CN109881238A - Magnesium-based surface has the active coating and preparation method thereof of self-healing function - Google Patents
Magnesium-based surface has the active coating and preparation method thereof of self-healing function Download PDFInfo
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Abstract
The invention discloses the active coatings and preparation method thereof that magnesium-based surface has self-healing function, phosphorous and calcium porous magnesia coating is prepared in magnesium or magnesium alloy surface layer using differential arc oxidization technique first, then spin-deposit process one layer of F-MSNs PLLA coating of spin coating on phosphorous and calcium porous magnesia coating is used, finally obtains the DCPD coating with high Integrated implant effect on surface with immersion deposition again.Obtained three-layer coating has the following structure and performance characteristic: internal layer is phosphorous and calcium porous magnesia coating, middle layer is the degradable PLLA coating containing F-MSNs's and with " self-healing " function, surface layer is the nanometer shape DCPD coating with high Integrated implant effect, without non-continuous face between the three-decker coating and matrix, with high bond strength, good bioactivity, and corrosion resistance in pseudo body fluid of magnesium and magnesium alloy can be significantly improved and there is good " self-healing " ability.
Description
Technical field
The invention belongs to technical field of biological medical material preparation, are related to a kind of medical implant surface bioactivity of magnesium-based
The preparation method of coating, this method include differential arc oxidation, spin coating and immersion deposition mode, can be planted in magnesium alloy by the technology
One kind is prepared by sealing of hole magnesia (MgO)/load fluorine ion (F in body surface face-) doped meso-porous SiO2Polylactic acid (the F- of nanosphere
MSNs@PLLA)/calcium dihydrogen phosphate (DCPD) composition the degradable biological coating with self-healing function.
Background technique
In bone in terms of provisional implantation instrument building material selection, magnesium alloy is since it with natural bone with matching
The features such as elasticity modulus, non-toxic good biocompatibility and degradable in vivo and catabolite, better than clinical institute now
The non-degradable material used, such as: titanium and its alloy, stainless steel, vitallium.However, big rule are still not implemented in magnesium alloy
Mould clinical application, mainly due to its degrade in animal body it is too fast, degradation extinction time be significantly shorter than both injured bones after fixation
Spontaneous healing time (3~6 months).It can be improved by two kinds of approach for this problem: on the one hand be prepared from ontology
Visual angle is set out, and is improved to a certain extent by techniques such as High Purity, alloying, the refinement of the second phase, decrystallized and crystal grain refinements
Magnesium alloy unsymmetrical corrosion；On the other hand from the modified visual angle in surface, it is non-that magnesium alloy is alleviated by coating protective coating
Uniformly degradation, and the latter is more efficient.
In the coating prepared by existing process for modifying surface, the MgO coating that differential arc oxidation is formed is in pseudo body fluid environment
Other coatings are higher than to the inhibiting effect of magnesium alloy degradation, and strong interface cohesion can be formed with magnesium matrix.However, due to applying
Layer is internal there are micron order hole, weakens its blocking effect to body fluid infiltration.Although this problem is frequent in existing research
It is solved by degradable macromolecule coating sealing of hole mode, but the coating after sealing of hole still cannot achieve complete densification, apply
It inevitably will appear some micro-crack/holes in layer, and as the generation internal defects of degradation also can gradually increase, because
This, the non-homogeneous degradation of magnesium alloy cannot effectively be inhibited by only relying on this " Passive Defence " mode of sealing of hole.
The above problem can be improved by way of loading degradation inhibitor in the coating, and coating is made to have " self-healing "
After function, i.e. coating or coating/basal body interface are corroded, degradation inhibitor is i.e. releasable to corrosion happening part, with matrix
The metal cation that corrosion generates forms relatively stable compound and blocks corrosion happening part, and corrosion is avoided to aggravate.But in coating
The degradation inhibitor of load answers nontoxicity, while the compound that degradation inhibitor and metal cation are formed should be able in vivo slowly
Degradation, the inflammatory reaction and osteolysis for avoiding the nanoparticle of fragmentation, peeling from inducing.Combine " Passive Defence " and " self-healing "
Dual function should be able to make coating have stronger Vaccine effectiveness to magnesium alloy substrate.
While studying corrosion resistance coating, the Integrated implant ability of also reply coating is considered.It is known that degradable
Class Ca-P active coating is such as: the change of calcium octahate phosphate (OCP), beta-calcium phosphate, hydroxyapatite (HA) and calcium dihydrogen phosphate (DCPD)
It is similar to main inorganic composition in bone matrix to learn component, (such as: Mg compared to degradable class inert coatings2F、MgO、Mg(OH)2、
PLLA polymer) functional expressions and the Integrated implant such as the significantly more attachment for promoting skeletonization relevant cell, proliferation and differentiation, by
This, while coating has high corrosion-resistant, also the surface Ying Qi coats degradable class Ca-P coating, assigns its high Integrated implant
Ability.
