CN103657996B - Method for bonding carboxymethyl chitosan bioactive molecules on surface of magnesium alloy - Google Patents
Method for bonding carboxymethyl chitosan bioactive molecules on surface of magnesium alloy Download PDFInfo
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- CN103657996B CN103657996B CN201310647164.9A CN201310647164A CN103657996B CN 103657996 B CN103657996 B CN 103657996B CN 201310647164 A CN201310647164 A CN 201310647164A CN 103657996 B CN103657996 B CN 103657996B
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Abstract
The invention discloses a method for bonding carboxymethyl chitosan bioactive molecules on the surface of magnesium alloy. According to the method, a dopamine polymer film is formed on the surface of the magnesium alloy subjected to cathode liquid phase plasma processing by means of spontaneous deposition and polymerization of dopamine hydrochloride in alkaline ethanol solutions, and the carboxymethyl chitosan can be bonded on the surface of the magnesium alloy through the amidation between amidogen and carboxyl in a dopamine polymer medium layer. According to the method, the operation is easy, a carboxymethyl chitosan film layer formed on the surface of the magnesium alloy is flat and smooth and not prone to falling off, corrosion resistance and biocompatibility of the magnesium alloy can be effectively improved, the defects that the surface of a coating obtained through the cathode liquid phase plasma processing is rough, multiporous and crackled are overcome, the defect that a polymer coating formed through a physical modification method is prone to falling off is also overcome, and therefore the method lays the foundation for magnesium alloy to be used as biomedical materials.
Description
Technical field
The invention belongs to Magnesiumalloy surface modifying technical field, be specifically related to one with poly-dopamine film for medium layer, negative electrode liquid phase plasma technology is combined with chemical modification technique, in the method for magnesium alloy surface chemical bonding CMC bioactive molecule.
Background technology
As a kind of novel bio-medical material, magnesium alloy because having excellent mechanical property, good biocompatibility and unique biological degradability by extensive concern.Magnesium alloy density is low, and specific strength, specific stiffness are high, and elastic modelling quantity, compressive strength and nature bone are close, and magnesium is the necessary element of human metabolism, has facilitation to the growth of bone tissue.Therefore, magnesium alloy has huge applications potentiality in orthopaedics and cardiovascular system reparation.But the corrosion-resistant of magnesium alloy, the degradation speed in human body does not mate with organization healing speed, directly the success rate implanted of impact, and then limits the application of magnesium alloy in clinical.
Surface modification is carried out to magnesium alloy, can effectively improve its corrosion resistance and not affect its mechanical performance.At present, the method for Magnesiumalloy surface modifying has a lot, but single method of modifying often can not meet the requirement of medical application.Such as, by technology such as alkali treatment, differential arc oxidation, catholyte are mutually plasma-deposited, effectively can improve the corrosion resistance of magnesium alloy, but formed be mostly coarse, porous, crackled surface, and not there is biologically active.Comparatively speaking, the surface texture that organic polymer coating opposed flattened is compact can provide corrosion protection effect better for magnesium alloy, and is conducive to the surface-functionalized of magnesium alloy.But so far; the preparation method of polymer coating mainly concentrates on physical modification method, by molecule Direct precipitation or stick to Mg alloy surface and be formed with organic coating, the coating of formation and the interaction force of base material weak; easily come off, do not reach the effect of long-time protection.
Dopamine is the important component part of the mucus of Mussels marine organisms byssus secretion, and in alkaline aqueous solution, (pH value is 8.5) easily spontaneous deposition polymerization occurs, and has general strong adhesion to inorganic and organic material.Can form poly-dopamine film at substrate surface by simple dip coating manner, the multifunction for material surface provides good platform, has been widely used in the surface modification of metal, metal oxide, polymeric material.But because the character of magnesium alloy is active, perishable in aqueous, therefore utilize the study on the modification of dopamine to magnesium alloy not yet to report.
Summary of the invention
Technical problem to be solved by this invention is the coating surface rough porous after overcoming existing magnesium alloy disposal methods, has slight crack, caducous shortcoming, there is provided one with poly-dopamine film for medium layer, negative electrode liquid phase plasma technology is combined with chemical modification technique, in the method for magnesium alloy surface chemical bonding CMC bioactive molecule, corrosion resistance and the biocompatibility of magnesium alloy after the method process, can be improved.
