CN103657996A - 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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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 a kind of take gather dopamine film as medium layer, negative electrode liquid phase plasma technology is combined with chemical modification technique, in the method for Mg alloy surface bonding CMC bioactive molecule.
Background technology
As a kind of novel bio-medical material, magnesium alloy is because having good mechanical property, good biocompatibility and unique biodegradability by extensive concern.Magnesium alloy density is low, and specific strength, specific stiffness are high, and elastic modelling quantity, compressive strength and nature bone approach, and magnesium is the necessary element of human body metabolism, and the growth of bone tissue is had to facilitation.Therefore, magnesium alloy has huge applications potentiality aspect 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, the success rate that directly impact is implanted, and then limited the application of magnesium alloy in clinical.
Magnesium alloy is carried out to surface modification, 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.For example, by technology such as alkali treatment, differential arc oxidation, negative electrode liquid phase plasma depositions, can effectively improve the corrosion resistance of magnesium alloy, but being mostly of forming is coarse, porous, crackled surface, and does not there is biologically active.Comparatively speaking, the surface texture of organic polymer coating opposed flattened compactness 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, a little less than the coating of formation and the interaction force of base material; 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) spontaneous deposition polymerization easily occurs, and inorganic and organic material are had to general strong adhesion.By simple dip-coating mode, can form poly-dopamine film at substrate surface, for the multifunction of material surface provides good platform, be widely used in the surface modification of metal, metal oxide, polymeric material.But because the character of magnesium alloy is active, perishable in the aqueous solution, therefore utilize dopamine not yet to report the study on the modification of magnesium alloy.
Summary of the invention
Technical problem to be solved by this invention is to overcome coating surface rough porous after existing magnesium alloy disposal methods, has slight crack, caducous shortcoming, provide a kind of take gather dopamine film as medium layer, negative electrode liquid phase plasma technology is combined with chemical modification technique, in the method for Mg alloy surface bonding CMC bioactive molecule, the method can improve corrosion resistance and the biocompatibility of magnesium alloy after processing.
Solving the problems of the technologies described above adopted technical scheme is comprised of following step:
1, negative electrode liquid phase plasma is processed
The water-ethanol solution of 0.05～0.12mol/L NaCl of take is 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 that 350～500V, frequency are that 100～150Hz, dutycycle are 25%～35%, cathode and anode spacing is 3～5cm, magnesium alloy is carried out to negative electrode liquid phase plasma deposition, the discharge process time is 10～20 minutes, at Mg alloy surface, forms MgO corrosion-resistant finishes.
2, the poly-dopamine thin layer of deposition
By 0.1mol/L NaOH aqueous solution quality of regulation-volumetric concentration, be pH value to 7～10 of the ethanolic solution of 1～3mg/mL Dopamine hydrochloride, magnesium alloy after step 1 is processed soaks 12～36 hours in this solution, obtains the magnesium alloy of the poly-dopamine thin layer of surface deposition.
3, surface bond CMC
Under condition of ice bath, the carboxymethyl chitosan sugar aqueous solution that is 1%～5% by mass fraction and the N that contains 0.1mol/L 1-ethyl-(3-dimethylaminopropyl) carbodiimide hydrochloride and 0.05mol/L N-hydroxy-succinamide, N '-dimethyl formamide solution is that mix 1:1～3 by volume, stir 2～3 hours, the magnesium alloy of the poly-dopamine thin layer of step 2 deposition is immersed in gained mixed liquor, oscillating reactions 4～10 hours, obtains the magnesium alloy of surface bond CMC bioactive molecule.
The optimum condition of above-mentioned negative electrode liquid phase plasma treatment step 1 is: the water-ethanol solution of 0.08mol/L NaCl of take is electrolyte, wherein the volume ratio of deionized water and absolute ethyl alcohol is 1:4, adopt direct current pulse power source, discharge voltage is that 400V, frequency are that 100Hz, dutycycle are 30%, cathode and anode spacing is 4cm, magnesium alloy is carried out to negative electrode liquid phase plasma deposition, the discharge process time is 15 minutes, at Mg alloy surface, forms MgO corrosion-resistant finishes.
