CN104711571A - Surface modification method of magnesium alloy - Google Patents
Surface modification method of magnesium alloy Download PDFInfo
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- CN104711571A CN104711571A CN201510113393.1A CN201510113393A CN104711571A CN 104711571 A CN104711571 A CN 104711571A CN 201510113393 A CN201510113393 A CN 201510113393A CN 104711571 A CN104711571 A CN 104711571A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
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Abstract
The invention discloses a surface modification method of a magnesium alloy. The method carries out magnesium alloy surface coating via layer-by-layer self-assembly; the coating is formed by repeatedly superposing polyethylene imine-sodium polystyrenesulfonate; and polyethylene imine and sodium polystyrenesulfonate are prepared into solutions by taking ionic liquid as a solvent and then spincoated on the surface of the magnesium alloy. According to the method, the functional coating is prepared on the surface of the magnesium alloy by taking the ionic liquid as the solvent; the corrosion resistance and cell responsivity of a magnesium alloy material are improved; the method overcomes the disadvantage that the traditional layer-by-layer self-assembly technology taking water as the water is difficultly applied to corrosive materials such as the magnesium alloy, has the advantages of simple technology, not need for special equipment and low preparation cost and establishes a foundation for taking the magnesium alloy as a biomedical material.
Description
Technical field
The invention belongs to medical metal material field, be specifically related to a kind of Magnesiumalloy surface modifying method.
Background technology
Magnesium alloy materials, as degradable medical metallic substance of new generation, is subject to extensive concern in recent years.Magnesium alloy materials has excellent comprehensive mechanical property and the biological degradability of uniqueness, easily shapes, and magnesium alloy materials density is the most close to skeleton density, and its Young's modulus is also close to skeleton.In addition, magnesium is again one of necessary magnanimity metallic element of human body, and the magnesium ion discharged after magnesium alloy degraded can promote the proliferation and growth of osteocyte.But corrosion of magnesium alloy speed is too fast, be difficult to meet the form of implant within the military service phase that needed by human body is wanted and mechanical requirements.On the other hand, the cellular response of magnesium alloy materials also needs further enhancing.And design surface coating can Effective Regulation magnesium alloy degradation rate, improves its corrosion resistance nature and cellular response.
Layer-by-layer is a kind of coat preparing technology, simple, without the need to main equipment, is widely used in biomaterial surface and modifies.But current biomaterial surface layer-by-layer is all carry out in water solution system, magnesium alloy materials meets water then can fast erosion, and therefore, surface modification tool layer-by-layer being used for Medical magnesium alloy material acquires a certain degree of difficulty.
In recent years the ionic liquid applied that begins one's study belongs to novel green and environment-friendly solvent, tasteless, do not fire, its vapour pressure is extremely low, can be used in high vacuum system, the problem of environmental pollution produced because of volatilization can be reduced, and ionic liquid has good solubility energy to organic and inorganics simultaneously, reaction can be made to carry out under homogeneous phase condition, have good thermostability and chemical stability, easy and other separating substances, can recycle.Because ionic liquid has above outstanding advantages, contriver intends starting with from ionic liquid, solves magnesium alloy in layer-by-layer and meets the corrosion-prone problem of water.
Summary of the invention
The object of the present invention is to provide a kind of Magnesiumalloy surface modifying method, this method solve the corrosion-prone difficult problem of magnesium alloy in layer-by-layer conventional in process for modifying surface.The present invention is based on following technical scheme to realize above-mentioned purpose:
A kind of Magnesiumalloy surface modifying method, the method obtains coating of magnesium alloy surface by LBL self-assembly, the mode that described coating repeats to superpose with polymine-sodium polystyrene sulfonate forms, and is spun on Mg alloy surface after described polymine and sodium polystyrene sulfonate ionic liquid are mixed with solution.
Preferably, comprise the steps:
(1) base material pre-treatment: Mg alloy surface is polished, cleaning;
(2) LBL self-assembly: be that the polymine of 1 ~ 10mg/mL and the ionic liquid solution of sodium polystyrene sulfonate are spun on step (1) pretreated Mg alloy surface successively by concentration, spin speed 300 ~ 4000rpm, spin-coating time 8 ~ 50s, namely every spin coating once cleans 1 minute with ultrapure water; Complete with two solution spin coatings is a LBL self-assembly circulation, and circulate 10 ~ 100 times, then nitrogen dries up.