Solve the problems of the technologies described above adopted technical scheme to be made up of following step:
1, negative electrode liquid phase plasma process
With the water-ethanol solution of 0.05 ~ 0.12mol/L NaCl for electrolyte, wherein the volume ratio of deionized water and absolute ethyl alcohol is 1:2 ~ 5, adopt direct current pulse power source, discharge voltage is 350 ~ 500V, frequency is 100 ~ 150Hz, dutycycle is 25% ~ 35%, cathode and anode spacing is 3 ~ 5cm, catholyte carries out to magnesium alloy mutually plasma-deposited, the discharge process time is 10 ~ 20 minutes, forms MgO corrosion-resistant finishes at Mg alloy surface.
2, the poly-dopamine thin layer of deposition
With pH value to 7 ~ 10 that 0.1mol/L NaOH aqueous solution quality of regulation-volumetric concentration is the ethanolic solution of 1 ~ 3mg/mL Dopamine hydrochloride, magnesium alloy after step 1 being processed soaks 12 ~ 36 hours in this solution, obtains the magnesium alloy that surface deposition gathers dopamine thin layer.
3, surface bond CMC
Under condition of ice bath, be the carboxymethyl chitosan sugar aqueous solution of 1% ~ 5% and the N containing 0.1mol/L 1-ethyl-(3-dimethylaminopropyl) carbodiimide hydrochloride and 0.05mol/L N-hydroxy-succinamide by mass fraction, N '-dimethyl formamide solution is that 1:1 ~ 3 mix by volume, stir 2 ~ 3 hours, magnesium alloy step 2 being deposited poly-dopamine thin layer immerses in gained mixed liquor, oscillating reactions 4 ~ 10 hours, obtains the magnesium alloy of surface chemistry bonding CMC bioactive molecule.
The optimum condition of above-mentioned negative electrode liquid phase plasma treatment step 1 is: with the water-ethanol solution of 0.08mol/L NaCl for electrolyte, wherein the volume ratio of deionized water and absolute ethyl alcohol is 1:4, adopt direct current pulse power source, discharge voltage is 400V, frequency is 100Hz, dutycycle is 30%, cathode and anode spacing is 4cm, catholyte carries out to magnesium alloy mutually plasma-deposited, the discharge process time is 15 minutes, forms MgO corrosion-resistant finishes at Mg alloy surface.
The optimum condition that above-mentioned deposition gathers dopamine thin layer step 2 is: the pH value to 8.5 by the NaOH aqueous solution quality of regulation-volumetric concentration of 0.1mol/L being the Dopamine hydrochloride ethanolic solution of 2mg/mL, magnesium alloy after step 1 being processed soaks 24 hours in this solution, obtains the magnesium alloy that surface deposition gathers dopamine thin layer.
The optimum condition of above-mentioned surface bond CMC step 3 is: under condition of ice bath, be the carboxymethyl chitosan sugar aqueous solution of 2% and the N containing 0.1mol/L 1-ethyl-(3-dimethylaminopropyl) carbodiimide hydrochloride and 0.05mol/L N-hydroxy-succinamide by mass fraction, N '-dimethyl formamide solution is 1:2 mixing by volume, stir 2 hours, the magnesium alloy of poly-for step (2) deposition dopamine thin layer is immersed in gained mixed liquor, oscillating reactions 6 hours, obtain the magnesium alloy of surface chemistry bonding CMC bioactive molecule.
The present invention utilizes the spontaneous deposition polymerization of Dopamine hydrochloride in alkaline ethanol solution, poly-dopamine film is formed at the Mg alloy surface of negative electrode liquid phase plasma process, by the amidation process of the amino in poly-dopamine medium layer and carboxyl, CMC is chemically bound in Mg alloy surface, both overcome negative electrode liquid phase plasma process gained coating surface rough porous, crackled shortcoming, also overcome the caducous shortcoming of polymer coating that physical modification method is formed.The present invention is simple to operate, at the composite biological coatings flat smooth that Mg alloy surface is formed, effectively can improve corrosion resistance and the biocompatibility of magnesium alloy, for magnesium alloy is laid a good foundation as bio-medical material.
Accompanying drawing explanation
Fig. 1 is the scanning electron microscope (SEM) photograph of original magnesium alloy in embodiment 1.
Fig. 2 is the scanning electron microscope (SEM) photograph that in embodiment 1, surface forms the magnesium alloy of MgO corrosion-resistant finishes.