The optimum condition of the poly-dopamine thin layer step 2 of above-mentioned deposition is: the pH value to 8.5 of the Dopamine hydrochloride ethanolic solution that is 2mg/mL by NaOH aqueous solution quality of regulation-volumetric concentration of 0.1mol/L, magnesium alloy after step 1 is processed soaks 24 hours in this solution, obtains the magnesium alloy of the poly-dopamine thin layer of surface deposition.
The optimum condition of above-mentioned surface bond CMC step 3 is: under condition of ice bath, the carboxymethyl chitosan sugar aqueous solution that is 2% by mass fraction and the N that contains 0.1mol/L 1-ethyl-(3-dimethylaminopropyl) carbodiimide hydrochloride and 0.05mol/L N-hydroxy-succinamide, N '-dimethyl formamide solution is by volume for 1:2 mixes, stir 2 hours, the magnesium alloy of the poly-dopamine thin layer of step 2 deposition is immersed in gained mixed liquor, oscillating reactions 6 hours, obtains the magnesium alloy of surface bond CMC bioactive molecule.
The present invention utilizes the spontaneous deposition polymerization of Dopamine hydrochloride in alkaline ethanol solution, the Mg alloy surface of processing at negative electrode liquid phase plasma forms poly-dopamine film, by the amino in poly-dopamine medium layer and the amidation process of carboxyl, CMC is bonded to Mg alloy surface, both overcome negative electrode liquid phase plasma and processed gained coating surface rough porous, crackled shortcoming, also overcome the caducous shortcoming of the formed polymer coating of physical modification method.The present invention is simple to operate, and the composite biological coatings forming at Mg alloy surface is smooth smooth, can effectively 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 of the magnesium alloy of the poly-dopamine thin layer of surface deposition in embodiment 1.
Fig. 4 is the scanning electron microscope (SEM) photograph of the magnesium alloy of surface bond CMC bioactive molecule in embodiment 1.
Fig. 5 is the XPS full scan spectrogram of different magnesium alloys 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 of the magnesium alloy of the poly-dopamine thin layer of surface deposition in embodiment 1.
Fig. 9 is the N1s high-resolution matching spectrogram of the magnesium alloy of surface bond CMC bioactive molecule in embodiment 1.
Figure 10 is that mtt assay is detected as osteocyte cultivates the cytoactive figure of 1,4 day in the magnesium alloy extract that original magnesium alloy and embodiment 1 obtain.
The specific embodiment
Below in conjunction with drawings and Examples, the present invention is described in more detail, but the invention is not restricted to these embodiment.
1, negative electrode liquid phase plasma is processed
With 2500 orders, 5000 object sand paper, Mg alloy surface polishing, to light, is removed to surperficial oxide layer successively, then use acetone ultrasonic cleaning 3 times, each 5 minutes, use again 5000 object sand paper that graphite rod surface finish is smooth, with ethanol ultrasonic cleaning 3 times, each 5 minutes.The water-ethanol solution of 0.08mol/L NaCl of take is electrolyte, wherein the volume ratio of deionized water and absolute ethyl alcohol is 1:4, using the magnesium alloy that cleans up as negative electrode, the graphite rod that cleans up as anode, immerse in electrolyte, adopt direct current pulse power source, adjusting discharge voltage is that 400V, frequency are that 100Hz, dutycycle are 30%, cathode and anode spacing is 4cm, magnesium alloy is carried out to negative electrode liquid phase plasma deposition, the discharge process time is 15 minutes, at Mg alloy surface, forms MgO corrosion-resistant finishes.
2, the poly-dopamine thin layer of deposition
The pH value to 8.5 of the Dopamine hydrochloride ethanolic solution that is 2mg/mL by NaOH aqueous solution quality of regulation-volumetric concentration of 0.1mol/L, magnesium alloy after step 1 is processed immerses in gained solution, soak 24 hours, take out, by deionized water, rinse well, 37 ℃ of vacuum drying 24 hours, obtain the magnesium alloy of the poly-dopamine thin layer of surface deposition.
