents
Mg alloy surface fine acicular hydroxyapatite micro nano structure coating and preparation method Download PDFInfo
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- CN109758605A CN109758605A CN201910137298.3A CN201910137298A CN109758605A CN 109758605 A CN109758605 A CN 109758605A CN 201910137298 A CN201910137298 A CN 201910137298A CN 109758605 A CN109758605 A CN 109758605A
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- fine acicular
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- 229910000861 Mg alloy Inorganic materials 0.000 title claims abstract description 93
- 229910052588 hydroxylapatite Inorganic materials 0.000 title claims abstract description 49
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 title claims abstract description 49
- 239000011248 coating agent Substances 0.000 title claims abstract description 37
- 238000000576 coating method Methods 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 239000002086 nanomaterial Substances 0.000 title claims abstract description 21
- 238000004070 electrodeposition Methods 0.000 claims abstract description 38
- 239000011247 coating layer Substances 0.000 claims abstract description 27
- 239000000758 substrate Substances 0.000 claims abstract description 22
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000003792 electrolyte Substances 0.000 claims abstract description 13
- 239000008151 electrolyte solution Substances 0.000 claims abstract description 13
- 238000010438 heat treatment Methods 0.000 claims abstract description 11
- 239000003513 alkali Substances 0.000 claims abstract description 8
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 8
- 230000001105 regulatory effect Effects 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- 238000000151 deposition Methods 0.000 claims description 17
- 239000008367 deionised water Substances 0.000 claims description 15
- 229910021641 deionized water Inorganic materials 0.000 claims description 15
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 14
- 229910019142 PO4 Inorganic materials 0.000 claims description 13
- 238000005498 polishing Methods 0.000 claims description 13
- 230000008021 deposition Effects 0.000 claims description 12
- 239000011575 calcium Substances 0.000 claims description 11
- 159000000007 calcium salts Chemical class 0.000 claims description 10
- 239000010410 layer Substances 0.000 claims description 9
- 239000011159 matrix material Substances 0.000 claims description 9
- 239000010452 phosphate Substances 0.000 claims description 9
- 238000013019 agitation Methods 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 238000004062 sedimentation Methods 0.000 claims description 7
- 238000005303 weighing Methods 0.000 claims description 7
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical group [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 6
- 239000004576 sand Substances 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 5
- 239000007836 KH2PO4 Substances 0.000 claims description 4
- 239000001110 calcium chloride Substances 0.000 claims description 4
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 4
- 229910000402 monopotassium phosphate Inorganic materials 0.000 claims description 4
- -1 phosphate dihydrogen salt Chemical class 0.000 claims description 4
- 239000012266 salt solution Substances 0.000 claims description 4
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 claims description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 2
- 229910045601 alloy Inorganic materials 0.000 claims description 2
- 239000000956 alloy Substances 0.000 claims description 2
- 229940062672 calcium dihydrogen phosphate Drugs 0.000 claims description 2
- 229910001424 calcium ion Inorganic materials 0.000 claims description 2
- 229910000389 calcium phosphate Inorganic materials 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-M dihydrogenphosphate Chemical compound OP(O)([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-M 0.000 claims description 2
- 239000011777 magnesium Substances 0.000 claims description 2
- 238000007781 pre-processing Methods 0.000 claims description 2
- 229910000162 sodium phosphate Inorganic materials 0.000 claims description 2
- 238000002604 ultrasonography Methods 0.000 claims description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-L Phosphate ion(2-) Chemical class OP([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-L 0.000 claims 1
- 229960005069 calcium Drugs 0.000 claims 1
- 229910052791 calcium Inorganic materials 0.000 claims 1
- 238000002242 deionisation method Methods 0.000 claims 1
- 238000005137 deposition process Methods 0.000 claims 1
- 239000007788 liquid Substances 0.000 claims 1
- 229910052749 magnesium Inorganic materials 0.000 claims 1
- 239000000203 mixture Substances 0.000 claims 1
- 238000009938 salting Methods 0.000 claims 1
- 239000004575 stone Substances 0.000 claims 1
- 238000005260 corrosion Methods 0.000 abstract description 8
- 230000007797 corrosion Effects 0.000 abstract description 7
- 239000007943 implant Substances 0.000 abstract description 6
- 238000012986 modification Methods 0.000 abstract description 4
- 230000004048 modification Effects 0.000 abstract description 4