Above-mentioned joint " Passive Defence " and " self-healing " double-mode protect magnesium matrix, and have the painting of processus styloideus radii integration ability
Layer Structural design idea and technology of preparing are rarely reported in existing research.
Summary of the invention
It is an object of the invention to effectively cannot inhibit magnesium alloy in physiological environment for existing coating of magnesium alloy surface
Too fast this problem of degradation provides a kind of system of degradable active coating in Mg alloy surface preparation with " self-healing " function
Preparation Method.
In order to achieve the above objectives, magnesium-based surface have self-healing function active coating, including from matrix surface outward according to
MgO coating, F-MSNs PLLA coating and the dicalcium phosphate of secondary setting, the thickness of the MgO coating are as follows: 8 μm~12 μm, F-
MSNs@PLLA coating with a thickness of 6 μm~10 μm；Dicalcium phosphate with a thickness of 10 μm~12 μm.In MgO coating containing phosphorus and
Calcium, stating has several holes in MgO coating, described hole is filled by the PLLA in F-MSNs PLLA coating.
Magnesium-based surface has the preparation method of the active coating of self-healing function, comprising the following steps:
The differential arc oxidation of step 1, magnesium and magnesium alloy:
Carry out differential arc oxidation, differential arc oxidation parameter setting are as follows: differential arc oxidation arc frequency 90Hz~110Hz, power supply are positive
400V~500V is pressed, duty ratio is 0~26%.In micro-arc oxidation process, using pure magnesium or magnesium alloy disk as anode, no
The steel electrolytic cell that becomes rusty is cathode, electrolyte composition and concentration are as follows: sodium hydroxide (NaOH) 0.1mol/L~0.2mol/L, calcium hydroxide
(Ca(OH)2) 0.1mol/L~0.2mol/L, β sodium glycero-phosphate (β-Na2GP) 0.01mol/L~0.03mol/L.Preparation process
The middle temperature using cooling system control micro-arc oxidation electrolyte is in 276K-278K.It obtains being coated with magnesia after differential arc oxidation
The sample of coating is put into spare in drying box by the sample prepared after alcohol and deionized water cleaning.
Step 2, on phosphorous and calcium porous magnesia coating with spin-coating method prepare F-MSNs@PLLA coating:
The preparation of step 2.1, mesoporous silica nanospheres (MSNs)
1.0g~2.0g cetyl trimethylammonium bromide (CTAB) is added in 450mL~550mL deionized water, it will
The sodium hydrate aqueous solution (3mL~5mL) of 1.5mol/L~2.5mol/L is introduced into CTAB solution, and solution temperature is adjusted to
343K, after stirring 0.5h~1h, under strong magnetic stirring condition by 5mL~6mL tetraethyl orthosilicate (TEOS) and 4.5mL~
5.5mL ethyl acetate (EA) pours into mixture, and reaction is continued until until forming white depositions；Then, successively filter,
Washing, precipitating, and dry 12h~18h in the baking oven of 333K；Finally by the product after synthesis in acid 2- propanol solution (2-
Propyl alcohol volume is 300mL~400mL, and HCl volume obtains mesoporous dioxy for reflux 3h~5h in 30~40mL) to remove CTAB
SiClx nanosphere (MSNs).
Step 2.2, Fluorin doped MSNs (F-MSNs) preparation
Firstly, in a nitrogen atmosphere, 0.5g-2g, MSNs correspond to 100mL~150mL dry toluene, MSNs is suspended in
In 100mL~150mL dry toluene, 2mL~4mL 1- (2- amino-ethyl) -3- TSL 8330 is added dropwise
(APTES) after, reactant is stirred in inert environments and the 12h~18h that flows back, temperature 353K；Then, reactant is filtered simultaneously
Precipitating is washed with dehydrated alcohol, 1g~2g FeCl is being added in sediment31- propanol solution (120mL~160mL) in suspend
5h~10h；Finally, obtaining Fe2O3 doping MSNs with after water and ethyl alcohol filtration washing, obtained Fe2O3 doping MSNs is transferred to
In sodium fluoride (NaF 1.3g~2.6g) solution of 150mL~200mL, after stirring for 24 hours~48h, make fluorine-ion-doped to MSNs
In, then filter, with ethanol washing, be placed in 303K-373K, baking oven in it is dry, obtain Fluorin doped MSNs after dry.
