CN102793947B - Degradable magnesium and surface modification method of alloy thereof - Google Patents
Degradable magnesium and surface modification method of alloy thereof Download PDFInfo
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- CN102793947B CN102793947B CN201210310003.6A CN201210310003A CN102793947B CN 102793947 B CN102793947 B CN 102793947B CN 201210310003 A CN201210310003 A CN 201210310003A CN 102793947 B CN102793947 B CN 102793947B
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Abstract
The invention relates to degradable magnesium and a surface modification method of alloy thereof, which are characterized in that the surface modification method comprises the following steps: polishing the magnesium and an alloy sample of the magnesium to remove foreign substances on the surface, cleaning acetone, and cleaning and blowing-drying anhydrous ethanol and distilled water; dipping the processed sample into solution containing sodium hydroxide and/or potassium hydroxide and sodium carbonate, cleaning with the distilled water, blowing-drying for standby or re-heating and cooling in air for standby; and dipping the processed sample into chloroformic solution containing polylactic acid or polycaprolactone, coating the processed sample by adopting a dip-coating, spraying or spin-coating method, and heating, drying and removing chloroform to obtain a degradable polymer coating. The surface protection coating prepared by the method has the characteristics of zero toxicity, degradability, good biocompatibility and the like, and the initial corrosion rate of a magnesium alloy matrix can be relieved. The invention provides a new concept for the surface modification of the degradable magnesium alloy.
Description
Technical field
The present invention relates to a kind of metallic surface method of modifying, particularly the surface modifying method of a kind of magnesium and alloy thereof.
Background technology
Magnesium metal just has clinical practice report as medical material as far back as 19 end of the centurys.Magnesium and alloy thereof have lower electrode potential, easily corrode in the internal milieu containing chloride ion/degrade, and can be degradable in vivo in the mode of slowly degrading, and its catabolite is to organism nonhazardous effect simultaneously.Because magnesium and alloy thereof have These characteristics, people expect to use it for degradable embedded material.
But, because magnesium and alloy thereof corrode too fast in human physiological environment, particularly at the implantation initial stage, corrosion rate causes magnesium implant surfaces and around pH is too high fast, thus cause magnesium implant surfaces poor biocompatibility, and the reaction that causes inflammation around, thus hinder wound healing.Meanwhile, because corrosion rate is too fast, the hydrogen of generation can not be absorbed in time by body, thus forms bubble coalescence in the tissue, and this is also unfavorable for treatment.Therefore, selecting suitable method to slow down the corrosion rate of magnesium and alloy thereof, particularly implant the corrosion rate at initial stage, is that promotion medical degradable magnesium and alloy thereof are applied to clinical necessary ways early.
Surface modification improves the effective ways of magnesium and alloy corrosion resistance energy thereof.Relevant process for treating surface has a lot, as be treated to chromate, stannate and cobaltatess representative chemical conversion process and anodic oxidation, differential arc oxidation, plating nickel on surface, aluminize or the surface modifying method such as titanizing and organic coating.But there is the potential hazard to health in part processing method, as chromate process, plating nickel on surface or aluminum; Some processing methods can not meet degradable requirement, and ceramic layer, titanium layer and the most of organic coating prepared as anodic oxidation or differential arc oxidation are all difficult to degrade in human body environment.
CN200710157568.4 discloses a kind of preparation method of magnesium alloy hydroxylapatite/polylactic acid composite biological coating.The biodegradability of the biological activity of hydroxyapatite and polylactic acid organically combines, for the corrosion protection of magnesium alloy in biotic environment by this invention.But can discharge calcium ion in hydroxyapatite degradation process, calcium ion has the effect of blood coagulation, therefore should not with blood Long Term Contact.In addition, often adhesion is poor for the organic coating directly prepared at Mg alloy surface.Owing to being that magnesium and alloy thereof are used as degradable embedded material, thus to developing nontoxic and there is good biocompatibility, can degrade in human body environment, and have the surface protecting layer of certain bond strength with magnesium and alloy thereof.
Summary of the invention
The object of this invention is to provide the surface modifying method of a kind of degradable magnesium and alloy thereof, surface protecting layer prepared by the method has nontoxic, the feature such as degradable, good biocompatibility, and can slow down the Initial Corrosion speed of magnesium alloy substrate.