3, surface bond CMC
Under condition of ice bath, the carboxymethyl chitosan sugar aqueous solution that is 2% by 10mL mass fraction joins 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 the poly-dopamine thin layer of deposition in step 2 is immersed in gained mixed liquor, with constant temperature oscillator normal temperature oscillating reactions 6 hours, take out, with N, after N '-dimethyl formamide cleans, by deionized water, clean up again, 37 ℃ of vacuum drying 24 hours, obtain the magnesium alloy of surface bond CMC bioactive molecule.
Adopt SEM and x-ray photoelectron spectroscopy to analyze the variation 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 of the magnesium alloy of the poly-dopamine thin layer of surface deposition, and curve d is the XPS full scan spectrogram of the magnesium alloy of surface bond CMC bioactive molecule.
From Fig. 1～4, negative electrode liquid phase plasma is processed Mg alloy surface rough porous afterwards, after the poly-dopamine thin layer of deposition, a large amount of micropores are filled to a certain extent, aperture diminishes, and it is dense that superficial film becomes, after bonding carboxymethyl chitosan glycan molecule, it is smooth smooth that Mg alloy surface becomes, and Carboxymethyl-chitosan Membranes layer is obviously visible uniformly.As seen from Figure 5, original Mg alloy surface and negative electrode liquid phase plasma are processed Mg alloy surface afterwards and are mainly comprised Mg, O, tri-kinds of elements of C, and negative electrode liquid phase plasma is processed O1s peak afterwards and is obviously strengthened, after the poly-dopamine thin layer of deposition, the characteristic element N peak that has occurred Dopamine hydrochloride, after surface bond CMC, N1s peak strengthens to some extent, shows that CMC is successfully bonded to Mg alloy surface and has introduced new N source.Known in conjunction with Fig. 6～9, negative electrode liquid phase plasma has generated MgO coating at Mg alloy surface after processing, and after the poly-dopamine thin layer of surface deposition, has occurred that the characteristic element N1s of dopamine is unimodal, in conjunction with being 400.0eV; After bonding CMC, at newly occurred-CO-NH-peak, 401.9eV place, show CMC by with poly-dopamine thin layer on amino generation amidation process be successfully bonded to Mg alloy surface.
Embodiment 2
In the negative electrode liquid phase plasma treatment step 1 of the present embodiment, the water-ethanol solution of 0.05mol/L NaCl of take is electrolyte, wherein the volume ratio of deionized water and absolute ethyl alcohol is 1:2, adopt direct current pulse power source, discharge voltage is that 350V, frequency are that 150Hz, dutycycle are 25%, cathode and anode spacing is 5cm, magnesium alloy is carried out to negative electrode liquid phase plasma deposition, and the discharge process time is 20 minutes, at Mg alloy surface, forms MgO corrosion-resistant finishes.Other steps are identical with embodiment 1, obtain the magnesium alloy of surface bond CMC bioactive molecule.
Embodiment 3
In the negative electrode liquid phase plasma treatment step 1 of the present embodiment, the water-ethanol solution of 0.12mol/L NaCl of take is electrolyte, wherein the volume ratio of deionized water and absolute ethyl alcohol is 1:5, adopt direct current pulse power source, discharge voltage is that 500V, frequency are that 130Hz, dutycycle are 35%, cathode and anode spacing is 3cm, magnesium alloy is carried out to negative electrode liquid phase plasma deposition, and the discharge process time is 10 minutes, at Mg alloy surface, forms MgO corrosion-resistant finishes.Other steps are identical with embodiment 1, obtain the magnesium alloy of surface bond CMC bioactive molecule.
In the poly-dopamine thin layer step 2 of deposition of the present embodiment, by 0.1mol/L NaOH aqueous solution quality of regulation-volumetric concentration, it is the pH value to 10 of the ethanolic solution of 3mg/mL Dopamine hydrochloride, magnesium alloy after step 1 is processed soaks 36 hours in this solution, obtains the magnesium alloy of the poly-dopamine thin layer of surface deposition.Other steps are identical with embodiment 1, obtain the magnesium alloy of surface bond CMC bioactive molecule.