Step 2.3, polylactic acid coating (the F-MSNs@PLLA) preparation for loading F-MSNs
By polylactic acid (PLLA) and F-MSNs with the weighing of 5:1~20:1 (w/w) ratio, then, F-MSNs is dispersed in poly-
In ethylene glycol, the mass/volume ratio of F-MSNs and polyethylene glycol is 1:5~1:10；And PLLA is dissolved in chloroform, to obtain
3%-5% (w/v) PLLA solution；Then, the F-MSNs dispersed with polyethylene glycol is added in PLLA solution, concussion, mixing
Uniformly, the PLLA solution containing F-MSNs is obtained；Then, PLLA solution of 40 μ of μ l~60 l containing F-MSNs is drawn with liquid-transfering gun, with
Guarantee that the surface magnesium alloy (r=0.7mm) all smoothens.In the item that revolving speed is 3000rpm~5000rpm, the time is 30s~50s
Under part, it is spun on the specimen surface with magnesium oxide coating that step 1 obtains, is repeated spin coating 3~5 times, to make differential of the arc oxygen
Change hole to be enclosed completely, obtains the magnesium alloy sample with F-MSNs@PLLA coating and magnesium oxide coating.
Step 3 prepares dicalcium phosphate (DCPD) coating in F-MSNs@PLLA coating surface
Firstly, the F-MSNs@PLLA coating ultraviolet light irradiation 2h~4h that Mg alloy surface will be coated on, to promote DCPD
The magnesium alloy sample with F-MSNs@PLLA coating and magnesium oxide coating after irradiation is impregnated in oversaturated by heterogeneous nucleation
Ca(H2PO4)2H212h in O solution~for 24 hours, temperature is 293K~298K, can generate DCPD in F-MSNs@PLLA coating surface
Coating.
Compared with prior art, the present invention at least has technical effect beneficial below:
1) three-decker coating prepared by the present invention is used, internal layer (adjoining with matrix) is to be sealed containing phosphorus and calcium and by PLLA
The MgO coating in hole can stop body fluid to be infiltrated up to matrix, inhibit magnesium and magnesium alloy degradation, while having good combination with matrix；
Middle layer is the degradable PLLA for loading F-MSNs, wherein F-The Mg that can be generated with matrix degradation2+Reaction generates relatively stable
MgF2Phase blocks corrosion happening part, inhibits corrosion propagation, coating is made to have " self-healing " function；Outer layer is with processus styloideus radii
The nano-sheet DCPD coating for integrating effect can significantly promote new bone formation around implant, promote the early stage of implant and host bone
It is fixed.Without non-continuous face between the three-decker coating and matrix, there is high bond strength, good bioactivity, and
Good " self-healing " ability can be showed in pseudo body fluid, be obviously improved the corrosion resistance of magnesium and magnesium alloy in pseudo body fluid.
2) micro-arc oxidation electrolyte ingredient is simple, and without ingredient is easily decomposed, process stabilizing is prepared used in three-layer coating
Chemical reagent, such as NaOH, CaOH, APTES, the equal non-toxic and safe such as TEOS are without side-effects to human body.
It 3) is growth in situ using the magnesium oxide coating of differential arc oxidation method preparation, and the hole formed on coating can be with
Mechanical riveted is formed with PLLA coating, promotes bond strength；Meanwhile the PLLA coating after UV activation keeps its surface DCPD former
Position forming core and growth, coating/matrix, interlayer prepared by technology all have strong interface cohesion through the invention, are implanting
It is not easy to peel off in the process.
4) invention raw material, such as NaOH, CaOH, APTES, TEOS used etc. can directly be bought in market, easily be obtained, and
Preparation section is simple, process stabilizing, so that the technique can be used for being mass produced preparation.