The surface modifying method of magnesium of the present invention and alloy thereof is as follows:
1. to polish magnesium and alloy sample thereof, remove Superficial Foreign Body, then ultrasonic cleaning 5 ~ 15 minutes in acetone, then clean with dehydrated alcohol and distilled water respectively and dry up;
2. the sample after above-mentioned process is immersed in the solution containing sodium hydroxide and/or potassium hydroxide and sodium carbonate, wherein sodium hydroxide is or/and the mass concentration of potassium hydroxide is 20 ~ 80g/L, the mass concentration of sodium carbonate is 5 ~ 15g/L, be heated to 40 ~ 90 DEG C, 2 ~ 20 hours time, take out sample distilled water to clean, dry up for subsequent use; Or heat 2 ~ 12 hours at 60 ~ 140 DEG C again, for subsequent use after cooling in air;
3. sample after step 2 being processed immerse 3 ~ 10% polylactic acid (PLLA) or the chloroformic solution dip-coating of polycaprolactone (PCL), spraying or spin coating method coating step 2 process after sample, heat drying removing chloroform, obtains degradable polymer coating.By adjusting the molecular weight of polymer, the method for solution concentration and spraying or spin coating obtains the degradable polymer coating of different-thickness.
Described degradable polymer be obtained at present FDA or SFDA certification can the degradable polymeric material with good biocompatibility of Clinical practice, include but not limited to polylactic acid or polycaprolactone.
After above-mentioned steps 2 processes, form transition zone on the surface of magnesium and alloy thereof, its phase composition is magnesium hydroxide, sees Fig. 1; In microcosmic porous pattern, see Fig. 2.On the one hand, have good adhesion between magnesium hydroxide itself and polymer, simultaneously microcosmic porous pattern can improve the bond strength of itself and polymer coating further; On the other hand, research shows, magnesium hydroxide can slow down the Initial Corrosion speed of magnesium and alloy thereof to a certain extent.Therefore, magnesium hydroxide transition zone can play to improve and slows down magnesium and alloy substrate Initial Corrosion speed thereof and improve the effect with polymer coating bond strength.The more important thing is, the catabolite of magnesium hydroxide to body fluid or blood harmless.
Degradable polymer coating on transition zone can slow down the corrosion rate of magnesium and alloy substrate thereof further, and by the degradable polymer coating adjusting the kind of degradable polymer, molecular weight, preparation method obtain variety classes, thickness, thus realize the object controlling magnesium and alloy substrate corrosion rate thereof.In addition, also according to actual user demand, medicine can be loaded in the process preparing degradable polymer coating, namely prepare medicine carrying degradable polymer coating.Optional medicine comprises antithrombotic reagent, anti-inflammatory medicaments, anti-proliferative drugs etc.
Feature of the present invention is:
1. the present invention is directed to the deficiency that the Initial Corrosion speed of degradable magnesium and alloy existence thereof is too fast, in conjunction with its handling characteristics as medical embedded material, propose and a kind ofly reduce magnesium alloy Initial Corrosion speed and there is the preparation method of the coating of good biocompatibility.Two-step method is adopted to carry out surface modification treatment, the object slowing down magnesium alloy Initial Corrosion speed is reached by transition zone and degradable polymer coating, simultaneously due to microcosmic porous pattern and the characteristic of itself thereof of transition zone, the effect improving itself and degradable polymer coating binding force can be played.
2. the present invention is that the surface modification of medical degradable magnesium alloy provides new thinking.Described transition zone and degradable polymer coating can not only play the effect slowing down magnesium and alloy substrate corrosion thereof, also possess the performance of degrading in vivo simultaneously.This is consistent with the application original intention of medical degradable magnesium alloy.
3. the present invention can reduce the Initial Corrosion speed of magnesium alloy, and coating has good biocompatibility, can prepare drug-carried coat according to actual needs simultaneously, thus make modified magnesium alloy more can meet the needs of actual therapeutic.
Accompanying drawing explanation
Fig. 1 is the X-ray diffractogram of the transition zone that magnesium and alloy surface thereof are formed;
Fig. 2 is the microcosmic porous pattern of the transition zone that magnesium and alloy surface thereof are formed.
Detailed description of the invention
Embodiment 1
Sample is the magnesium metal of 99.95%.By sample with after sand paper grinding, ultrasonic cleaning 5 minutes in acetone and dehydrated alcohol respectively, cleans with distilled water and dries up; Will containing Na0H40g/L and Na
2cO
3the solution of 6g/L is heated to 80 DEG C, puts into sample and soaks 6 hours, cleans and dry up for subsequent use after taking-up with distilled water; It is 50,000 polylactic acid chloroformic solution that sample after base extraction is immersed the mean molecule quantity of mass concentration 8g/L, slowly lifts out solution after 3 minutes, and after so repeating 3 times, after dry, gained polylactic acid coating layer thickness is about 30 microns.
After said method surface modification, in the simulated body fluids of 37 DEG C (ion concentration: Na
+142.0mM/L, K
+5.0mM/L, Mg
2+1.5mM/L, Ca
2+2.5mM/L, Cl
-147.8mM/L, HCO
3 -4.2mM/L, HPO
4 2-1.0mM/L, SO
4 2-0.5mM/L, original ph is 7.4) in soak after 5 days, the pH of simulated body fluid is 8.2, and under the same terms, only have the pH of the simulated body fluid of magnesium hydroxide transition zone to be 9.6, the pH of the simulated body fluid of 99.95% magnesium metal of long time without surface modification is then 10.9, illustrate in immersion process, this surface reforming layer effectively slows down pH value of solution and rises, and slows down degradation rate.
