CN103372232A - Micro-arc oxidation self-sealing hole active coating of magnesium-based implant material and preparation method of micro-arc oxidation self-sealing hole active coating - Google Patents
Micro-arc oxidation self-sealing hole active coating of magnesium-based implant material and preparation method of micro-arc oxidation self-sealing hole active coating Download PDFInfo
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- A61L2430/02—Materials or treatment for tissue regeneration for reconstruction of bones; weight-bearing implants
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Abstract
The invention relates to the field of the surface modification of a biomedical degradable magnesium-based metal material, and particularly relates to a micro-arc oxidation self-sealing hole active coating of a magnesium-based implant material and a preparation method of the micro-arc oxidation self-sealing hole active coating. The surface microtopography of the coating obtained by the preparation method is different from that of a conventional micro-arc oxidation coating (having porous characteristic). The vast majority of holes formed through micro-arc oxidation discharge are directly filled with materials containing calcium and phosphorus; the coating has high density; and the corrosion resistance of the coating is improved without follow-up hole-sealing treatment. In addition, a porous structure formed by discharging or filling compounds in multiple holes comprises identical chemical components, the atomic percentages of the calcium and the phosphorus contained in the surface respectively reach 3-6% and 9-15%, and the calcium, the phosphorus and fluorine contained in the coating greatly improve the biological activity of the coating. Certain follow-up hole-sealing treatment processes needed after conventional micro-arc oxidation are abandoned due to the characteristics of the self-sealing holes. The method is simple and practicable, has very strong practicability and can be used for the surface treatment of the various magnesium-based implant materials.
Description
Technical field
The invention belongs to the surface modification field of bio-medical material, be specially a kind of magnesium-base metal embedded material differential arc oxidation pore self-sealing active coating and preparation method thereof, can be applicable to the surface modification treatment of all kinds of degradable magnesium Base Metal implantation instruments.
Background technology
Magnesium-base metal material with biodegradable characteristics has unique advantage in reparation both injured bones organizational aspects.On the one hand, these materials have higher specific strength and specific stiffness, elastic modelling quantity is about 45GPa, more approaching with human body natural's bone, can effectively alleviate stress-shielding effect after the implantation, and can in human body, dissolve, absorb or excrete, after the osseous tissue healing, can die away, need not second operation, alleviate patient's misery.On the other hand, a large amount of magnesium ions that the magnesium-base metal material produces in degradation process can promote the deposition of synthos, accelerate osteoblastic differentiation, induce the formation of new bone, have good bone biocompatibility and osteoinductive.So the degradable magnesium Base Metal has tempting application potential as hard tissue implanting material.
But because the chemical property of magnesium-base metal is very active, particularly corrosion rate is too fast under physiological environment, cause thus local alkalization, can cause subcutaneous bubbling and liberation of hydrogen is too fast, be unfavorable for organization healing, and very likely before organization healing, just lose mechanical integrity.Therefore, in order to improve the decay resistance of degradable magnesium Base Metal, it is technical that many researchs all concentrate on face coat, such as alkali heat treatment, plasma spraying, chemical conversion film, electrochemical deposition, anodic oxidation etc.But all there is certain problem in these coatings, be in particular in that the adhesion of coating and substrate is relatively poor, wear no resistance, fine and close not, the degraded of control coating is not ideal enough etc.
In recent years, differential arc oxidation has been applied to biomedical materials field as a kind of easy process for modifying surface, this technology can be on titanium, magnesium and alloy surface thereof growth in situ one deck fine and close and with matrix the ceramic membrane of stronger adhesion is arranged.But in the differential arc oxidization surface modification to magnesium-base metal, most of coatings all concentrate on the silicate coating system, and the research of the bioactivity coatings of effects on surface calcic phosphorus is less.The people such as P.Bala Srinivasan of Germany adopt calcium hydroxide and tertiary sodium phosphate electrolyte to tie up to the differential arc oxidation coating of having prepared calcic phosphorus on the AM50 Mg alloy surface, and studied the impact of different electrolytes composition proportion on coating performance and structure, prepared coating surface is the open architecture of porous, and all than the low of AM50 alloy of being untreated, corrosion tendency is larger for the corrosion potential of coating.It is worth mentioning that selected electrolyte calcium hydroxide is slightly soluble in water, the adding that affiliation causes generating the calcium phosphate of indissoluble more of tertiary sodium phosphate and so that electrolyte precipitates, the electrolyte poor stability is unfavorable for the recycling of electrolyte.In addition, domestic Harbin Institute of Technology has also prepared the differential arc oxidation coating of calcic phosphorus on the AZ91D Mg alloy surface, and by the adjusting process gain of parameter coating of Different Ca/P ratio, but still distributing many micron-sized micropores on these coatings, the micropore that has even be communicated to the matrix magnesium alloy.These differential arc oxidation coating surfaces all are open loose structures, corrosive liquid is easy to penetrate into substrate and the reaction of magnesium corrosion by these holes, thereby spot corrosion occurs, bring out large-area corrosion, so these coatings can't be controlled the degradation rate of magnesium-base metal embedded material well.So the sealing of hole that some differential arc oxidation coating also needs to carry out the later stage is processed, thereby treatment process and cost have been increased, and the follow-up sealing of hole processing as the magnesium-base metal embedded material also need be considered its biological safety and degradability, and this has just increased a lot of problems for its clinical practice.
