CN103614718B - A kind of method obtaining the coating of biological functional and low corrosion speed at pure magnesium surface - Google Patents
A kind of method obtaining the coating of biological functional and low corrosion speed at pure magnesium surface Download PDFInfo
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- CN103614718B CN103614718B CN201310524913.9A CN201310524913A CN103614718B CN 103614718 B CN103614718 B CN 103614718B CN 201310524913 A CN201310524913 A CN 201310524913A CN 103614718 B CN103614718 B CN 103614718B
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Abstract
Obtain a method for the coating of biological functional and low corrosion speed at pure magnesium surface, the steps include: A, be the plant acid solution of 2-10g/L by concentration, by ammoniacal liquor adjust ph to 5-8, obtain corrosion inhibition agent solution; B, heparin or Bivalirudin to be dissolved in corrosion inhibition agent solution, to obtain modified solution; In modified solution, the concentration of heparin or Bivalirudin is 2-5g/L; C, by the pure magnesium of cleaning temperature be 50-80 DEG C, concentration is soak 12-24 hour in the NaOH solution of 1-6mol/L, obtains the pure magnesium of alkali activation; D, by alkali activate pure magnesium be immersed in modified solution, be warming up to 50-80 DEG C insulation 20-80 minute, namely obtain biological functional and corrosion-resistant finishes at pure magnesium surface.The coating that the method obtains is biological functional coating, has good biocompatibility, and effectively can reduce the erosion rate of pure magnesium.
Description
Technical field
The present invention relates to the preparation method of Biofunctional materials, particularly relate to a kind of method obtaining the coating of biological functional and low corrosion speed at pure magnesium surface.
Background technology
Magnesium and magnesium alloy thereof be burn into degradable in vivo very easily, and the Young's modulus of its Young's modulus and skeleton is close, it is used widely at osseous tissue material as biological implantation material, and in intravascular stent material, there is applications well prospect.But because the chemically reactive of magnesium and magnesium alloy thereof is higher, very easily corroded by the environment of surrounding after being implanted to human body as embedded material, make it too early lose its mechanical property; Therefore, during as embedded material, the control of its corrosion just seems particularly important.In addition, unavoidably produce biology rejection as foreign matter implant into body, its biological functionality (biocompatibility) is also of equal importance.
For intravascular stent, present vascular stent material mostly is the nondegradable materials such as stainless steel, vitallium, Ni-Ti alloy.The nondegradable support of long-term implantation can cause a series of immune response of human body, causes the inflammation that local is long-term, and the infringement of theca interna, thus causes unstriated muscle hyper-proliferative, causes restenosis.Therefore, Full degradation type support becomes and addresses these problems most effective means, and magnesium and magnesium alloy thereof become one of most promising material.For intravascular stent mg-based material, its corrosion control and biocompatibility are problem demanding prompt solution all the time.
Summary of the invention
The object of this invention is to provide a kind of method obtaining the coating of biological functional and low corrosion speed at pure magnesium surface, the coating that the method obtains is biological functional coating, has good biocompatibility, and effectively can reduce the erosion rate of pure magnesium.
The present invention realizes the technical scheme that its goal of the invention adopts, and a kind of method obtaining the coating of biological functional and low corrosion speed at pure magnesium surface, the steps include:
A, be the plant acid solution of 2-10g/L by concentration, by ammoniacal liquor adjust ph to 5-8, obtain corrosion inhibition agent solution;
B, heparin or Bivalirudin to be dissolved in the corrosion inhibition agent solution of A step, to obtain corrosion inhibitor and the blended modified solution of biomolecules; In modified solution, the concentration of heparin or Bivalirudin is 2-5g/L;
C, by the pure magnesium of cleaning temperature be 50-80 DEG C, concentration is soak 12-24 hour in the NaOH solution of 1-6mol/L, obtains the pure magnesium of alkali activation;
D, pure magnesium C being walked the alkali activation obtained are immersed in the modified solution of B step, and be warming up to 50-80 DEG C of insulation 20-80 minute, the pure magnesium that itself and alkali are activated reacts, and namely obtains biological functional and corrosion-resistant finishes at pure magnesium surface.