Detailed description of the invention
Fig. 1 is in embodiment 1 by phosphorous and calcium porous magnesia coating surface topography prepared by micro-arc oxidation treatment
SEM photograph；
Fig. 2 a is the pattern SEM photograph that mesoporous silica nanospheres are prepared using the present invention；
Fig. 2 b is the power spectrum spectral line that mesoporous silica nanospheres are prepared using the present invention；
Fig. 3 is the TEM bright field image using mesoporous silica nanospheres prepared by the present invention；
Fig. 4 a is to use F-doped mesoporous silica nanospheres pattern SEM photograph prepared by the present invention and power spectrum spectral line；
Fig. 4 b is the power spectrum spectral line using F-doped mesoporous silica nanospheres prepared by the present invention；
Fig. 5 is the TEM bright field image using F-MSNs prepared by the present invention；
Fig. 6 is F-MSNs@PLLA coating morphology SEM photograph prepared by spin-coating method in embodiment 1；
Fig. 7 is the surface topography SEM photograph using DCPD coating prepared by the present invention；
Fig. 8 is MgO/F-MSNs@PLLA/DCPD three-decker coatings cross-section SEM photograph prepared by embodiment 1；
Fig. 9 is F-MSNs@PLLA coating morphology SEM photograph prepared by spin-coating method in embodiment 2；
Figure 10 is MgO/F-MSNs@PLLA/DCPD three-decker coatings cross-section SEM photograph prepared by embodiment 2；
Figure 11 is F-MSNs@PLLA coating morphology SEM photograph prepared by spin-coating method in embodiment 3；
Figure 12 is MgO/F-MSNs@PLLA/DCPD three-decker coatings cross-section SEM photograph prepared by embodiment 3.
Specific embodiment
The following describes the present invention in detail with reference to the accompanying drawings and specific embodiments.
The Structural design idea of floating coat of the present invention are as follows: start in devising in terms of " Passive Defence " and " self-healing " two
Layer sealing of hole MgO and middle layer F-MSNs@PLLA, and " chemical activation " theory is utilized to devise biologically active DCPD table
Layer, make coating have it is strong it is corrosion proof simultaneously, there is processus styloideus radii integration ability；Floating coat preparation method of the present invention has innovation: applying
More micropore MgO layers have been prepared in situ first with differential arc oxidation mode in layer, so that it is had strong―binding interface with matrix, secondly utilize
PLLA loads F-MSNs and prepares F-MSNs@PLLA in more microporous alumina magnesium surfaces with spin coating mode, makes MgO and F- using micropore
MSNs PLLA forms the effect of physics riveted, and promote interface cohesion enables DCPD to exist finally by ultraviolet irradiation activation method
PLLA surface in situ nucleation, therefore good boundary is all had between coating interlayer and coating/matrix prepared by mode through the invention
Face combines.
Referring to Fig. 8, magnesium-based surface has the active coating of self-healing function, including what is set gradually outward from matrix surface
MgO coating, F-MSNs PLLA coating and dicalcium phosphate, the thickness of the MgO coating are as follows: 8 μm~12 μm, F-MSNs PLLA
Coating with a thickness of 6 μm~10 μm；Dicalcium phosphate with a thickness of 10 μm~12 μm.Contain phosphorus and calcium in MgO coating, states MgO
There are several holes, described hole is filled by the PLLA in F-MSNs PLLA coating in coating.
The present invention uses differential arc oxidization technique to prepare phosphorous and calcium porous MgO coating in magnesium or magnesium alloy surface layer first,
I.e. using phosphorous and calcium aqueous solution as electrolyte, magnesium or magnesium alloy are carried out at differential arc oxidation under high voltages using the pulse power
Then reason uses spin-coating method one layer of F-MSNs@PLLA coating of spin coating on phosphorous and calcium porous MgO coating, finally again with dipping
Sedimentation obtains the DCPD coating with high Integrated implant effect on surface.
Embodiment 1
Magnesium-based surface has the preparation method of the active coating of self-healing function, comprising the following steps:
Step 1 carries out differential arc oxidation, differential arc oxidation parameter setting are as follows: differential arc oxidation arc frequency 100Hz, positive pressure 450V,
Duty ratio is 26%.In micro-arc oxidation process, as anode, stainless steel electrolytic cell is cathode for pure magnesium or magnesium alloy disk,
Electrolyte composition and concentration are as follows: NaOH 0.125mol/L, Ca (OH)20.0135mol/L, β-Na2GP 0.02mol/L.Preparation
In the process using cooling system control micro-arc oxidation electrolyte temperature in 273K.By the sample prepared through alcohol and deionized water
After cleaning, it is put into spare in drying box.Obtain phosphorous and calcium magnesium oxide coating, surface SEM photograph refering to fig. 1, from Fig. 1
It can be seen that the fine and close hole that will form on magnesium oxide coating.