Summary of the invention
The purpose of this invention is to provide a kind of magnesio embedded material differential arc oxidation pore self-sealing active coating and preparation method thereof, by adjusting the formula combination of differential arc oxidation electrolyte, the bioactivity coatings that can directly prepare pore self-sealing and calcic phosphorus at the magnesium-base metal material surface, this coating has improved the decay resistance of magnesium-base metal greatly, has improved simultaneously the biological activity on differential arc oxidation coating surface.This coating can be applicable to the surface modification of degradable magnesium Base Metal implanted medical device, the problems such as thereby the degradation speed that solves degradable magnesium Base Metal embedded material/device is fast, the degraded matching is poor, be conducive to the combination between embedded material/device and the osseous tissue, accelerate knitting.
The invention provides a kind of magnesio embedded material differential arc oxidation pore self-sealing active coating, this coating is the differential arc oxidation active coating of a kind of calcic phosphorus and pore self-sealing, and described coating contains biologically actived calcium, P elements; The shared atom content percentage ratio of Ca is 3～6%, P elements, the atom content percentage ratio 9～15% that P is shared.
Magnesio embedded material differential arc oxidation pore self-sealing active coating provided by the invention, described coating is different from conventional differential arc oxidation coating microscopic appearance, in the differential arc oxidation process, realized pore self-sealing, the porous hole overwhelming majority on surface is filled with, the coating density is high, the contained chemical constituent of filling chemical compound and other positions are conformed to each others of surface, and the calcium P elements that contains of surface is evenly distributed, and greatly improved the biological activity of coating.
The preparation method of the differential arc oxidation active coating of a kind of magnesium-base metal implantation material surface calcic phosphorus and pore self-sealing is fairly simple, only needs one step of differential arc oxidation to finish.Its key point is the preparation of electrolyte and the selection of technological parameter.
Electrolyte prescription is combined as: calcium hydroxide 0.2～2g/L, potassium fluoride 3～12g/L, sodium hexameta phosphate 1～8g/L.The complete rear employing supersonic oscillations of electrolyte quota are fully dissolved it.
The selection of technological parameter: differential arc oxidation is processed voltage 280～500V, processing time 3～20min, and a-c cycle is chosen in 500～1000Hz.
Described differential arc oxidation active coating is before preparation, and the magnesium-base metal material is through acetone, each ultrasonic cleaning 10min of ethanol, natural drying in the air.Coating preparation finishes, and deionized water rinsing naturally dries and gets final product.
The coating layer thickness that obtains is 10～30 μ m, and thickness can be regulated by technological parameter.Immersion test is found in simulated body fluid, this coating can realize relatively evenly degrading, pH value of solution changes more stable, thereby be conducive to histiocytic tactophily and organization healing, increase the stability of embedded material, made the growth of the degraded of embedded material and cambium reach good coupling, shown excellent degraded matching, and in degradation process, be accompanied by the deposition of calcium P elements, show good biological activity.
In the described differential arc oxidation process, formed sample surfaces loose structure is directly contained the material filling of calcium phosphorus, and filling rate can reach more than 60%, need not carry out follow-up sealing of hole and process.
The preparation method of magnesio embedded material differential arc oxidation pore self-sealing active coating provided by the invention is applied to binary or the multicomponent alloy magnesium-base metal material surface of pure magnesium, Mg-Zn system, Mg-Ca system, Mg-Al system, Mg-RE system, Mg-Mn system.