Fig. 3 is the scanning electron microscope (SEM) photograph that in embodiment 1, surface deposition gathers the magnesium alloy of dopamine thin layer.
Fig. 4 is the scanning electron microscope (SEM) photograph of the magnesium alloy of surface chemistry bonding CMC bioactive molecule in embodiment 1.
Fig. 5 is the XPS full scan spectrogram of different magnesium alloy in embodiment 1.
Fig. 6 is the O1s high-resolution matching spectrogram of original magnesium alloy in embodiment 1.
Fig. 7 is the O1s high-resolution matching spectrogram that in embodiment 1, surface forms the magnesium alloy of MgO corrosion-resistant finishes.
Fig. 8 is the N1s high-resolution matching spectrogram that in embodiment 1, surface deposition gathers the magnesium alloy of dopamine thin layer.
Fig. 9 is the N1s high-resolution matching spectrogram of the magnesium alloy of surface chemistry bonding CMC bioactive molecule in embodiment 1.
Figure 10 is that mtt assay is detected as in the magnesium alloy extract that osteocyte obtains at original magnesium alloy and embodiment 1 the cytoactive figure cultivated 1,4 day.
Detailed description of the invention
Below in conjunction with drawings and Examples, the present invention is described in more detail, but the invention is not restricted to these embodiments.
Embodiment 1
1, negative electrode liquid phase plasma process
With 2500 orders, 5000 object sand paper, Mg alloy surface polishing, to light, is removed the oxide layer on surface, then uses acetone ultrasonic cleaning 3 times successively, each 5 minutes, use 5000 object sand paper by smooth for graphite rod surface finish again, clean 3 times with EtOH Sonicate, each 5 minutes.With the water-ethanol solution of 0.08mol/L NaCl for electrolyte, wherein the volume ratio of deionized water and absolute ethyl alcohol is 1:4, using the magnesium alloy cleaned up as negative electrode, the graphite rod that cleans up is as anode, immerse in electrolyte, adopt direct current pulse power source, adjustment discharge voltage is 400V, frequency is 100Hz, dutycycle is 30%, cathode and anode spacing is 4cm, catholyte carries out to magnesium alloy mutually plasma-deposited, the discharge process time is 15 minutes, forms MgO corrosion-resistant finishes at Mg alloy surface.
2, the poly-dopamine thin layer of deposition
By the pH value to 8.5 that the NaOH aqueous solution quality of regulation-volumetric concentration of 0.1mol/L is the Dopamine hydrochloride ethanolic solution of 2mg/mL, magnesium alloy after step 1 being processed immerses in gained solution, soak 24 hours, take out, clean with deionized water rinsing, 37 DEG C of vacuum drying 24 hours, obtain the magnesium alloy that surface deposition gathers dopamine thin layer.
3, surface bond CMC
Under condition of ice bath, by 10mL mass fraction be 2% carboxymethyl chitosan sugar aqueous solution join the N of 20mL 1-ethyl-(3-dimethylaminopropyl) carbodiimide hydrochloride and N-hydroxy-succinamide, in N '-dimethyl formamide solution, the concentration of 1-ethyl in solution-(3-dimethylaminopropyl) carbodiimide hydrochloride is 0.1mol/L, the concentration of N-hydroxy-succinamide is 0.05mol/L, stirring at normal temperature 2 hours, the magnesium alloy of poly-for deposition in step 2 dopamine thin layer is immersed in gained mixed liquor, with constant temperature oscillator normal temperature oscillating reactions 6 hours, take out, with N, after N '-dimethyl formamide cleaning, clean by washed with de-ionized water again, 37 DEG C of vacuum drying 24 hours, obtain the magnesium alloy of surface chemistry bonding CMC bioactive molecule.
SEM and x-ray photoelectron spectroscopy is adopted to analyze the change of Mg alloy surface pattern and chemical composition, the results are shown in Figure 1 ~ 9, in Fig. 5, curve a is the XPS full scan spectrogram of original magnesium alloy, curve b is the XPS full scan spectrogram that surface forms the magnesium alloy of MgO corrosion-resistant finishes, curve c is the XPS full scan spectrogram that surface deposition gathers the magnesium alloy of dopamine thin layer, and curve d is the XPS full scan spectrogram of the magnesium alloy of surface chemistry bonding CMC bioactive molecule.