Step 2, on phosphorous and calcium porous magnesia coating with spin-coating method prepare F-MSNs@PLLA coating:
1.0g CTAB is added in 480mL deionized water by step 2.1, obtains CTAB solution, is by 3.5mL concentration
The sodium hydroxide solution of 2mol/L is introduced into CTAB solution, and adjusting CTAB is alkalinity, and temperature is adjusted to 343K, is stirred half small
Shi Hou pours into 5mL TEOS and 5.5mL ethyl acetate (EA) in alkaline CTAB solution under the stirring of strong magnetic, and reaction is continued for
Until forming white depositions；Then, successively filter, washing precipitating and is dried overnight in the baking oven of 333K, obtain with
CTAB is the MSNs of template micella；And in acid 2- propyl alcohol (volume of acid 2- propyl alcohol is 340mL, and HCl volume is 34mL)
To remove CTAB, mesoporous silica nanospheres are obtained within reflux 2 hours, surface microscopic topographic and element are constituted respectively refering to figure
2a and Fig. 3, in figure it can be seen that silica nanosphere surface it is hexagonal mesoporous, Fig. 2 b is to prepare mesoporous dioxy using the present invention
The power spectrum spectral line of SiClx nanosphere.
Step 2.2, preparation F-MSNs.
Firstly, in a nitrogen atmosphere, MSNs is suspended in 120mL dry toluene, after 3mL APTES is added dropwise, will react
Object is stirred and is refluxed overnight in inert environments, temperature 353K；Then, it filters and washs precipitating with dehydrated alcohol, will precipitate
1.4g FeCl is being added in object31- propanol solution (140mL) in suspend 6 hours；Finally, with after water and ethyl alcohol filtration washing,
Fe2O3 doping MSNs is obtained, obtained Fe2O3 doping MSNs is transferred in the solution of 150mL sodium fluoride containing 1.0g, mistake after stirring 1 day
Filter, it is with ethanol washing filtrate, filtrate is dry in the baking oven of 333K temperature, obtain Fluorin doped MSNs.Its surface topography
It constitutes with element respectively refering to Fig. 4 and Fig. 5, it can be seen that sample shows rougher surface, and keeps spherical structure.
Step 2.3, polylactic acid coating (the F-MSNs@PLLA) preparation for loading F-MSNs
By PLLA and F-MSNs with the weighing of 5:1 (w/w) ratio, then, F-MSNs is dispersed in polyethylene glycol, to prevent
It is reunited, and the ratio of F-MSNs and polyethylene glycol is 1:10 (w/v), PLLA is dissolved in chloroform, to obtain 3% (w/v)
The F-MSNs dispersed with polyethylene glycol is then added in PLLA solution by PLLA solution, and it is molten to obtain the PLLA containing F-MSNs
Liquid, concussion are uniformly mixed, and then, draw PLLA solution of the 50 μ l containing F-MSNs with liquid-transfering gun, are 5000rpm, time in revolving speed
Under conditions of 30s, magnesium alloy sample surfaces are spun on, are repeated spin coating 3 times.It obtains with F-MSNs@PLLA coating and oxidation
The magnesium alloy sample of magnesium coating, surface SEM photograph is refering to Fig. 6.
Step 3, F-MSNs@PLLA coating surface dicalcium phosphate (DCPD) preparation technology of coating
Firstly, the F-MSNs@PLLA coating ultraviolet light irradiation 2h that Mg alloy surface will be coated on, to promote DCPD out-phase
Nucleation, is then impregnated in oversaturated Ca (H for the magnesium alloy sample after irradiation2PO4)2H2It, can be in F- 12 hours in O solution
MSNs@PLLA coating surface generates DCPD coating.Its surface and cross section microscopic appearance photo are respectively refering to Fig. 7 and Fig. 8.
Embodiment 2
Magnesium-based surface has the preparation method of the active coating of self-healing function, comprising the following steps:
Step 1 carries out differential arc oxidation, differential arc oxidation parameter setting are as follows: differential arc oxidation arc frequency 100Hz, positive pressure 450V,
Duty ratio is 26%.In micro-arc oxidation process, as anode, stainless steel electrolytic cell is cathode for pure magnesium or magnesium alloy disk,
Electrolyte composition and concentration are as follows: NaOH 0.125mol/L, Ca (OH)20.0135mol/L, β-Na2GP 0.02mol/L.Preparation
In the process using cooling system control micro-arc oxidation electrolyte temperature in 273K.By the sample prepared through alcohol and deionized water
After cleaning, it is put into spare in drying box.Obtain phosphorous and calcium magnesium oxide coating, surface SEM photograph refering to fig. 1, from Fig. 1
It can be seen that the fine and close hole that will form on magnesium oxide coating.