It is emphasized that, the present invention can directly obtain on the magnesium-base metal surface bioactivity coatings of pore self-sealing and calcic phosphorus by differential arc oxidation, the coating that obtains has the surface texture that conventional differential arc oxidation coating does not possess, the direct filling of most discharge combined thing of hole.Can infer, in the moment of differential arc oxidation spark discharge, high temperature is so that a large amount of fused mass sprays from discharge channel in the region of discharge, and then around cooled and solidified was deposited on discharge channel, this discharge breakdown had caused the formation of coating surface loose structure.Yet, because the particularity of the selected electrolyte of the present invention, in micro-arc discharge, ion in part fused mass and the electrolyte reacts and may be filled in by the mode of electrophoretic deposition in the discharge channel of differential arc oxidation as the filling chemical compound, this has just formed the surface texture of pore self-sealing, the surface compact degree improves greatly, and the chemical compound of institute's filling has the chemical constituent consistent with loose structure, has realized again the homogeneity of composition.
Description of drawings
(a), (b) are respectively surface and the cross-section morphology of the pure magnesium surface differential arc oxidation bioactivity coatings that adopts the present invention's preparation among Fig. 1;
Fig. 2 is the EDS power spectrum that adopts the pure magnesium bioactivity coatings porous surface structure place of the present invention's preparation;
Fig. 3 is the EDS power spectrum that adopts the pure magnesium bioactivity coatings surface micropore inner stuffing of the present invention's preparation;
Fig. 4 is that the pure magnesium of bioactivity coatings (b) that do not carry out pure magnesium (a) that coating the processes calcic phosphorus prepared with adopting the present invention and pore self-sealing soaks the macro morphology after 30 days in Hank ' s solution;
Fig. 5 is the Nyquist electrochemical impedance spectroscopy comparison diagram of conventional silicate systems coating and gained pore self-sealing calcium phosphor coating of the present invention.
The specific embodiment
Following examples will be further described the present invention, but not thereby limiting the invention.
Take as cast condition commercially pure magnesium (purity is as 99.99%) as object of study, pure magnesium is cut into the circular disc test specimen of Φ 11 * 2mm, water-proof abrasive paper is polished step by step to 2000#, uses successively acetone, ethanol ultrasonic cleaning 10min, and air drying is stand-by.
Differential arc oxidation electrolyte chemical composition is as follows: sodium hexameta phosphate 1.5g/L, and potassium fluoride 5g/L, calcium hydroxide 0.4g/L, all the other are deionized water.Adopt sonic oscillation to make each form fully dissolving, behind the abundant mix homogeneously of solution, be poured into the differential arc oxidation electrolyzer.Pure magnesium is immersed in the electrolyte as anode, and stainless electrolyzer is as negative electrode.It is 360V that differential arc oxidation is processed voltage, and a-c cycle 1000Hz processes 5mm.After differential arc oxidation finishes, sample deionized water rinsing, natural drying.
Fig. 1 (a) is the SEM microscopic appearance figure of the pure magnesium surface bioactivity coatings that adopts present embodiment and prepare.As can be seen from the figure, directly prepare the differential arc oxidation coating of pore self-sealing at pure magnesium surface by technique of the present invention, the hole more than 80% is by the direct filling of canescence compound particle, and resulting coating density is high.Fig. 1 (b) is the Cross Section Morphology of this coating, and coating layer thickness is about 10 μ m, can find out that equally coating is dense.
Fig. 2, Fig. 3 are respectively the EDS power spectrum of coating surface loose structure and canescence filling chemical compound, can find out, charges have identical chemical composition in the loose structure that forms coating and the hole, all contain the elements such as Mg, F, Ca, P, O, the elements such as the Ca that the surface is contained, P are so that this coating has had again certain biological activity.In the simulated body fluid immersion process, coating is evenly degraded, and lip-deep Ca, P content constantly increase, and shows excellent biological activity.Degrade after 8 weeks, near degradable, SEM can be observed base metal to face coat, still is stabilized in about 7.8 at degraded later stage pH value, illustrates that this coating can control the degraded of pure magnesium effectively, and lower pH value is conducive to the tactophily of cell.
Take the AZ91 magnesium alloy as object of study, be cut to the circular disc test specimen of Φ 11 * 2mm, water-proof abrasive paper is polished step by step to 2000#, uses successively acetone, ethanol ultrasonic cleaning 10mm, and air drying is stand-by.
Differential arc oxidation electrolyte chemical composition is as follows: sodium hexameta phosphate 3g/L, and potassium fluoride 6g/L, calcium hydroxide 0.6g/L, all the other are deionized water.Adopt sonic oscillation to make each form fully dissolving, behind the abundant mix homogeneously of solution, be poured into the differential arc oxidation electrolyzer.AZ91 magnesium alloy disk is immersed in the electrolyte as anode, and stainless electrolyzer is as negative electrode.It is 400V that differential arc oxidation is processed voltage, and a-c cycle 1000Hz processes 8min.After differential arc oxidation finishes, sample deionized water rinsing, natural drying.