Mechanism of the present invention is:
By pure magnesium alkali is activated, obtain magnesium hydroxide coating on the surface of pure magnesium, subsequently, the pure magnesium that alkali activates is immersed in phytic acid and the blended modified solution of biomolecules, the magnesium hydroxide of the pure magnesium surface that phytic acid can activate with alkali reacts, and is fixed on the surface of pure magnesium; Biomolecules is then wrapped up because the magnesium hydroxide of phytic acid and pure magnesium surface reacts the machinery produced, and is fixed on the surface of pure magnesium, realizes its corrosion-resistant and function that is biocompatibility.
Compared with prior art, the invention has the beneficial effects as follows:
One, obtain magnesium hydroxide coating by alkali activation on the surface of pure magnesium, namely strengthen corrosion inhibitor-phytic acid fixing at pure magnesium surface, it also avoid the matrix corrosion effect of plant acid solution to pure magnesium simultaneously, protect the matrix of pure magnesium.In use (degraded) process, magnesium matrix is corroded and discharges magnesium ion, simultaneously corrosion inhibitor---phytic acid can with the magnesium ion generation chelatropic reaction that discharges in corrosion process, form fine and close chelate products layer on surface, thus play a good protection at the corrosive medium initial stage; Its erosion rate is low, avoids too early to lose its mechanical property.Meanwhile, by regulating modified solution soak time to regulate the thickness of coating, thus regulate erosion rate to meet different treatments, rehabilitation requirement.
Two, biomolecules is that magnesium hydroxide after corrosion inhibitor and alkali the activate machinery produced that reacts wraps up the surface being fixed on pure magnesium, and biomolecules chemical transformation does not occur, and the biological activity of biomolecules keeps.In use (degraded) process, the biomolecules that surface is fixed constantly is released in corrosive medium, the effect of biological functional occurs, has good biocompatibility.
Three, preparation method is middle temperature liquid phase cracking process, and mild condition, easy to operate, preparation cost is low, be applicable to large-scale industrial production.
Below in conjunction with the drawings and specific embodiments, the present invention is described in further detail.
Accompanying drawing explanation
Fig. 1 is the obtained thing (Mg-OH-PA & Hep) of embodiment 1 and the dynamic potential polarization curve figure of pure magnesium (Mg).
Fig. 2 is the obtained thing (Mg-OH-PA & BVLD) of embodiment 4 and the dynamic potential polarization curve figure of pure magnesium (Mg).
Embodiment
Embodiment 1
Obtain a method for the coating of biological functional and low corrosion speed at pure magnesium surface, the steps include:
A, be the plant acid solution of 2g/L by concentration, by ammoniacal liquor adjust ph to 5, obtain corrosion inhibition agent solution;
B, heparin to be dissolved in the corrosion inhibition agent solution of A step, to obtain corrosion inhibitor and the blended modified solution of biomolecules; In modified solution, the concentration of heparin is 2g/L;
C, by the pure magnesium of cleaning temperature be 60 DEG C, concentration be in the NaOH solution of 3mol/L soak 24 hours, obtain alkali activation pure magnesium; The pure magnesium of this example is the pure magnesium of as cast condition.
D, pure magnesium C being walked the alkali activation obtained are immersed in the modified solution of B step, and be warming up to 60 DEG C of insulations 40 minutes, the pure magnesium that itself and alkali are activated reacts, and namely obtains biological functional and corrosion-resistant finishes at pure magnesium surface.
Fig. 1 is the obtained thing (referred to as Mg-OH-PA & Hep in figure, wherein PA is phytic acid, Hep is heparin) of this example and the dynamic potential polarization curve figure of pure magnesium (referred to as Mg in figure).Fig. 1 shows this example, and after pure magnesium surface obtains biological functional and corrosion-resistant finishes, its corrosion current is compared with pure magnesium, and decline two orders of magnitude, and erosion rate significantly reduces.
The obtained thing (Mg-OH-PA & Hep) of this example with contrast (Mg-OH-PA, its preparation method is substantially identical with this example with step, just remove the operation of B step, the pure magnesium that the alkali that the corrosion inhibition agent solution directly walked by A and C walk activates carries out immersion and reacts) carry out clotting time test, test shows that the clotting time contrasted is 75 seconds, and the obtained thing of this example its clotting time after pure magnesium surface obtains biological functional and corrosion-resistant finishes raises, full test time value-150 second of instrument are exceeded.