- 239000007800 oxidant agent Substances 0.000 abstract description 2
- 230000001590 oxidative effect Effects 0.000 abstract description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 19
- 239000000243 solution Substances 0.000 description 13
- 210000000988 bone and bone Anatomy 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 229910017677 NH4H2 Inorganic materials 0.000 description 4
- MWKXCSMICWVRGW-UHFFFAOYSA-N calcium;phosphane Chemical compound P.[Ca] MWKXCSMICWVRGW-UHFFFAOYSA-N 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000011282 treatment Methods 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- ZQBZAOZWBKABNC-UHFFFAOYSA-N [P].[Ca] Chemical compound [P].[Ca] ZQBZAOZWBKABNC-UHFFFAOYSA-N 0.000 description 2
- 238000000627 alternating current impedance spectroscopy Methods 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000010894 electron beam technology Methods 0.000 description 2
- 230000035876 healing Effects 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 230000000051 modifying effect Effects 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 229910014497 Ca10(PO4)6(OH)2 Inorganic materials 0.000 description 1
- 241000186216 Corynebacterium Species 0.000 description 1
- 206010061218 Inflammation Diseases 0.000 description 1
- 244000137852 Petrea volubilis Species 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229910001069 Ti alloy Inorganic materials 0.000 description 1
- 206010060872 Transplant failure Diseases 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910052586 apatite Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- CGMRCMMOCQYHAD-UHFFFAOYSA-J dicalcium hydroxide phosphate Chemical compound [OH-].[Ca++].[Ca++].[O-]P([O-])([O-])=O CGMRCMMOCQYHAD-UHFFFAOYSA-J 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000002513 implantation Methods 0.000 description 1
- 230000004054 inflammatory process Effects 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- VSIIXMUUUJUKCM-UHFFFAOYSA-D pentacalcium;fluoride;triphosphate Chemical compound [F-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O VSIIXMUUUJUKCM-UHFFFAOYSA-D 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- GNSKLFRGEWLPPA-UHFFFAOYSA-M potassium dihydrogen phosphate Chemical compound [K+].OP(O)([O-])=O GNSKLFRGEWLPPA-UHFFFAOYSA-M 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000007751 thermal spraying Methods 0.000 description 1
- 238000004506 ultrasonic cleaning Methods 0.000 description 1
Landscapes
- Materials For Medical Uses (AREA)
Abstract
The invention belongs to degradable magnesium alloy implant surface technical field of modification, and in particular to Mg alloy surface fine acicular hydroxyapatite micro nano structure coating and preparation method thereof.Preparation method is the following steps are included: pretreated magnesium alloy substrate is soaked in electrochemical deposition electrolyte solution, using platinum electrode as cathode, magnesium alloy is as anode, connect D.C. regulated power supply, carry out electrochemical deposition, alkali heat-treatment is carried out later, obtains Mg alloy surface hydroxyapatite coating layer.The electrochemical deposition electrolyte prescription that the present invention uses is simple, without adding any promotor or oxidant, and without adjusting electrolyte ph；Using the electrochemical deposition mode of low temperature, low current density, easily controllable, cost is relatively low；Prepared hydroxyapatite coating layer even compact, purity is higher, corrosion resistance and good, and the micro nano structure with fine acicular, is conducive to cell in the adherency and growth of coating surface, that improves magnesium alloy implant is implanted to power.
Description
Technical field
The invention belongs to degradable magnesium alloy implant surface technical field of modification, and in particular to Mg alloy surface fine acicular
Hydroxyapatite micro nano structure coating and preparation method.
Background technique
Magnesium alloy has good biocompatibility and bioactivity and excellent as a kind of biological and medicinal implant material
Biodegradability.Compared with the metal materials such as the common cobalt-base alloys of clinical medicine, stainless steel, titanium alloy, magnesium alloy
Elasticity modulus and density are all closest with people's bone, are a kind of ideal bone renovating materials.But since magnesium alloy is in physiologic ring
Corrosion resistance under border is poor, and degradation rate is too fast, often will cause implant site local environment pH value is excessively high and hydrogen
Short-term a large amount of releases so that implant site healing slow is even resulted in graft failure so as to cause inflammation generation；In addition, too fast
Degradation speed keep its mechanical properties decrease during one's term of military service very fast, be not able to satisfy the time requirement of bone tissue healing.Therefore, right
It is mesh that medical magnesium alloy, which carries out surface modification treatment to improve its corrosion resistance and biocompatibility in physiological environment,
One of the important directions of preceding research.