Preferred, comprise the steps:
(1) base material pre-treatment: by magnesium alloy polishing to surface-brightening, and clean to Mg alloy surface with acetone ultrasonic cleaning;
(2) LBL self-assembly: be that the polymine of 5mg/mL and the 1-ethyl-3-methylimidazole sulfovinic acid salts solution of sodium polystyrene sulfonate are spun on step (1) pretreated Mg alloy surface successively by concentration, spin speed 1500rpm, spin-coating time 15s, namely every spin coating once cleans 1 minute with ultrapure water; Complete with two solution spin coatings is a LBL self-assembly circulation, and circulate 25 times, then nitrogen dries up; Described 1-ethyl-3-methylimidazole sulfovinic acid concentration of salt solution is 5mg/mL.
Beneficial effect of the present invention is: the present invention is by adopting ionic liquid to be solvent, functional coating is prepared at Mg alloy surface, improve erosion resistance and the cellular response of magnesium alloy materials, overcoming tradition take water as the shortcoming that the layer-by-layer of solvent is difficult to be applied to the corrosion susceptible materials such as magnesium alloy, have technique simple, without the need to specific installation, the advantage that preparation cost is low, for magnesium alloy is laid a good foundation as bio-medical material.
Accompanying drawing explanation
In order to make object of the present invention, technical scheme and beneficial effect clearly, the invention provides following accompanying drawing:
The scanning electron microscope (SEM) photograph of the original magnesium alloy of Fig. 1;
The scanning electron microscope (SEM) photograph of magnesium alloy after Fig. 2 surface modification;
The x-ray photoelectron spectroscopy figure of magnesium alloy after Fig. 3 surface modification;
The dynamic potential polarization curve figure of magnesium alloy before and after Fig. 4 surface modification;
Fig. 5 mtt assay is detected as the cytoactive figure that osteocyte is cultivated in magnesium alloy extracting solution 1,4,7 day after original magnesium alloy and surface modification.
Embodiment
Below the preferred embodiments of the present invention are described in detail.The experimental technique of unreceipted actual conditions in embodiment, the usually conveniently conditioned disjunction condition of advising according to manufacturer.
A kind of Magnesiumalloy surface modifying method, concrete steps are as follows:
(1) base material pre-treatment: Mg alloy surface is polished, cleaning;
(2) LBL self-assembly: be that the ionic liquid solution of 1 ~ 10mg/mL polymine and sodium polystyrene sulfonate is spun on step (1) pretreated Mg alloy surface successively by concentration, spin speed 300 ~ 4000rpm, spin-coating time 8 ~ 50s, namely every spin coating once cleans 1 minute with ultrapure water; Complete two solution of spin coating circulate as a LBL self-assembly, and circulate altogether 10 ~ 100 times, then nitrogen dries up.
Embodiment 1
A kind of Magnesiumalloy surface modifying method, concrete steps are as follows:
(1) base material pre-treatment
By magnesium alloy polishing to surface-brightening, use acetone ultrasonic cleaning, obtain clean metallic surface;
(2) LBL self-assembly
Be that the 1-ethyl-3-methylimidazole sulfovinic acid salts solution of 5mg/mL polymine and sodium polystyrene sulfonate is spun on step (1) pretreated Mg alloy surface successively by concentration, spin speed 1500rpm, spin-coating time 15s, namely every spin coating once cleans 1 minute with ultrapure water, complete two solution of spin coating circulate as a LBL self-assembly, circulate 25 times altogether, then nitrogen dries up; Described 1-ethyl-3-methylimidazole sulfovinic acid concentration of salt solution is 5mg/mL.
Embodiment 2
A kind of Magnesiumalloy surface modifying method, concrete steps are as follows:
(1) base material pre-treatment
By magnesium alloy polishing to surface-brightening, use acetone ultrasonic cleaning, obtain clean metallic surface;
(2) LBL self-assembly
Be that the 1-ethyl-3-methylimidazole sulfovinic acid salts solution of 1mg/mL polymine and sodium polystyrene sulfonate is spun on step (1) pretreated Mg alloy surface successively by concentration, spin speed 300rpm, spin-coating time 8s, namely every spin coating once cleans 1 minute with ultrapure water, complete two solution of spin coating circulate as a LBL self-assembly, circulate 10 times altogether, then nitrogen dries up; Described 1-ethyl-3-methylimidazole sulfovinic acid concentration of salt solution is 5mg/mL.