Step 2, on phosphorous and calcium porous magnesia coating with spin-coating method prepare F-MSNs@PLLA coating:
1.0g CTAB is added in 480mL deionized water by step 2.1, obtains CTAB solution, is by 3.5mL concentration
The sodium hydroxide solution of 2mol/L is introduced into CTAB solution, and adjusting CTAB is alkalinity, and temperature is adjusted to 343K, is stirred half small
Shi Hou pours into 5mL TEOS and 5.5mL ethyl acetate (EA) in alkaline CTAB solution under the stirring of strong magnetic, and reaction is continued for
Until forming white depositions；Then, successively filter, washing precipitating and is dried overnight in the baking oven of 333K, obtain with
CTAB is the MSNs of template micella；And in acid 2- propyl alcohol (volume of acid 2- propyl alcohol is 340mL, and HCl volume is 34mL)
To remove CTAB, mesoporous silica nanospheres are obtained within reflux 2 hours, surface microscopic topographic and element are constituted respectively refering to figure
2a and Fig. 3, there are many mesoporous in figure it can be seen that silica nanosphere surface.
Step 2.2, preparation F-MSNs.
Firstly, in a nitrogen atmosphere, MSNs is suspended in 120mL dry toluene, after 3mL APTES is added dropwise, will react
Object is stirred and is refluxed overnight in inert environments, temperature 353K；Then, it filters and washs precipitating with dehydrated alcohol, will precipitate
1.4g FeCl is being added in object31- propanol solution (140mL) in suspend 6 hours；Finally, with after water and ethyl alcohol filtration washing,
Fe2O3 doping MSNs is obtained, obtained Fe2O3 doping MSNs is transferred in the solution of 150mL sodium fluoride containing 1.0g, mistake after stirring 1 day
Filter, it is with ethanol washing filtrate, filtrate is dry in the baking oven of 333K temperature, obtain Fluorin doped MSNs.Its surface topography
It constitutes with element respectively refering to Fig. 4 a and Fig. 5, it can be seen that sample shows rougher surface, and keeps spherical structure, figure
4b is the power spectrum spectral line using F-doped mesoporous silica nanospheres prepared by the present invention.
Step 2.3, polylactic acid coating (the F-MSNs@PLLA) preparation for loading F-MSNs
By PLLA and F-MSNs with the weighing of 10:1 (w/w) ratio, then, F-MSNs is dispersed in polyethylene glycol, to prevent
Only it is reunited, and the ratio of F-MSNs and polyethylene glycol is 1:10 (w/v), PLLA is dissolved in chloroform, to obtain 3% (w/v)
The F-MSNs dispersed with polyethylene glycol is then added in PLLA solution by PLLA solution, and it is molten to obtain the PLLA containing F-MSNs
Liquid, concussion are uniformly mixed, and then, draw PLLA solution of the 50 μ l containing F-MSNs with liquid-transfering gun, are 4000rpm, time in revolving speed
Under conditions of 20s, magnesium alloy sample surfaces are spun on, are repeated spin coating 4 times.It obtains with F-MSNs@PLLA coating and oxidation
The magnesium alloy sample of magnesium coating, surface SEM photograph is refering to Fig. 9.
Step 3, F-MSNs@PLLA coating surface dicalcium phosphate (DCPD) preparation technology of coating
Firstly, the F-MSNs@PLLA coating ultraviolet light irradiation 1.5h that Mg alloy surface will be coated on, to promote DCPD different
It is mutually nucleated, the magnesium alloy sample after irradiation is then impregnated in oversaturated Ca (H2PO4)2H2It, can be in F- 9 hours in O solution
MSNs@PLLA coating surface generates DCPD coating.Its cross section microscopic appearance photo refering to fig. 10.
Embodiment 3
Magnesium-based surface has the preparation method of the active coating of self-healing function, comprising the following steps:
Step 1 carries out differential arc oxidation, differential arc oxidation parameter setting are as follows: differential arc oxidation arc frequency 100Hz, positive pressure 450V,
Duty ratio is 26%.In micro-arc oxidation process, as anode, stainless steel electrolytic cell is cathode for pure magnesium or magnesium alloy disk,
Electrolyte composition and concentration are as follows: NaOH 0.125mol/L, Ca (OH)20.0135mol/L, β-Na2GP 0.02mol/L.Preparation
In the process using cooling system control micro-arc oxidation electrolyte temperature in 273K.By the sample prepared through alcohol and deionized water
After cleaning, it is put into spare in drying box.Obtain phosphorous and calcium magnesium oxide coating, surface SEM photograph refering to fig. 1, from Fig. 1
It can be seen that the fine and close hole that will form on magnesium oxide coating.