Hydroxyapatite (Ca10(PO4)6(OH)2, Hydroxyapatite, HAp) be skeleton and tooth main nothing
Machine component part has excellent bioactivity and biocompatibility, it is considered to be a kind of most potential human body planting body replaces
For material.But because of the disadvantages of HAp brittleness is big, and intensity is low, and toughness is poor, it is largely limited at human bearing position
Using.Hydroxyapatite coating layer is prepared in Mg alloy surface, the mechanical property of magnesium alloy and the biology of hydroxyapatite can be made
Activity combines.And keyness bonding can be formed with the bone tissue of human body in a short time after being implanted into human body, can also stablize and drop
The corrosion rate of low magnesium alloy preferably plays important function of the magnesium alloy in Bone Defect Repari treatment, therefore in Mg alloy surface
Hydroxyapatite coating layer is prepared with good development prospect.
The method that people have developed a variety of Magnesiumalloy surface modifyings at present, common surface coating means mainly have:
Sol-gal process, laser melting coating, differential arc oxidation, thermal spraying and electrochemical deposition etc..Wherein, electrochemical deposition method is due to deposition temperature
It spends lower and can be deposited on complicated workpiece, therefore receive significant attention.Chinese invention patent (application No. is
CN201710881395) " a kind of preparation method of medical magnesium alloy surface active coating " discloses a kind of hydro-thermal electrochemical deposition
Method uses the anti-of high temperature and pressure in the preparation method of medical magnesium alloy surface deposition hydroxyapatite coating layer during the preparation process
Condition is answered, the HAp coating of preparation is corynebacterium, and purity is higher；Chinese invention patent (application No. is CN201510310437) " one
The surface modifying method of kind medical magnesium alloy " discloses a kind of method of pulse electrodeposition in the medical magnesium alloy for having remelted layer
The surface of material prepares hydroxyapatite coating layer, completes the modification of medical magnesium alloy surface, uses high-current pulsed electron beam first
Medical magnesium alloy matrix surface is irradiated, hydroxyapatite coating layer is then deposited on surface using electrodeposition method,
So that HAp coating is formed mechanical closing component structure using the rough surface generated in high-current pulsed electron beam irradiation process, improves painting
The bond strength and biocompatibility of layer and matrix；" one kind has Chinese invention patent (application No. is CN201510125339)
The method of high bioactivity and low degradation rate biologic medical magnesium or Mg alloy surface electrochemical treatments " discloses a kind of by the differential of the arc
Oxidation and electrochemical deposition combine the method for preparing HAp composite coating, improve the corrosion resistance and bioactivity of material.
But the above-mentioned method for preparing hydroxyapatite coating layer in medical magnesium alloy surface often has that the device is complicated, item
Part requires height, is formulated the problems such as cumbersome, the reaction condition of high temperature and pressure is such as usually required during preparation, adulterate other adds
Add agent to improve coating performance, electrochemical deposition etc. is carried out using pulse current using electrochemical workstation；Some also needs
It first carries out surface to magnesium alloy before electrochemical deposition to be modified, so that process is complex.
Summary of the invention
It is an object of the invention to overcome preparation temperature height in the prior art, holiday is more, inadequate even compact, equipment
And the disadvantage that formula is complicated, it provides and a kind of prepares fine acicular hydroxyapatite micro nano structure coating in medical magnesium alloy surface
Preparation method, without using additive and pulse current, one-step synthesis under the conditions of relatively mild, and the hydroxyapatite prepared
The coating is uniform and compact, the micro nano structure with fine acicular, and has good corrosion resistance.