Embodiment 5
In the surface bond CMC step 3 of the present embodiment, under condition of ice bath, the carboxymethyl chitosan sugar aqueous solution that is 5% by 10mL mass fraction joins 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, the magnesium alloy of the poly-dopamine thin layer of step 2 deposition is immersed in gained mixed liquor, oscillating reactions 10 hours, other steps are identical with embodiment 4, obtain the magnesium alloy of surface bond CMC bioactive molecule.
Embodiment 6
In the poly-dopamine thin layer step 2 of deposition of embodiment 1～5, the pH value to 7 of the Dopamine hydrochloride ethanolic solution that is 1mg/mL by NaOH aqueous solution quality of regulation-volumetric concentration of 0.1mol/L, magnesium alloy after step 1 is processed immerses in gained solution, soak 12 hours, take out, by deionized water, rinse well, 37 ℃ of vacuum drying 24 hours, obtain the magnesium alloy of the poly-dopamine thin layer of surface deposition.Other steps are identical with corresponding embodiment, obtain the magnesium alloy of surface bond CMC bioactive molecule.
Embodiment 7
In the surface bond CMC step 3 of embodiment 1～6, under condition of ice bath, the carboxymethyl chitosan sugar aqueous solution that is 1% by 10mL mass fraction joins 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 the poly-dopamine thin layer of deposition in step 2 is immersed in gained mixed liquor, with constant temperature oscillator normal temperature oscillating reactions 4 hours, take out, with N, after N '-dimethyl formamide cleans, by deionized water, clean up again, 37 ℃ of vacuum drying 24 hours, other steps are identical with corresponding embodiment, obtain the magnesium alloy of surface bond CMC bioactive molecule.
In order to prove beneficial effect of the present invention, inventor adopts electrochemical workstation, magnesium alloy after original magnesium alloy and embodiment 1～5 being processed by electrokinetic potential polarization curve electrochemical measuring method in SBF simulated body fluid carries out corrosion resistance measurement, by Tafel method, electrokinetic potential polarization curve is carried out to matching, the corrosion potential (E obtaining
corr) and corrosion electric current density (i
corr) in Table 1.
The corrosion potential of the different magnesium alloys of table 1 and corrosion current
| ? | E corr(V) | i corr(A/cm 2) |
| Original magnesium alloy | -1.60 | 2.44×10 -3 |
| Embodiment 1 | -1.47 | 7.00×10 -5 |
| Embodiment 2 | 1.55 | 1.30×10 -4 |
| Embodiment 3 | -1.49 | 9.26×10 -5 |
| Embodiment 4 | -1.50 | 8.53×10 -5 |
| Embodiment 5 | -1.52 | 9.72×10 -5 |
From table 1, to compare 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 wherein the corrosion electric current density of the magnesium alloy after embodiment 1 processing is reduced to 7.00 * 10
-5a/cm
2, lowered 2 orders of magnitude, corrosion potential E
corrbe elevated to-1.47V, best to the decay resistance effect of enhancing magnesium alloy.
Adopt Gegenbaur's cell, the magnesium alloy of surface bond CMC bioactive molecule embodiment 1 being obtained by mtt assay carries out biocompatibility test, 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 bond CMC bioactive molecule that Gegenbaur's cell obtains in the present invention reaches respectively 84.0% and 85.9%, apparently higher than original magnesium alloy, show to gather dopamine film and be medium layer at Mg alloy surface bonding CMC bioactive molecule, can effectively improve the biocompatibility of magnesium alloy.