Embodiment 2
Sample is AZ91 magnesium alloy.Sample after polishing, cleaning dries up; Will containing KOH30g/L and Na
2cO
3the solution of 10g/L is heated to 90 DEG C, puts into sample and soaks 8 hours, cleans and dry up for subsequent use after taking-up with distilled water, then heats 4 hours at 80 DEG C; Service property (quality) concentration to be the mean molecule quantity of 5g/L be 80,000 polycaprolactone chloroformic solution the sample after base extraction is sprayed, spraying conditions is nozzle liquid inventory 0.6mL/ hour, and spray time is 12 minutes; After dry, gained polycaprolactone coating layer thickness is about 70 microns.
AZ91, after said method surface modification, carries out cell culture experiments in vitro according to ISO10993-5, cultivates after 3 days, and the AZ91 surface adhesion through modification has a large amount of cells and its growth conditions is good, and cell quantity is about 85/mm
2, under the same terms, untreated AZ91 surface then only has only a few cell to exist, and cell quantity is about 20/mm
2, illustrate that coating that this surface modifying method obtains improves the biocompatibility of magnesium and alloy substrate thereof.
Claims (1)
1. a surface modifying method for degradable magnesium and alloy thereof, is characterized in that being made up of following steps:
1) to polish magnesium and alloy sample thereof, remove Superficial Foreign Body, then ultrasonic cleaning 5 ~ 15 minutes in acetone, then clean with dehydrated alcohol and distilled water respectively and dry up;
2) sample after above-mentioned process is immersed in the solution containing sodium hydroxide and/or potassium hydroxide and sodium carbonate, wherein sodium hydroxide is or/and the mass concentration of potassium hydroxide is 20 ~ 80g/L, the mass concentration of sodium carbonate is 5 ~ 15g/L, be heated to 40 ~ 90 DEG C, 2 ~ 20 hours time, take out sample distilled water to clean, dry up for subsequent use; Or heat 2 ~ 12 hours at 60 ~ 140 DEG C again, for subsequent use after cooling in air;
3) by step 2) to immerse the mean molecule quantity of mass concentration 8g/L be 50,000 polylactic acid chloroformic solution for sample after process, slowly lift out solution after 3 minutes, so repeat 3 times; Or be 80,000 polycaprolactone chloroformic solution spraying with the mean molecule quantity that mass concentration is 5g/L, spraying conditions is nozzle liquid inventory 0.6mL/ hour, and spray time is 12 minutes, and heat drying removing chloroform, obtains degradable polymer coating.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103934184B (en) * | 2014-03-27 | 2016-03-02 | 同济大学 | The preparation method of degradable magnesium alloy/polydactyl acid coating composite material |
| CN104189963B (en) * | 2014-05-13 | 2017-01-04 | 江苏沣沅医疗器械有限公司 | Reduction can the preparation method of surface coating of degradable magnesium alloy blood vessel rack degradation rate |
| CN105536045B (en) * | 2016-02-03 | 2018-11-30 | 东阳市特意新材料科技有限公司 | A kind of preparation method of silk-fibroin polydactyl acid magnesium alloy active coating |
| CN108159507B (en) * | 2018-01-24 | 2021-01-08 | 太原科技大学 | Antibacterial magnesium alloy material for short-term contraceptive ring and preparation method thereof |
| CN108660494B (en) * | 2018-03-23 | 2020-04-24 | 郑州大学 | Macromolecular composite film layer with covalent bond combination on surface of magnesium and magnesium alloy and preparation process thereof |
| CN111012955A (en) * | 2019-11-04 | 2020-04-17 | 南京大学 | Modified medical magnesium alloy material and preparation method thereof |
| CN111893534A (en) * | 2020-06-13 | 2020-11-06 | 郑州大学 | Preparation method of polycaprolactone coating on surface of biological magnesium alloy |
| CN115708896B (en) * | 2022-11-16 | 2024-03-19 | 南京友德邦医疗科技有限公司 | Degradable magnesium alloy composite material and preparation method thereof |
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Effective date of registration: 20171207 Address after: 510651 Changxin Road, Guangzhou, Guangdong, No. 363, No. Patentee after: NEW MATERIALS RESEARCH INSTITUTE OF GUANGDONG PROVINCE Address before: 510651 Changxin Road, Guangzhou, Guangdong, No. 363, No. Patentee before: Guangzhou Research Institute of Non-ferrous Metals |
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Address after: 510651 Changxin Road, Guangzhou, Guangdong, No. 363, No. Patentee after: Institute of new materials, Guangdong Academy of Sciences Address before: 510651 Changxin Road, Guangzhou, Guangdong, No. 363, No. Patentee before: GUANGDONG INSTITUTE OF NEW MATERIALS |