Used technical solution is as follows to solve above-mentioned technical problem by the present invention:
The present invention provides a kind of preparation method of Mg alloy surface fine acicular hydroxyapatite micro nano structure coating, described
Preparation method the following steps are included:
(1) pretreatment of magnesium alloy substrate: magnesium alloy substrate is polished, and is cleaned, drying；
(2) it prepares electrochemical deposition electrolyte solution: weighing soluble calcium salt, dihydric phosphate, be dissolved separately in
In ionized water, so that the concentration of calcium salt is 0.01-0.05mol/L, the concentration of dihydric phosphate is 0.006-0.03mol/L；It is mixed
Calcium salt soln and phosphate dihydrogen salt solution are closed, electrochemical deposition electrolyte is obtained；
(3) electrochemical deposition: using platinum electrode as cathode, and magnesium alloy obtains pretreatment in step (1) as anode
Magnesium alloy substrate be immersed in electrochemical deposition electrolyte, cathode anode is placed in parallel, connect D.C. regulated power supply, carry out
Electrochemical deposition process；
(4) it post-processes: post-depositional magnesium alloy being placed in lye and carries out alkali heat-treatment, then is dried after being rinsed with deionized water
It is dry, i.e., one layer of fine and close hydroxyapatite coating layer is formed in the magnesium alloy matrix surface that pretreatment obtains.
Further, the preprocessing process in step (1) be magnesium alloy substrate is successively used 400#, 600#, 800#,
The sand paper of 1200# is polished, and the magnesium alloy substrate after polishing is successively clear with ultrasonic wave in dehydrated alcohol, acetone, deionized water
Wash instrument ultrasonic cleaning, drying.
Further, in step (2) calcium salt soln and phosphate dihydrogen salt solution according to calcium ion and dihydrogen phosphate mole
It is mixed than 1.67:1.
Further, cathode anode distance is 2-4cm, current density 0.5-2.5mA/cm in step (3)2, deposition temperature
85 DEG C, sedimentation time 0.5-1.5h of degree, when deposition, carry out magnetic agitation.
Further, the concentration of lye is 0.01-0.1mol/L in step (4), and heat treatment temperature is 70-90 DEG C, at heat
The reason time is 2-4h.
Further, calcium salt described in step (2) is Ca (NO3)2·4H2O、CaCl2One of or combinations thereof；Phosphorus
Acid dihydride salt is NH4H2PO4、KH2PO4Or NaH2PO4One of or combinations thereof.
Further, the magnesium alloy substrate is medical magnesium alloy, preferably AZ31B magnesium alloy.
The present invention also provides a kind of Mg alloy surface fine acicular hydroxyapatites being prepared by the preparation method
Micro nano structure coating.
Technical effect of the invention is as follows:
(1) present invention prepares hydroxyapatite coating layer using the electrochemical deposition method of low temperature, low current density, due to electrification
Learning deposition is carried out under low current density, can significantly reduce concentration polarization to the adverse effect of coating, so that coating has
There is the structure of even compact；The preparation condition of low temperature can guarantee that the mechanical property of magnesium alloy substrate is unaffected；Electrochemistry is heavy
Magnetic agitation is carried out during product, it can be to avoid hydrogen evolution phenomenon, so that the knot between hydroxyapatite coating layer and magnesium alloy substrate
It is higher to close intensity.
(2) the electrochemical deposition electrolyte prescription that the present invention uses is simple, is only made of calcium salt and dihydric phosphate, nothing
Any promotor or oxidant need to be added, without adjusting electrolyte ph, it is ensured that the growth of hydroxyapatite is not added
The influence of agent can be grown along its c-axis, to grow into the micro nano structure of fine acicular.
(3) present invention process is simple, and cost is relatively low, can prepare even compact, hydroxyl with high purity in Mg alloy surface
Base apatite coating, and coating has the micro nano structure of fine acicular, while raising magnesium alloy imitates anti-corrosion capability, also
Conducive to cell in the adherency and growth of coating surface, to promote being bonded between implantation material and bone tissue, raising is implanted to
Power.
Detailed description of the invention
Fig. 1 is the SEM photograph of hydroxyapatite coating layer prepared by the embodiment of the present invention 1；
Fig. 2 is the section SEM photograph of hydroxyapatite coating layer prepared by the embodiment of the present invention 1；
Fig. 3 is the XRD spectrum of hydroxyapatite coating layer prepared by the embodiment of the present invention 1；
Fig. 4 is the SEM photograph of hydroxyapatite coating layer prepared by the embodiment of the present invention 2；
Fig. 5 is Nyquist spectrum of the hydroxyapatite coating layer of the preparation of the embodiment of the present invention 2 in SBF；
Fig. 6 is that Nyquist of the hydroxyapatite coating layer of the preparation of the embodiment of the present invention 2 in SBF is composed in abscissa in 20-
400Ω·cm2Partial enlarged view in range.