Step 2, on phosphorous and calcium porous magnesia coating with spin-coating method prepare F-MSNs@PLLA coating:
1.0g CTAB is added in 480mL deionized water by step 2.1, obtains CTAB solution, is by 3.5mL concentration
The sodium hydroxide solution of 2mol/L is introduced into CTAB solution, and adjusting CTAB is alkalinity, and temperature is adjusted to 343K, is stirred half small
Shi Hou pours into 5mL TEOS and 5.5mL ethyl acetate (EA) in alkaline CTAB solution under the stirring of strong magnetic, and reaction is continued for
Until forming white depositions；Then, successively filter, washing precipitating and is dried overnight in the baking oven of 333K, obtain with
CTAB is the MSNs of template micella；And in acid 2- propyl alcohol (volume of acid 2- propyl alcohol is 340mL, and HCl volume is 34mL)
To remove CTAB, mesoporous silica nanospheres are obtained within reflux 2 hours, surface microscopic topographic and element are constituted respectively refering to figure
2a and Fig. 3, there are many mesoporous in figure it can be seen that silica nanosphere surface.
Step 2.2, preparation F-MSNs.
Firstly, in a nitrogen atmosphere, MSNs is suspended in 120mL dry toluene, after 3mL APTES is added dropwise, will react
Object is stirred and is refluxed overnight in inert environments, temperature 353K；Then, it filters and washs precipitating with dehydrated alcohol, will precipitate
1.4g FeCl is being added in object31- propanol solution (140mL) in suspend 6 hours；Finally, with after water and ethyl alcohol filtration washing,
Fe2O3 doping MSNs is obtained, obtained Fe2O3 doping MSNs is transferred in the solution of 150mL sodium fluoride containing 1.0g, mistake after stirring 1 day
Filter, it is with ethanol washing filtrate, filtrate is dry in the baking oven of 333K temperature, obtain Fluorin doped MSNs.Its surface topography
It constitutes with element respectively refering to Fig. 4 and Fig. 5, it can be seen that sample shows rougher surface, and keeps spherical structure.
Step 2.3, polylactic acid coating (the F-MSNs@PLLA) preparation for loading F-MSNs
By PLLA and F-MSNs with the weighing of 20:1 (w/w) ratio, then, F-MSNs is dispersed in polyethylene glycol, to prevent
Only it is reunited, and the ratio of F-MSNs and polyethylene glycol is 1:10 (w/v), PLLA is dissolved in chloroform, to obtain 3% (w/v)
The F-MSNs dispersed with polyethylene glycol is then added in PLLA solution by PLLA solution, and it is molten to obtain the PLLA containing F-MSNs
Liquid, concussion are uniformly mixed, and then, draw PLLA solution of the 50 μ l containing F-MSNs with liquid-transfering gun, are 3000rpm, time in revolving speed
Under conditions of 10s, magnesium alloy sample surfaces are spun on, are repeated spin coating 5 times.It obtains with F-MSNs@PLLA coating and oxidation
The magnesium alloy sample of magnesium coating, surface SEM photograph refering to fig. 11.
Step 3, F-MSNs@PLLA coating surface dicalcium phosphate (DCPD) preparation technology of coating
Firstly, the F-MSNs@PLLA coating ultraviolet light irradiation 1h that Mg alloy surface will be coated on, to promote DCPD out-phase
Nucleation, is then impregnated in oversaturated Ca (H for the magnesium alloy sample after irradiation2PO4)2H2It, can be in F- 6 hours in O solution
MSNs@PLLA coating surface generates DCPD coating.Its cross section microscopic appearance photo refering to fig. 12.
Embodiment can enumerate many, as space is limited, not list one by one here, in short, in range provided by the invention,
Using differential arc oxidation, after spin coating and the processing of immersion deposition combination process, three-decker can be obtained in magnesium or Mg alloy surface and is applied
Layer: internal layer is that body fluid can be stopped to be infiltrated up to matrix containing phosphorus and calcium and by the MgO layer of PLLA sealing of hole, inhibits magnesium and magnesium alloy drop
Solution, while there is good combination with matrix；Middle layer is the degradable PLLA for loading F-MSNs, wherein F-It can be produced with degradation
Raw Mg2+Reaction generates relatively stable MgF2Phase blocks corrosion happening part, inhibits corrosion propagation, coating is made to have " self-healing
Close " function；Outer layer is the nano-sheet DCPD with high Integrated implant effect.The composite coating has high bond strength, good
Bioactivity closed so as to be obviously improved magnesium and magnesium and since it shows good " self-healing " ability in pseudo body fluid
Anti-corrosion capability of the gold in pseudo body fluid.The above content is merely illustrative of the invention's technical idea, and cannot be limited with this of the invention
Protection scope, it is all according to the technical idea provided by the invention, any changes made on the basis of the technical scheme each falls within this
Within the protection scope of invention claims.
Claims (8)
1. the active coating that magnesium-based surface has self-healing function, which is characterized in that including being set gradually outward from matrix surface
MgO coating, F-MSNs@PLLA coating and dicalcium phosphate, phosphorus and calcium are contained in the MgO coating.