Embodiment 3
A kind of Magnesiumalloy surface modifying method, concrete steps are as follows:
(1) base material pre-treatment
By magnesium alloy polishing to surface-brightening, use acetone ultrasonic cleaning, obtain clean metallic surface;
(2) LBL self-assembly
Be that the 1-ethyl-3-methylimidazole sulfovinic acid salts solution of 10mg/mL polymine and sodium polystyrene sulfonate is spun on step (1) pretreated Mg alloy surface successively by concentration, spin speed 4000rpm, spin-coating time 50s, namely every spin coating once cleans 1 minute with ultrapure water, complete two solution of spin coating circulate as a LBL self-assembly, circulate 100 times altogether, then nitrogen dries up; Described 1-ethyl-3-methylimidazole sulfovinic acid concentration of salt solution is 5mg/mL.
Embodiment 4
A kind of Magnesiumalloy surface modifying method, concrete steps are as follows:
(1) base material pre-treatment
By magnesium alloy polishing to surface-brightening, use acetone ultrasonic cleaning, obtain clean metallic surface;
(2) LBL self-assembly
Be that the 1-ethyl-3-methylimidazole sulfovinic acid salts solution of 4mg/mL polymine and sodium polystyrene sulfonate is spun on step (1) pretreated Mg alloy surface successively by concentration, spin speed 1000rpm, spin-coating time 10s, namely every spin coating once cleans 1 minute with ultrapure water, complete two solution of spin coating circulate as a LBL self-assembly, circulate 20 times altogether, then nitrogen dries up; Described 1-ethyl-3-methylimidazole sulfovinic acid concentration of salt solution is 5mg/mL.
The Properties of Magnesium Alloy test that the method for the invention is modified
The modified magnesium alloy that the surface obtained with the present invention forms cellular response corrosion-resistant finishes carries out following experiment, and wherein with the original magnesium alloy of non-coating in contrast, described original magnesium alloy is the pretreatment operation of only carrying out base material.
1, with scanning electronic microscope (FEI Nova 400, Philips company) observe the change of Mg alloy surface pattern, from Fig. 1 and Fig. 2, original Mg alloy surface presents the fine scratches formed in a lot of bruting process, and assist after LBL self-assembly process through ionic liquid, the Mg alloy surface of modification is more coarse, generates new coating.
2, with x-ray photoelectron spectroscopy (FEI Nova 400, Philips company) analyze Mg alloy surface element variation, as seen from Figure 3, assist the modification Mg alloy surface after LBL self-assembly process to occur the peak of carbon, nitrogen, oxygen and element sulphur through ionic liquid, show multilayer film successful deposition in material surface.
3, dynamic potential polarization curve mensuration is carried out with electrochemical workstation sample (AutoLab, Wan Tong company of Switzerland).Test is carried out in Artificial Bodys, and adopt three-electrode system to carry out electro-chemical test, with saturated calomel electrode (SCE) for reference electrode, Pt electrode is supporting electrode, and sample is as working electrode, and potential scanning speed is 0.05V/s.Fig. 4 is that ionic liquid assists the electrokinetic potential scanning polarization curve of magnesium alloy in SBF simulated body fluid before and after LBL self-assembly process respectively, by Tafel method, matching is carried out to dynamic potential polarization curve, obtain corrosion potential (Ecorr) and corrosion electric current density (icorr), the results are shown in Table 1.
The corrosion potential of the different magnesium alloy of table 1 and corrosion current
As can be seen from Table 1, containing magnesium alloy after the surface modification of corrosion-resistant cellular response coating, corrosion electric current density reduces 1 order of magnitude than the corrosion electric current density of original non-coating magnesium alloy, corrosion potential improves about 100mV, shows to assist LBL self-assembly process can improve the erosion resistance of magnesium alloy through ionic liquid.