Specific embodiment
It is clearly and completely described below in conjunction with the technical solution in the embodiment of the present invention, it is clear that described reality
Applying example is only a part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, this field is general
Logical technical staff every other embodiment obtained without making creative work belongs to what the present invention protected
Range.
Embodiment 1:
(1) AZ31B magnesium alloy substrate successively the pretreatment of magnesium alloy substrate: is used to the sand of 400#, 600#, 800#, 1200#
Paper polishing；Magnesium alloy substrate after polishing is successively clear with ultrasonic washing instrument ultrasound in dehydrated alcohol, acetone, deionized water
10min is washed, is dried；
(2) it prepares electrochemical deposition electrolyte solution: weighing Ca (NO3)2·4H2O and NH4H2PO4, it is dissolved separately in
In ionized water, so that Ca (NO3)2·4H2The concentration of O is 0.01mol/L, NH4H2PO4Concentration be 0.006mol/L；It will be above-mentioned
Two kinds of solution are uniformly mixed in the ratio that calcium phosphorus molar ratio is 1.67 ︰ 1, obtain electrochemical deposition electrolyte；
(3) electrochemical deposition: using platinum electrode as cathode, and magnesium alloy is immersed in electrolyte solution as anode, yin
Pole anode is placed in parallel, and is kept at a distance as 2cm, and D.C. regulated power supply is connected, and adjustings current density is 1.5mA/cm2, deposition temperature
85 DEG C, sedimentation time 1h of degree, when deposition, carry out magnetic agitation, revolving speed 500rpm；
(4) it post-processes: post-depositional sample is placed in 80 DEG C of alkali heat-treatment 2h in the NaOH solution of 1mol/L, then by sample
It is dried after being rinsed with deionized water, i.e., forms one layer of fine and close hydroxyapatite coating layer in magnesium alloy matrix surface.
The SEM of hydroxyapatite coating layer prepared by the present embodiment is as shown in Figure 1, the coating is uniform and compact, by fine acicular
Structure interts into flower-shaped and acanthosphere shape structure, and acicular texture diameter is about 230-670nm, and length is about 2.5-15 μm.
The section SEM of the present embodiment hydroxyapatite coating layer is as shown in Fig. 2, uniform coating thickness, about 10 μm, and and basal body interface
It is well combined.Fig. 3 is the XRD diagram of prepared coating, through X-ray diffraction analysis as can be seen that prepared coating is hydroxyl
Apatite, and purity is higher.
Embodiment 2:
(1) medical magnesium alloy sample successively the pretreatment of magnesium alloy substrate: is used to the sand of 400#, 600#, 800#, 1200#
Paper polishing；Magnesium alloy after polishing is successively cleaned by ultrasonic in dehydrated alcohol, acetone, deionized water with ultrasonic washing instrument
15min, drying.
(2) it prepares electrochemical deposition electrolyte solution: weighing CaCl2And KH2PO4, it is dissolved separately in deionized water,
So that CaCl2Concentration be 0.05mol/L, KH2PO4Concentration be 0.03mol/L；Above two solution is pressed into calcium phosphorus molar ratio
It is uniformly mixed for the ratio of 1.67 ︰ 1, obtains electrochemical deposition electrolyte.
(3) electrochemical deposition: using platinum electrode as cathode, and magnesium alloy is immersed in electrolyte solution as anode, yin
Pole anode is placed in parallel, and is kept at a distance as 2cm, connection D.C. regulated power supply, adjusting current density 2.5mA/cm2, depositing temperature
85 DEG C, sedimentation time 0.5h, when deposition, carries out magnetic agitation, revolving speed 500rpm；
(4) it post-processes: post-depositional sample is placed in 80 DEG C of alkali heat-treatment 2h in the NaOH solution of 1mol/L, then by sample
It is dried after being rinsed with deionized water, i.e., forms one layer of fine and close hydroxyapatite coating layer in magnesium alloy matrix surface.
The SEM of hydroxyapatite coating layer prepared by the present embodiment is as shown in figure 4, the coating is uniform and compact, by acicular texture
It is formed with flower-like structure, acicular texture diameter is about 200-600nm, and length is about 2-13 μm.Fig. 5 is that the present embodiment is made
The AC impedance spectroscopy of standby coating, Fig. 6 is the partial enlarged view of AC impedance spectroscopy, and the AC impedance of magnesium alloy bare die is
94ohm·cm2, the AC impedance of Coated With Hydroxyapatite magnesium alloy is 780ohmcm2, corrosion resistance improves significant.