Embodiment 2
Obtain a method for the coating of biological functional and low corrosion speed at pure magnesium surface, the steps include:
A, be the plant acid solution of 5g/L by concentration, by ammoniacal liquor adjust ph to 7, obtain corrosion inhibition agent solution;
B, heparin to be dissolved in the corrosion inhibition agent solution of A step, to obtain corrosion inhibitor and the blended modified solution of biomolecules; In modified solution, the concentration of heparin is 3g/L;
C, by the pure magnesium of cleaning temperature be 50 DEG C, concentration be in the NaOH solution of 6mol/L soak 12 hours, obtain alkali activation pure magnesium; The pure magnesium of this example is the pure magnesium of as cast condition.
D, pure magnesium C being walked the alkali activation obtained are immersed in the modified solution of B step, and be warming up to 80 DEG C of insulations 80 minutes, the pure magnesium that itself and alkali are activated reacts, and namely obtains biological functional and corrosion-resistant finishes at pure magnesium surface.
Embodiment 3
Obtain a method for the coating of biological functional and low corrosion speed at pure magnesium surface, the steps include:
A, be the plant acid solution of 10g/L by concentration, by ammoniacal liquor adjust ph to 8, obtain corrosion inhibition agent solution;
B, heparin to be dissolved in the corrosion inhibition agent solution of A step, to obtain corrosion inhibitor and the blended modified solution of biomolecules; In modified solution, the concentration of heparin is 5g/L;
C, by the pure magnesium of cleaning temperature be 80 DEG C, concentration be in the NaOH solution of 1mol/L soak 20 hours, obtain alkali activation pure magnesium; The pure magnesium of this example is the pure magnesium of As-extruded.
D, pure magnesium C being walked the alkali activation obtained are immersed in the modified solution of B step, and be warming up to 50 DEG C of insulations 20 minutes, the pure magnesium that itself and alkali are activated reacts, and namely obtains biological functional and corrosion-resistant finishes at pure magnesium surface.
Embodiment 4
Obtain a method for the coating of biological functional and low corrosion speed at pure magnesium surface, the steps include:
A, be the plant acid solution of 5g/L by concentration, by ammoniacal liquor adjust ph to 5, obtain corrosion inhibition agent solution;
B, Bivalirudin to be dissolved in the corrosion inhibition agent solution of A step, to obtain corrosion inhibitor and the blended modified solution of biomolecules; In modified solution, the concentration of Bivalirudin is 3/L;
C, by the pure magnesium of cleaning temperature be 50 DEG C, concentration be in the NaOH solution of 6mol/L soak 12 hours, obtain alkali activation pure magnesium; The pure magnesium of this example is the pure magnesium of As-extruded.
D, pure magnesium C being walked the alkali activation obtained are immersed in the modified solution of B step, and be warming up to 80 DEG C of insulations 40 minutes, the pure magnesium that itself and alkali are activated reacts, and namely obtains biological functional and corrosion-resistant finishes at pure magnesium surface.
Fig. 2 is the obtained thing (referred to as Mg-OH-PA & BVLD in figure, wherein PA is phytic acid, BVLD is Bivalirudin) of this example and the dynamic potential polarization curve figure of pure magnesium (referred to as Mg in figure).Fig. 2 shows this example, and after pure magnesium surface obtains biological functional and corrosion-resistant finishes, its corrosion current is compared with pure magnesium, and decline two orders of magnitude, and erosion rate significantly reduces.
The obtained thing (Mg-OH-PA & BVLD) of this example with contrast (Mg-OH-PA, its preparation method is substantially identical with this example with step, just remove the operation of B step, the pure magnesium that the alkali that the corrosion inhibition agent solution directly walked by A and C walk activates carries out immersion and reacts) carry out clotting time test, test shows that the clotting time contrasted is 75 seconds, and the obtained thing of this example its clotting time after pure magnesium surface obtains biological functional and corrosion-resistant finishes raises, full test time value-150 second of instrument are exceeded.
Embodiment 5
Obtain a method for the coating of biological functional and low corrosion speed at pure magnesium surface, the steps include:
A, be the plant acid solution of 10g/L by concentration, by ammoniacal liquor adjust ph to 8, obtain corrosion inhibition agent solution;
B, Bivalirudin to be dissolved in the corrosion inhibition agent solution of A step, to obtain corrosion inhibitor and the blended modified solution of biomolecules; In modified solution, the concentration of Bivalirudin is 2.5g/L;
C, by the pure magnesium of cleaning temperature be 80 DEG C, concentration be in the NaOH solution of 4mol/L soak 24 hours, obtain alkali activation pure magnesium; The pure magnesium of this example is the pure magnesium of As-extruded.