From Fig. 1 ~ 4, Mg alloy surface rough porous after the process of negative electrode liquid phase plasma, after the poly-dopamine thin layer of deposition, a large amount of micropore is filled to a certain extent, aperture diminishes, and superficial film becomes dense, after bonding carboxymethyl chitosan glycan molecule, Mg alloy surface becomes flat smooth, and uniform Carboxymethyl-chitosan Membranes layer is obviously visible.As seen from Figure 5, Mg alloy surface after original Mg alloy surface and the process of negative electrode liquid phase plasma mainly comprises Mg, O, C tri-kinds of elements, and O1s peak obviously strengthens after the process of negative electrode liquid phase plasma, after the poly-dopamine thin layer of deposition, there is the peak of the characteristic element N of Dopamine hydrochloride, after surface bond CMC, the peak of N1s strengthens to some extent, shows that CMC is successfully bonded to Mg alloy surface and introduces new N source.Composition graphs 6 ~ 9 is known, after the process of negative electrode liquid phase plasma, generates the coating of MgO at Mg alloy surface, and after surface deposition gathers dopamine thin layer, surface has occurred that the characteristic element N1s of dopamine is unimodal, in conjunction with being 400.0eV; After bonding CMC, newly there is-CO-NH-peak at 401.9eV, having shown that CMC is by being successfully bonded to Mg alloy surface with the amino generation amidation process on poly-dopamine thin layer.
Embodiment 2
In the negative electrode liquid phase plasma treatment step 1 of the present embodiment, with the water-ethanol solution of 0.05mol/L NaCl for electrolyte, wherein the volume ratio of deionized water and absolute ethyl alcohol is 1:2, adopt direct current pulse power source, discharge voltage is 350V, frequency is 150Hz, dutycycle is 25%, cathode and anode spacing is 5cm, carry out catholyte to magnesium alloy mutually plasma-deposited, the discharge process time is 20 minutes, forms MgO corrosion-resistant finishes at Mg alloy surface.Other steps are identical with embodiment 1, obtain the magnesium alloy of surface chemistry bonding CMC bioactive molecule.
Embodiment 3
In the negative electrode liquid phase plasma treatment step 1 of the present embodiment, with the water-ethanol solution of 0.12mol/L NaCl for electrolyte, wherein the volume ratio of deionized water and absolute ethyl alcohol is 1:5, adopt direct current pulse power source, discharge voltage is 500V, frequency is 130Hz, dutycycle is 35%, cathode and anode spacing is 3cm, carry out catholyte to magnesium alloy mutually plasma-deposited, the discharge process time is 10 minutes, forms MgO corrosion-resistant finishes at Mg alloy surface.Other steps are identical with embodiment 1, obtain the magnesium alloy of surface chemistry bonding CMC bioactive molecule.
Embodiment 4
The deposition of the present embodiment is gathered in dopamine thin layer step 2, by the pH value to 10 that 0.1mol/L NaOH aqueous solution quality of regulation-volumetric concentration is the ethanolic solution of 3mg/mL Dopamine hydrochloride, magnesium alloy after step 1 being processed soaks 36 hours in this solution, obtains the magnesium alloy that surface deposition gathers dopamine thin layer.Other steps are identical with embodiment 1, obtain the magnesium alloy of surface chemistry bonding CMC bioactive molecule.
Embodiment 5
In the surface bond CMC step 3 of the present embodiment, under condition of ice bath, by 10mL mass fraction be 5% carboxymethyl chitosan sugar aqueous solution join the N of 30mL 1-ethyl-(3-dimethylaminopropyl) carbodiimide hydrochloride and N-hydroxy-succinamide, in N '-dimethyl formamide solution, the concentration of 1-ethyl in solution-(3-dimethylaminopropyl) carbodiimide hydrochloride is 0.1mol/L, the concentration of N-hydroxy-succinamide is 0.05mol/L, stirring at normal temperature 3 hours, magnesium alloy step 2 being deposited poly-dopamine thin layer immerses in gained mixed liquor, oscillating reactions 10 hours, other steps are identical with embodiment 4, obtain the magnesium alloy of surface chemistry bonding CMC bioactive molecule.