Embodiment 3:
(1) medical magnesium alloy sample successively the pretreatment of magnesium alloy substrate: is used to the sand of 400#, 600#, 800#, 1200#
Paper polishing；Magnesium alloy after polishing is successively cleaned by ultrasonic in dehydrated alcohol, acetone, deionized water with ultrasonic washing instrument
10min, drying；
(2) it prepares electrochemical deposition electrolyte solution: weighing Ca (NO3)2·4H2O and NH4H2PO4, it is dissolved separately in
In ionized water, so that Ca (NO3)2·4H2The concentration of O is 0.0417mol/L, NH4H2PO4Concentration be 0.025mol/L；It will be upper
It states two kinds of solution to be uniformly mixed in the ratio that calcium phosphorus molar ratio is 1.67 ︰ 1, obtains electrochemical deposition electrolyte；
(3) electrochemical deposition: using platinum electrode as cathode, and magnesium alloy is immersed in electrolyte solution as anode, yin
Pole anode is placed in parallel, and is kept at a distance as 4cm, connection D.C. regulated power supply, adjusting current density 0.5mA/cm2, depositing temperature
85 DEG C, sedimentation time 1.5h, when deposition, carries out magnetic agitation, revolving speed 500rpm；
(4) it post-processes: post-depositional sample is placed in 70 DEG C of alkali heat-treatment 2h in the NaOH solution of 1mol/L, then by sample
It is dried after being rinsed with deionized water, i.e., forms one layer of fine and close hydroxyapatite coating layer in magnesium alloy matrix surface.
Embodiment 4:
(1) medical magnesium alloy sample successively the pretreatment of magnesium alloy substrate: is used to the sand of 400#, 600#, 800#, 1200#
Paper polishing；Magnesium alloy after polishing is successively cleaned by ultrasonic in dehydrated alcohol, acetone, deionized water with ultrasonic washing instrument
10min, drying；
(2) it prepares electrochemical deposition electrolyte solution: weighing Ca (NO3)2·4H2O and NH4H2PO4, it is dissolved separately in
In ionized water, so that Ca (NO3)2·4H2The concentration of O is 0.0417mol/L, NH4H2PO4Concentration be 0.025mol/L；It will be upper
It states two kinds of solution to be uniformly mixed in the ratio that calcium-phosphorus ratio is 1.67 ︰ 1, obtains electrochemical deposition electrolyte；
(3) electrochemical deposition: using platinum electrode as cathode, and magnesium alloy is immersed in electrolyte solution as anode, yin
Pole anode is placed in parallel, and is kept at a distance as 2cm, connection D.C. regulated power supply, adjusting current density 1mA/cm2, depositing temperature 85
DEG C, sedimentation time 1h, when deposition, carries out magnetic agitation, revolving speed 500rpm；
(4) it post-processes: post-depositional sample is placed in 90 DEG C of alkali heat-treatment 2h in the NaOH solution of 1mol/L, then by sample
It is dried after being rinsed with deionized water, i.e., forms one layer of fine and close hydroxyapatite coating layer in magnesium alloy matrix surface.
Embodiment 5:
(1) medical magnesium alloy sample successively the pretreatment of magnesium alloy substrate: is used to the sand of 400#, 600#, 800#, 1200#
Paper polishing；Magnesium alloy after polishing is successively cleaned by ultrasonic in dehydrated alcohol, acetone, deionized water with ultrasonic washing instrument
10min, drying；
(2) it prepares electrochemical deposition electrolyte solution: weighing Ca (NO3)2·4H2O and NH4H2PO4, it is dissolved separately in
In ionized water, so that Ca (NO3)2·4H2The concentration of O is 0.0417mol/L, NH4H2PO4Concentration be 0.025mol/L；It will be upper
It states two kinds of solution to be uniformly mixed in the ratio that calcium-phosphorus ratio is 1.67 ︰ 1, obtains electrochemical deposition electrolyte；
(3) electrochemical deposition: using platinum electrode as cathode, and magnesium alloy is immersed in electrolyte solution as anode, yin
Pole anode is placed in parallel, and is kept at a distance as 2cm, connection D.C. regulated power supply, adjusting current density 1.5mA/cm2, depositing temperature
85 DEG C, sedimentation time 1h, when deposition, carries out magnetic agitation, revolving speed 500rpm；
(4) it post-processes: post-depositional sample is placed in 80 DEG C of alkali heat-treatment 4h in the NaOH solution of 0.1mol/L, then by sample
Product are dried after being rinsed with deionized water, i.e., form one layer of fine and close hydroxyapatite coating layer in magnesium alloy matrix surface.