4, adopt scleroblast, carry out cell compatibility test by mtt assay effects on surface modification magnesium alloy, with the original magnesium alloy of non-coating for contrast.Often organizing magnesium alloy sample surfaces inoculation rat osteoblast, inoculum density is 1 × 10
4individual/hole, with containing 10% serum, 1% dual anti-RPMI 1640 culture medium culturing, cultivate 1 day, 4 days and 7 days respectively, then every hole adds MTT 100 μ L, cultivate 4 hours for 37 DEG C, inhale and abandon supernatant liquor, more every hole adds DMSO 0.5mL, measure absorbancy by microplate reader in wavelength 490nm place, the results are shown in Figure 5.As seen from Figure 5, scleroblast cultivates the cytoactive of 1,4,7 day all higher than original magnesium alloy at the Mg alloy surface of surface modification, wherein the result of 4 days and 7 days presents significant difference, shows that method of the present invention can improve the cell compatibility of magnesium alloy effectively.
What finally illustrate is, above preferred embodiment is only in order to illustrate technical scheme of the present invention and unrestricted, although by above preferred embodiment to invention has been detailed description, but those skilled in the art are to be understood that, various change can be made to it in the form and details, and not depart from claims of the present invention limited range.
Claims (3)
1. a Magnesiumalloy surface modifying method, the method obtains coating of magnesium alloy surface by LBL self-assembly, it is characterized in that, the mode that described coating repeats to superpose with polymine-sodium polystyrene sulfonate forms, and is spun on Mg alloy surface after described polymine and sodium polystyrene sulfonate ionic liquid are mixed with solution.
2. Magnesiumalloy surface modifying method as claimed in claim 1, is characterized in that, comprise the steps:
(1) base material pre-treatment: Mg alloy surface is polished, cleaning;
(2) LBL self-assembly: be that the polymine of 1 ~ 10mg/mL and the ionic liquid solution of sodium polystyrene sulfonate are spun on step (1) pretreated Mg alloy surface successively by concentration, spin speed 300 ~ 4000rpm, spin-coating time 8 ~ 50s, namely every spin coating once cleans 1 minute with ultrapure water; Complete with two solution spin coatings is a LBL self-assembly circulation, and circulate 10 ~ 100 times, then nitrogen dries up.
3. Magnesiumalloy surface modifying method as claimed in claim 2, is characterized in that, comprise the steps:
(1) base material pre-treatment: by magnesium alloy polishing to surface-brightening, and clean to Mg alloy surface with acetone ultrasonic cleaning;
(2) LBL self-assembly: be that the polymine of 5mg/mL and the 1-ethyl-3-methylimidazole sulfovinic acid salts solution of sodium polystyrene sulfonate are spun on step (1) pretreated Mg alloy surface successively by concentration, spin speed 1500rpm, spin-coating time 15s, namely every spin coating once cleans 1 minute with ultrapure water; Complete with two solution spin coatings is a LBL self-assembly circulation, and circulate 25 times, then nitrogen dries up; Described 1-ethyl-3-methylimidazole sulfovinic acid concentration of salt solution is 5mg/mL.
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| CN201510113393.1A CN104711571A (en) | 2015-03-16 | 2015-03-16 | Surface modification method of magnesium alloy |
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| CN201510113393.1A CN104711571A (en) | 2015-03-16 | 2015-03-16 | Surface modification method of magnesium alloy |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109290736A (en) * | 2017-07-24 | 2019-02-01 | 嘉瑞科技（惠州）有限公司 | A kind of magnesium alloy workpiece processing method with primary colors bloom texture |
| CN111842070A (en) * | 2020-07-01 | 2020-10-30 | 安徽新大陆特种涂料有限责任公司 | Construction method of self-assembled environment-friendly long-acting easy-to-clean anticorrosive coating |
-
2015
- 2015-03-16 CN CN201510113393.1A patent/CN104711571A/en active Pending
Non-Patent Citations (2)
| Title |
|---|
| TAKUYA NAKASHIMA ET AL.: "Polyelectrolyte and carbon nanotube multilayers made from ionic liquid solutions", 《NANOSCALE》 * |
| 雎晓静: "镁合金表面修饰及其抗腐蚀性和生物相容性研究", 《中国优秀硕士学位论文全文数据库 医药卫生科技辑》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109290736A (en) * | 2017-07-24 | 2019-02-01 | 嘉瑞科技（惠州）有限公司 | A kind of magnesium alloy workpiece processing method with primary colors bloom texture |
| CN111842070A (en) * | 2020-07-01 | 2020-10-30 | 安徽新大陆特种涂料有限责任公司 | Construction method of self-assembled environment-friendly long-acting easy-to-clean anticorrosive coating |
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Application publication date: 20150617 |
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