Embodiment 6
Gather in dopamine thin layer step 2 in the deposition of embodiment 1 ~ 5, by the pH value to 7 that the NaOH aqueous solution quality of regulation-volumetric concentration of 0.1mol/L is the Dopamine hydrochloride ethanolic solution of 1mg/mL, magnesium alloy after step 1 being processed immerses in gained solution, soak 12 hours, take out, clean with deionized water rinsing, 37 DEG C of vacuum drying 24 hours, obtain the magnesium alloy that surface deposition gathers dopamine thin layer.Other steps are identical with corresponding embodiment, obtain the magnesium alloy of surface chemistry bonding CMC bioactive molecule.
Embodiment 7
In the surface bond CMC step 3 of embodiment 1 ~ 6, under condition of ice bath, by 10mL mass fraction be 1% carboxymethyl chitosan sugar aqueous solution join the N of 10mL 1-ethyl-(3-dimethylaminopropyl) carbodiimide hydrochloride and N-hydroxy-succinamide, in N '-dimethyl formamide solution, the concentration of 1-ethyl in solution-(3-dimethylaminopropyl) carbodiimide hydrochloride is 0.1mol/L, the concentration of N-hydroxy-succinamide is 0.05mol/L, stirring at normal temperature 2 hours, the magnesium alloy of poly-for deposition in step 2 dopamine thin layer is immersed in gained mixed liquor, with constant temperature oscillator normal temperature oscillating reactions 4 hours, take out, with N, after N '-dimethyl formamide cleaning, clean by washed with de-ionized water again, 37 DEG C of vacuum drying 24 hours, other steps are identical with corresponding embodiment, obtain the magnesium alloy of surface chemistry bonding CMC bioactive molecule.
In order to prove beneficial effect of the present invention, inventor adopts electrochemical workstation, in SBF simulated body fluid, by dynamic potential polarization curve electrochemical measuring method, corrosion resistance measurement is carried out to the magnesium alloy after original magnesium alloy and embodiment 1 ~ 5 process, by Tafel method, matching is carried out to dynamic potential polarization curve, the corrosion potential (E obtained
corr) and corrosion electric current density (i
corr) in table 1.
The corrosion potential of the different magnesium alloy of table 1 and corrosion current
| E corr(v) | i corr(A/cm 2) | |
| Original magnesium alloy | -1.596 | 2.44×10 -3 |
| Embodiment 1 | -1.472 | 7.00×10 -5 |
| Embodiment 2 | 1.546 | 1.3×10 -4 |
| Embodiment 3 | -1.493 | 9.26×10 -5 |
| Embodiment 4 | -1.501 | 8.53×10 -5 |
| Embodiment 5 | -1.521 | 9.72×10 -5 |
From table 1, compared with original magnesium alloy, the corrosion electric current density of the magnesium alloy after embodiment 1 ~ 5 processes obviously reduces, and corrosion potential also has rising in various degree, and the corrosion electric current density of the magnesium alloy wherein after embodiment 1 process is reduced to 7.00 × 10
-5a/cm
2, reduce 2 orders of magnitude, corrosion potential E
corrbe elevated to-1.472V, best to the decay resistance effect strengthening magnesium alloy.
Adopt Gegenbaur's cell, carry out biocompatibility test by the magnesium alloy of mtt assay to the surface chemistry bonding CMC bioactive molecule that embodiment 1 obtains, the results are shown in Figure 10.As seen from the figure, the cytoactive of cultivating 1,4 day in the magnesium alloy extract of the surface chemistry bonding CMC bioactive molecule that Gegenbaur's cell obtains in the present invention reaches 84.04% and 85.88% respectively, apparently higher than original magnesium alloy, to show with poly-dopamine film, for medium layer is at Mg alloy surface bonding CMC bioactive molecule, effectively to improve the biocompatibility of magnesium alloy.