In the present embodiment, the hole of resulting coating more than 70% is by the direct filling of canescence compound particle, coating is dense, coating layer thickness is about 16 μ m, the elements such as lip-deep Ca, P, O are evenly distributed, and the corrosion current ratio of the coating not AZ91 magnesium alloy of coating has improved two orders of magnitude.
As different from Example 1, selected magnesium alloy is ZK60, and the processing voltage that differential arc oxidation adopts is higher, has reached 450V, and the prepared hole of face coat more than 90% is by the direct filling of canescence compound particle, white smooth appearance.But can find out that from the coating surface microscopic appearance block gathering has occured part canescence implant.Coating layer thickness has reached about 22 μ m, and corrosion resistance is further enhanced, and lip-deep Ca, P constituent content promote to some extent.Fig. 4 is that be untreated ZK60 magnesium alloy and this example differential arc oxidation processed coating soaks macro morphology after 30 days in simulated body fluid, can see through the ZK60 surface topography after the coating processing substantially not changing.The calcium phosphorus bioactivity coatings of this pore self-sealing can protect the ZK60 matrix not to be corroded in the early stage well.The coating layer thickness that higher processing voltage is prepared is thicker, and through the immersion degradation experiment in 8 weeks, the Partial digestion degeneration has only occured coating, and coating layer thickness is still about 15 μ m.
Embodiment 4
Take the WE43 magnesium alloy as object of study, be cut to little side's sheet of 10 * 10 * 2mm, water-proof abrasive paper is polished step by step to 2000#, uses successively acetone, ethanol ultrasonic cleaning 10min, and air drying is stand-by.
Differential arc oxidation electrolyte chemical composition is as follows: sodium hexameta phosphate 8g/L, and potassium fluoride 4g/L, calcium hydroxide 1g/L, all the other are deionized water.Adopt sonic oscillation to make each form fully dissolving, behind the abundant mix homogeneously of solution, be poured into the differential arc oxidation electrolyzer.The WE43 magnesium alloy is immersed in the electrolyte as anode, and stainless electrolyzer is as negative electrode.It is 450V that differential arc oxidation is processed voltage, and a-c cycle 1000Hz processes 5min.After differential arc oxidation finishes, sample deionized water rinsing, natural drying.
Resulting calcium phosphorus pore self-sealing bioactivity coatings soaks after 7 days in PBS solution in this example, and pH value is about 8.35, and the pH value of the WE43 magnesium alloy that is untreated has reached about 10.4.By contrast, illustrate that this coating has higher decay resistance, establishment the corrosion of WE43 magnesium alloy substrate.
Take the Mg-1.0Zn-0.8Mn magnesium alloy as object of study, be cut to the sequin of Φ 11 * 2mm, water-proof abrasive paper is polished step by step to 2000#, uses successively acetone, ethanol ultrasonic cleaning 10min, and air drying is stand-by.
Differential arc oxidation electrolyte chemical composition is as follows: sodium hexameta phosphate 3g/L, and potassium fluoride 4g/L, calcium hydroxide 0.4g/L, all the other are deionized water.Adopt sonic oscillation to make each form fully dissolving, behind the abundant mix homogeneously of solution, be poured into the differential arc oxidation electrolyzer.This magnesium alloy is immersed in the electrolyte as anode, and stainless electrolyzer is as negative electrode.It is 410V that differential arc oxidation is processed voltage, and a-c cycle 1000Hz processes 10min.After differential arc oxidation finishes, sample deionized water rinsing, natural drying.
This example is prepared the pore self-sealing bioactivity coatings of calcic phosphorus at the Mg-1.0Zn-0.8Mn Mg alloy surface, and the sealing of hole rate is greater than 70%, and coating compactness is higher.Lip-deep calcium phosphorus content and embodiment 1～4 are similar, are evenly distributed.Simulated body fluid soaked after 1 day, and the magnesium alloy pH value of coating does not rise to 11.4, only was about 8.35 and adopt the magnesium alloy pH value of coating of the present invention.Therefore prepared coating has excellent decay resistance in this example, has suppressed well the fast degradation of this magnesium alloy.