D, pure magnesium C being walked the alkali activation obtained are immersed in the modified solution of B step, and be warming up to 70 DEG C of insulations 80 minutes, the pure magnesium that itself and alkali are activated reacts, and namely obtains biological functional and corrosion-resistant finishes at pure magnesium surface.
Embodiment 6
Obtain a method for the coating of biological functional and low corrosion speed at pure magnesium surface, the steps include:
A, be the plant acid solution of 2g/L by concentration, by ammoniacal liquor adjust ph to 6, obtain corrosion inhibition agent solution;
B, Bivalirudin to be dissolved in the corrosion inhibition agent solution of A step, to obtain corrosion inhibitor and the blended modified solution of biomolecules; In modified solution, the concentration of Bivalirudin is 2g/L;
C, by the pure magnesium of cleaning temperature be 60 DEG C, concentration be in the NaOH solution of 1mol/L soak 15 hours, obtain alkali activation pure magnesium; The pure magnesium of this example is the pure magnesium of as cast condition.
D, pure magnesium C being walked the alkali activation obtained are immersed in the modified solution of B step, and be warming up to 50 DEG C of insulations 20 minutes, the pure magnesium that itself and alkali are activated reacts, and namely obtains biological functional and corrosion-resistant finishes at pure magnesium surface.
Claims (2)
1. obtain a method for the coating of biological functional and low corrosion speed at pure magnesium surface, the steps include:
A, be the plant acid solution of 2-10g/L by concentration, by ammoniacal liquor adjust ph to 5-8, obtain corrosion inhibition agent solution;
B, heparin or Bivalirudin to be dissolved in the corrosion inhibition agent solution of A step, to obtain corrosion inhibitor and the blended modified solution of biomolecules; In modified solution, the concentration of heparin or Bivalirudin is 2-5g/L;
C, by the pure magnesium of cleaning temperature be 50-80 DEG C, concentration is soak 12-24 hour in the NaOH solution of 1-6mol/L, obtains the pure magnesium of alkali activation;
D, pure magnesium C being walked the alkali activation obtained are immersed in the modified solution of B step, and be warming up to 50-80 DEG C of insulation 20-80 minute, the pure magnesium that itself and alkali are activated reacts, and namely obtains biological functional and corrosion-resistant finishes at pure magnesium surface.
2. a kind of method obtaining the coating of biological functional and low corrosion speed at pure magnesium surface according to claim 1, it is characterized in that, described pure magnesium is the pure magnesium of as cast condition, the pure magnesium of As-extruded.
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| CN105803446B (en) * | 2016-03-17 | 2018-08-17 | 西南交通大学 | A method of functional coating being prepared in situ in Mg alloy surface |
| CN106835094B (en) * | 2017-02-23 | 2019-05-17 | 西南交通大学 | A kind of preparation method for the pure magnesium surface biological functional coating that corrosion rate is low |
| CN107119269B (en) * | 2017-04-17 | 2019-05-17 | 西南交通大学 | In the method that magnesium based metal building has the winestone of corrosion protection effect acid coated |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101214395A (en) * | 2008-01-02 | 2008-07-09 | 西南交通大学 | Inorganic material surface biological method |
| CN101549170A (en) * | 2009-05-05 | 2009-10-07 | 先健科技(深圳)有限公司 | Human body absorbable blood vessel support and its manufacturing method |
| CN102268668A (en) * | 2011-07-28 | 2011-12-07 | 中国人民解放军第三军医大学 | Preparation method of magnesium alloy surface conversion film |
| CN102268639A (en) * | 2011-07-13 | 2011-12-07 | 西南交通大学 | Method for preparing heparinized interface material with high biological functionality |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101214395A (en) * | 2008-01-02 | 2008-07-09 | 西南交通大学 | Inorganic material surface biological method |
| CN101549170A (en) * | 2009-05-05 | 2009-10-07 | 先健科技(深圳)有限公司 | Human body absorbable blood vessel support and its manufacturing method |
| CN102268639A (en) * | 2011-07-13 | 2011-12-07 | 西南交通大学 | Method for preparing heparinized interface material with high biological functionality |
| CN102268668A (en) * | 2011-07-28 | 2011-12-07 | 中国人民解放军第三军医大学 | Preparation method of magnesium alloy surface conversion film |
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