Claims (4)
1. a method for Mg alloy surface bonding CMC bioactive molecule, is characterized in that it is comprised of following step:
(1) negative electrode liquid phase plasma is processed
The water-ethanol solution of 0.05～0.12mol/L NaCl of take is 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 that 350～500V, frequency are that 100～150Hz, dutycycle are 25%～35%, cathode and anode spacing is 3～5cm, magnesium alloy is carried out to negative electrode liquid phase plasma deposition, the discharge process time is 10～20 minutes, at Mg alloy surface, forms MgO corrosion-resistant finishes;
(2) the poly-dopamine thin layer of deposition
By 0.1mol/L NaOH aqueous solution quality of regulation-volumetric concentration, be pH value to 7～10 of the ethanolic solution of 1～3mg/mL Dopamine hydrochloride, magnesium alloy after step (1) is processed soaks 12～36 hours in this solution, obtains the magnesium alloy of the poly-dopamine thin layer of surface deposition;
(3) surface bond CMC
Under condition of ice bath, the carboxymethyl chitosan sugar aqueous solution that is 1%～5% by mass fraction and the N that contains 0.1mol/L1-ethyl-(3-dimethylaminopropyl) carbodiimide hydrochloride and 0.05mol/L N-hydroxy-succinamide, N '-dimethyl formamide solution is that mix 1:1～3 by volume, stir 2～3 hours, the magnesium alloy of the poly-dopamine thin layer of step (2) deposition is immersed in gained mixed liquor, oscillating reactions 4～10 hours, obtains the magnesium alloy of surface bond CMC bioactive molecule.
2. the method for Mg alloy surface bonding CMC bioactive molecule according to claim 1, it is characterized in that: in described negative electrode liquid phase plasma treatment step (1), the water-ethanol solution of 0.08mol/L NaCl of take is 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, magnesium alloy is carried out to negative electrode liquid phase plasma deposition, the discharge process time is 15 minutes, at Mg alloy surface, form MgO corrosion-resistant finishes.
3. the method for Mg alloy surface bonding CMC bioactive molecule according to claim 1, it is characterized in that: in the poly-dopamine thin layer step (2) of described deposition, the pH value to 8.5 of the Dopamine hydrochloride ethanolic solution that is 2mg/mL by NaOH aqueous solution quality of regulation-volumetric concentration of 0.1mol/L, magnesium alloy after step (1) is processed soaks 24 hours in this solution, obtains the magnesium alloy of the poly-dopamine thin layer of surface deposition.
4. the method for Mg alloy surface 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, the carboxymethyl chitosan sugar aqueous solution that is 2% by mass fraction and the N that contains 0.1mol/L 1-ethyl-(3-dimethylaminopropyl) carbodiimide hydrochloride and 0.05mol/L N-hydroxy-succinamide, N '-dimethyl formamide solution is by volume for 1:2 mixes, stir 2 hours, the magnesium alloy of the poly-dopamine thin layer of step (2) deposition is immersed in gained mixed liquor, oscillating reactions 6 hours, obtain the magnesium alloy of surface bond CMC bioactive molecule.
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| CN104746073A (en) * | 2015-04-08 | 2015-07-01 | 重庆大学 | Magnesium alloy surface modification method |
| CN105126168A (en) * | 2015-09-07 | 2015-12-09 | 上海交通大学 | Multifunctional bionic coating for magnesium-base medical materials and devices as well as preparation method and application of multifunctional bionic coating |
| 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 |
| CN111850552A (en) * | 2020-06-19 | 2020-10-30 | 淮阴工学院 | Multifunctional surface modification method for synergistically improving corrosion resistance and biocompatibility of magnesium alloy |
| CN111939331A (en) * | 2020-08-25 | 2020-11-17 | 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 |
| CN116407677A (en) * | 2023-05-30 | 2023-07-11 | 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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| CN104746073A (en) * | 2015-04-08 | 2015-07-01 | 重庆大学 | Magnesium alloy surface modification method |
| CN104746073B (en) * | 2015-04-08 | 2018-04-03 | 重庆大学 | Magnesiumalloy surface modifying method |
| CN105126168A (en) * | 2015-09-07 | 2015-12-09 | 上海交通大学 | Multifunctional bionic coating for magnesium-base medical materials and devices as well as preparation method and application of multifunctional bionic coating |
| 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 |
| CN111850552A (en) * | 2020-06-19 | 2020-10-30 | 淮阴工学院 | Multifunctional surface modification method for synergistically improving corrosion resistance and biocompatibility of magnesium alloy |
| CN111939331A (en) * | 2020-08-25 | 2020-11-17 | 南京工程学院 | Degradable metal surface gradient polymer layer and preparation method thereof |
| 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 |
| CN116407677A (en) * | 2023-05-30 | 2023-07-11 | 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 |
| 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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