Take as cast condition commercially pure magnesium as object of study, pure magnesium is cut into the circular disc test specimen of Φ 11 * 2mm, water-proof abrasive paper is polished step by step to 2000#, uses successively acetone, ethanol ultrasonic cleaning 10min, and air drying is stand-by.
Adopt conventional silicate electrolyte system and electrolyte system of the present invention that pure magnesium is carried out differential arc oxidation and process, process voltage 360V, processing time 5min, the gained coating is labeled as respectively MAO-1 and MAO-2.Silicate electrolyte system composed as follows: sodium silicate 10g/L, potassium hydroxide 1g/L, potassium fluoride 8g/L; Electrolyte system of the present invention consists of: sodium hexameta phosphate 3g/L, potassium fluoride 8g/L, calcium hydroxide 0.4g/L.Then the sample of above-mentioned two kinds of differential arc oxidations being processed carries out electro-chemical test.
Fig. 5 is the Nyquist figure of electrochemical impedance spectroscopy, can find out that the capacitive reactance arc of coating that electrolyte system of the present invention obtains (MAO-2) has improved about 30 times than the obvious increase of silicate systems coating (MAO-1).The decay resistance that the pore self-sealing calcium phosphor coating that adopts gained of the present invention is described has been compared obvious lifting with the silica-based coating of routine.
Above result shows that the present invention directly prepares the bioactivity coatings of pore self-sealing and calcic phosphorus at the magnesium-base metal implantation material surface by differential arc oxidation in specific electrolyte.The method is simple to operate, gained coating density is higher, the characteristic of pore self-sealing so that decay resistance be further enhanced, has simultaneously good biological activity, and coating has certain controlled degradation, thereby can effectively control magnesium-base metal embedded material degradation speed in vivo, so that the surrounding tissue growth can be mated mutually with the coating degraded.This invention can be applicable to the surface modification treatment that hard tissue repair is used degradable magnesium Base Metal material/device.
Claims (7)
1. magnesio embedded material differential arc oxidation pore self-sealing active coating, it is characterized in that: this coating is the differential arc oxidation active coating of a kind of calcic phosphorus and pore self-sealing.
2. according to the described magnesio embedded material of claim 1 differential arc oxidation pore self-sealing active coating, it is characterized in that: described coating contains biologically actived calcium, P elements; The shared atom content percentage ratio of Ca is the shared atom content percentage ratio 9～15% of 3～6%, P.
3. the preparation method of the described magnesio embedded material of claim 1 differential arc oxidation pore self-sealing active coating is characterized in that: behind the electrolyte mix homogeneously, pour into and carry out differential arc oxidation in the differential arc oxidation electrolyzer.
4. according to the preparation method of the described magnesio embedded material of claim 3 differential arc oxidation pore self-sealing active coating, it is characterized in that: described electrolyte consists of sodium hexameta phosphate 1～8g/L, calcium hydroxide 0.2～2g/L, potassium fluoride 3～12g/L.
5. according to the preparation method of the described magnesio embedded material of claim 3 differential arc oxidation pore self-sealing active coating, it is characterized in that: described differential arc oxidation voltage is 280～500V, and the differential arc oxidation time is 3～20min, and a-c cycle is 500～1000Hz.
6. according to the preparation method of the described magnesio embedded material of claim 3 differential arc oxidation pore self-sealing active coating, it is characterized in that: in the described differential arc oxidation process, formed sample surfaces loose structure is directly contained the material filling of calcium phosphorus, filling rate can reach more than 60%, need not carry out follow-up sealing of hole and process.
7. the preparation method of the described magnesio embedded material of claim 3 differential arc oxidation pore self-sealing active coating is applied to binary or the multicomponent alloy magnesium-base metal material surface of pure magnesium, Mg-Zn system, Mg-Ca system, Mg-Al system, Mg-RE system, Mg-Mn system.
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| CN201210127249.XA CN103372232B (en) | 2012-04-27 | 2012-04-27 | Micro-arc oxidation self-sealing hole active coating of magnesium-based implant material and preparation method of micro-arc oxidation self-sealing hole active coating |
| PCT/CN2012/083752 WO2013159500A1 (en) | 2012-04-27 | 2012-10-30 | Micro-arc oxidized, self-closing-pore, active coating of magnesium-based implant material and preparation method therefor |
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| CN201210127249.XA CN103372232B (en) | 2012-04-27 | 2012-04-27 | Micro-arc oxidation self-sealing hole active coating of magnesium-based implant material and preparation method of micro-arc oxidation self-sealing hole active coating |
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| WO2013159500A1 (en) | 2013-10-31 |
| CN103372232B (en) | 2015-06-10 |
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