Claims (3)
1. a method for magnesium alloy surface chemical bonding CMC bioactive molecule, is characterized in that it is made up of following step:
(1) negative electrode liquid phase plasma process
With the water-ethanol solution of 0.05 ~ 0.12mol/L NaCl for electrolyte, wherein the volume ratio of deionized water and absolute ethyl alcohol is 1:2 ~ 5, adopt direct current pulse power source, discharge voltage is 350 ~ 500V, frequency is 100 ~ 150Hz, dutycycle is 25% ~ 35%, cathode and anode spacing is 3 ~ 5cm, catholyte carries out to magnesium alloy mutually plasma-deposited, the discharge process time is 10 ~ 20 minutes, forms MgO corrosion-resistant finishes at Mg alloy surface;
(2) the poly-dopamine thin layer of deposition
By the pH value to 8.5 that the NaOH aqueous solution quality of regulation-volumetric concentration of 0.1mol/L is the Dopamine hydrochloride ethanolic solution of 2mg/mL, magnesium alloy after step (1) being processed soaks 24 hours in this solution, obtains the magnesium alloy that surface deposition gathers dopamine thin layer;
(3) surface bond CMC
Under condition of ice bath, be the carboxymethyl chitosan sugar aqueous solution of 1% ~ 5% and the N containing 0.1mol/L 1-ethyl-(3-dimethylaminopropyl) carbodiimide hydrochloride and 0.05mol/L N-hydroxy-succinamide by mass fraction, N '-dimethyl formamide solution is that 1:1 ~ 3 mix by volume, stir 2 ~ 3 hours, the magnesium alloy of poly-for step (2) deposition dopamine thin layer is immersed in gained mixed liquor, oscillating reactions 4 ~ 10 hours, obtains the magnesium alloy of surface chemistry bonding CMC bioactive molecule.
2. the method for magnesium alloy surface chemical bonding CMC bioactive molecule according to claim 1, it is characterized in that: in described negative electrode liquid phase plasma treatment step (1), with the water-ethanol solution of 0.08mol/L NaCl for electrolyte, wherein the volume ratio of deionized water and absolute ethyl alcohol is 1:4, adopt direct current pulse power source, discharge voltage is 400V, frequency is 100Hz, dutycycle is 30%, cathode and anode spacing is 4cm, catholyte carries out to magnesium alloy mutually plasma-deposited, the discharge process time is 15 minutes, MgO corrosion-resistant finishes is formed at Mg alloy surface.
3. the method for magnesium alloy surface chemical bonding CMC bioactive molecule according to claim 1, it is characterized in that: in described surface bond CMC step (3), under condition of ice bath, be the carboxymethyl chitosan sugar aqueous solution of 2% and the N containing 0.1mol/L 1-ethyl-(3-dimethylaminopropyl) carbodiimide hydrochloride and 0.05mol/L N-hydroxy-succinamide by mass fraction, N '-dimethyl formamide solution is 1:2 mixing by volume, stir 2 hours, the magnesium alloy of poly-for step (2) deposition dopamine thin layer is immersed in gained mixed liquor, oscillating reactions 6 hours, obtain the magnesium alloy of surface chemistry bonding CMC bioactive molecule.
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| CN104746073B (en) * | 2015-04-08 | 2018-04-03 | 重庆大学 | Magnesiumalloy surface modifying method |
| CN105126168B (en) * | 2015-09-07 | 2019-01-25 | 上海交通大学 | Multifunctional bionic coating and preparation, purposes for magnesium-based medical material and device |
| CN108273125A (en) * | 2018-01-17 | 2018-07-13 | 中国科学院上海硅酸盐研究所 | A kind of imitative mussel surface is modified magnesium alloy and its preparation method and application |
| CN111850552B (en) * | 2020-06-19 | 2022-08-23 | 淮阴工学院 | Multifunctional surface modification method for synergistically improving corrosion resistance and biocompatibility of magnesium alloy |
| CN111939331B (en) * | 2020-08-25 | 2022-06-03 | 南京工程学院 | Degradable metal surface gradient polymer layer and preparation method thereof |
| CN113558068A (en) * | 2021-07-26 | 2021-10-29 | 中诚国联（河南）生物科技有限公司 | Preparation method and application of pesticide-fertilizer granules containing dinotefuran and bifenthrin |
| CN114086030A (en) * | 2021-11-22 | 2022-02-25 | 江苏时代铭阳生物新技术研究院有限公司 | Degradable high-compatibility biomedical material and preparation method thereof |
| CN116407677B (en) * | 2023-05-30 | 2023-11-03 | 广州医科大学附属第三医院（广州重症孕产妇救治中心、广州柔济医院） | Magnesium alloy layered coating with wear-resistant self-healing function and preparation method thereof |
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| CN103088380A (en) * | 2013-02-18 | 2013-05-08 | 哈尔滨工业大学 | Methods for preparing super-hydrophobic coatings on surfaces of magnesium and magnesium alloy |
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