2. magnesium-based surface according to claim 1 has the active coating and preparation method thereof of self-healing function, feature
It is that there are several holes in the MgO coating, described hole is filled by the PLLA in F-MSNs PLLA coating.
3. the active coating that magnesium-based surface according to claim 1 has self-healing function, which is characterized in that the MgO
The thickness of coating are as follows: 8 μm~12 μm, F-MSNs PLLA coating with a thickness of 6 μm~10 μm；Dicalcium phosphate with a thickness of 10 μ
M~12 μm.
4. the preparation method that a kind of magnesium-based surface has the active coating of self-healing function, which comprises the following steps:
Step 1 carries out differential arc oxidation to pure magnesium or magnesium alloy, obtains the sample coated with magnesium oxide coating；In differential arc oxidation mistake
Cheng Zhong, using pure magnesium or magnesium alloy disk as anode, stainless steel electrolytic cell is cathode；
Step 2 with spin-coating method prepares F-MSNs@PLLA coating, including following step on phosphorous and calcium porous magnesia coating
It is rapid:
Step 2.1 prepares mesoporous silica nanospheres MSNs；
Step 2.2, preparation F-MSNs；
The polylactic acid coating of step 2.3, preparation load F-MSNs, and the polylactic acid coating for loading F-MSNs is spun on step 1
The obtained specimen surface with magnesium oxide coating；
Step 3, the F-MSNs@PLLA coating that Mg alloy surface is coated on ultraviolet light irradiation will have F-MSNs@after irradiation
The magnesium alloy sample of PLLA coating and magnesium oxide coating is impregnated in oversaturated Ca (H2PO4)2H26h~12h in O solution
DCPD coating is generated in F-MSNs@PLLA coating surface.
5. magnesium-based surface according to claim 1 has the preparation method of the active coating of self-healing function, feature exists
In the detailed process of step 2.1 are as follows: the sodium hydrate aqueous solution of 1.5mol/L~2.5mol/L is introduced cetyl trimethyl
Obtain mixture A in ammonium bromide solution, the concentration of the cetyl trimethylammonium bromide solution be 0.0018g/mL~
The volume ratio of 0.004g/mL, the sodium hydrate aqueous solution and cetyl trimethylammonium bromide solution be (0.005~
0.011): 1, tetraethyl orthosilicate and ethyl acetate are poured into mixture A under strong magnetic stirring condition, form white precipitate
Object；Then, it is successively filtered, washed, precipitates and dries；Product after drying is flowed back in acid 2- propanol solution, to remove
Cetyl trimethylammonium bromide obtains mesoporous silica nanospheres MSNs.
6. magnesium-based surface according to claim 1 has the preparation method of the active coating of self-healing function, feature exists
In the detailed process of step 2.2 are as follows: under protective atmosphere, MSNs is suspended in dry toluene, 1- (2- amino second is added dropwise
Base) after -3- TSL 8330, reactant is stirred and flowed back in inert environments；Then it is filtered, washed, sinks
It forms sediment, obtains sediment, FeCl is being added in sediment31- propanol solution in suspension 5h~10h；Then filtration washing obtains
Fe2O3 doping MSNs is transferred in Fluorinse, stirs evenly by Fe2O3 doping MSNs, make it is fluorine-ion-doped into MSNs, then
It is filtered, washed, dries, obtain Fluorin doped MSNs, i.e. F-MSNs after dry.
7. magnesium-based surface according to claim 1 has the preparation method of the active coating of self-healing function, feature exists
In the detailed process of step 2.3 are as follows: polylactic acid and F-MSNs are weighed with the ratio of 5:1~20:1, then disperse F-MSNs
In polyethylene glycol, the mass/volume ratio of F-MSNs and polyethylene glycol is 1:5~1:10；Polylactic acid is dissolved in chloroform, is obtained
Obtain 3%-5% PLA solution；Then, the F-MSNs dispersed with polyethylene glycol is added in PLA solution, shaken and mixed
It closes uniformly, obtains the PLA solution containing F-MSNs；Then, revolving speed is 3000rpm~5000rpm, the time is 10s~30s
Under conditions of, the PLA solution containing F-MSNs is spun on the specimen surface with magnesium oxide coating that step 1 obtains, is repeated
Spin coating 3~5 times, obtain the magnesium alloy with F-MSNs@PLLA coating and magnesium oxide coating.
8. magnesium-based surface according to claim 1 has the preparation method of the active coating of self-healing function, feature exists
In comprising calcium ion and phosphonium ion in electrolyte.
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