Embodiment described above is only that preferred embodiment of the invention is described, and is not carried out to the scope of the present invention
It limits, without departing from the spirit of the design of the present invention, those of ordinary skill in the art make technical solution of the present invention
Various changes and improvements, should all fall into claims of the present invention determine protection scope in.
Claims (9)
1. a kind of preparation method of Mg alloy surface fine acicular hydroxyapatite micro nano structure coating, which is characterized in that described
Preparation method the following steps are included:
(1) pretreatment of magnesium alloy substrate: magnesium alloy substrate is polished, and is cleaned, drying；
(2) it prepares electrochemical deposition electrolyte solution: weighing soluble calcium salt, dihydric phosphate, be dissolved separately in deionization
In water, so that the concentration of calcium salt is 0.01-0.05mol/L, the concentration of dihydric phosphate is 0.006-0.03mol/L；Calcium mixture
Salting liquid and phosphate dihydrogen salt solution obtain electrochemical deposition electrolyte；
(3) electrochemical deposition: use platinum electrode as cathode, magnesium alloy is as anode, by the magnesium that pretreatment obtains in step (1)
Alloy substrate is immersed in electrochemical deposition electrolyte, and cathode anode is placed in parallel, and connects D.C. regulated power supply, carries out electrification
Learn deposition process；
(4) it post-processes: post-depositional magnesium alloy being placed in lye and carries out alkali heat-treatment, then is dried after being rinsed with deionized water,
One layer of fine and close hydroxyapatite coating layer is formed in the magnesium alloy matrix surface that pretreatment obtains.
2. the preparation method of Mg alloy surface fine acicular hydroxyapatite micro nano structure coating according to claim 1,
It is characterized in that, the preprocessing process in step (1) is the sand that magnesium alloy substrate is successively used to 400#, 600#, 800#, 1200#
Paper polishing, the magnesium alloy substrate after polishing is successively clear with ultrasonic washing instrument ultrasound in dehydrated alcohol, acetone, deionized water
It washes, dries.
3. the preparation method of Mg alloy surface fine acicular hydroxyapatite micro nano structure coating according to claim 1,
It is characterized in that, calcium salt soln and phosphate dihydrogen salt solution are according to calcium ion and dihydrogen phosphate molar ratio 1.67 in step (2):
1 is mixed.
4. the preparation method of Mg alloy surface fine acicular hydroxyapatite micro nano structure coating according to claim 1,
It is characterized in that, cathode anode distance is 2-4cm, current density 0.5-2.5mA/cm in step (3)2, 85 DEG C of depositing temperature,
Sedimentation time 0.5-1.5h, when deposition, carry out magnetic agitation.
5. the preparation method of Mg alloy surface fine acicular hydroxyapatite micro nano structure coating according to claim 1,
It is characterized in that, the concentration of lye is 0.01-0.1mol/L in step (4), heat treatment temperature is 70-90 DEG C, heat treatment time
For 2-4h.
6. the preparation method of Mg alloy surface fine acicular hydroxyapatite micro nano structure coating according to claim 3,
It is characterized in that, calcium salt described in step (2) is Ca (NO3)2·4H2O、CaCl2One of or combinations thereof；Biphosphate
Salt is NH4H2PO4、KH2PO4Or NaH2PO4One of or combinations thereof.
7. the preparation method of Mg alloy surface fine acicular hydroxyapatite micro nano structure coating according to claim 1,
It is characterized in that, the magnesium alloy substrate is medical magnesium alloy.
8. the preparation method of Mg alloy surface fine acicular hydroxyapatite micro nano structure coating according to claim 1,
It is characterized in that, the hydroxyapatite coating layer is the hydroxyapatite micro nano structure coating of fine acicular.
9. a kind of Mg alloy surface fine acicular hydroxy-apatite being prepared by the described in any item preparation methods of claim 1-8
Stone micro nano structure coating.
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