CN102747405A - Preparation method of composite ceramic coating for improving bioactivity of medical magnesium alloy - Google Patents
Preparation method of composite ceramic coating for improving bioactivity of medical magnesium alloy Download PDFInfo
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- CN102747405A CN102747405A CN2012102257177A CN201210225717A CN102747405A CN 102747405 A CN102747405 A CN 102747405A CN 2012102257177 A CN2012102257177 A CN 2012102257177A CN 201210225717 A CN201210225717 A CN 201210225717A CN 102747405 A CN102747405 A CN 102747405A
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Abstract
The invention discloses a preparation method of a composite ceramic coating for improving bioactivity of medical magnesium alloy. A micro-arc oxidation technology is employed, and a silicate / phosphate electrolyte is added with nano hydroxyapatite granules, so as to grow a self sealing composite ceramic coating with high corrosion resistance and excellent biological activity on a surface of medical magnesium alloy in situ. Compared with a conventional magnesium alloy micro-arc oxidation coating, the ceramic coating of the invention has advantages of self sealing, uniform thickness, few surface pores, better corrosion resistance and biological activity.
Description
Technical field
The present invention relates to bio-medical metal implant material or interventional technique field, be specifically related to a kind of preparation method who improves the bioactive composite ceramics rete of medical magnesium alloy.
Background technology
Magnesium and magnesiumalloy have better biocompatibility and mechanical compatibility, become the research emphasis of biodegradable metallic substance in recent years.As the medical embedded material of a new generation, its moderate Young's modulus is the relieve stresses occlusion effect effectively, union of fracture, planting body is stablized have vital role.Animal experiment study is the result show, magnesiumalloy is too short as the time that bone implant material exists in animal body, can not satisfy the requirement of bone growth to its mechanical property and corrosion resisting property.Therefore, through magnesiumalloy is carried out the corrosion resisting property that surface-treated is improved magnesiumalloy, slowing down the rate of release of hydrogen, is that magnesium and magnesiumalloy are implanted into field acquisition key in application at human body.In addition, through improving the corrosion resisting property of magnesiumalloy, can prolong the time of bringing into play function in vivo, thereby reach the double goal of biodegradable and treatment.
Differential arc oxidation is handled through the spark discharge under electrochemical oxidation and the solution mesohigh; At a kind of ceramic film of magnesium alloy matrix surface growth in situ; Can improve the corrosion resistance nature of magnesiumalloy preferably, be a kind of magnesium alloy surface treatment with application prospect.Generally, the composition of MgO is on the high side relatively in the coating that magnesiumalloy obtains after differential arc oxidation is handled, and the less stable of MgO in the aqueous solution limited the further provide protection of sull to matrix to a certain extent.Relevant research shows; Sauerstoffatom is easier to be adsorbed onto magnesium alloy substrate or sull surface than high acid ion, forms the impurity discharge centers, makes sull surface breakdown discharge; Thereby produce one deck oxysalt rete at Mg alloy surface, can effectively improve the corrosion resisting property of rete.In recent years, study and use maximum electrolyte systems silicate electrolytic solution, phosphoric acid salt electrolytic solution and aluminate electrolytic solution etc. are arranged.Consider the toxic action of Al element, scarcely consider to use the aluminate electrolyte system in the biomaterial Application Areas to human body.And in silicate systems, the speed of growth of differential arc oxidation film layer is relatively slow, and rete is also comparatively fine and close, and therefore, the corrosion resistance nature of rete is better relatively, but biological activity is general; Coating growth rapid speed in the phosphate system, but tectorium large percentage in the sull that obtains, wherein hole and tiny crack are interlaced, for the intrusion of corrosive fluid provides passage, have a strong impact on the corrosion resistance of rete.
Summary of the invention
The objective of the invention is to: a kind of preparation method who improves the bioactive composite ceramics rete of medical magnesium alloy; Have high anti-corrosion and good bioactive pore self-sealing composite ceramics rete in the growth of medical magnesium alloy surface in situ; Improve the biological activity and the corrosion resistance of medical magnesium alloy, for being applied to the medical osseous tissue equivalent material of human body.
Technical standpoint scheme of the present invention is: adopt differential arc oxidization technique, through in silicate/phosphate electrolytic solution, adding nano-hydroapatite particles, at medical magnesium alloy surface in situ growth pore self-sealing composite ceramics rete; Every liter of electrolytic solution is grouped into by following one-tenth: 10～15g/L water glass, and 15～20g/L sodium phosphate, 2～4g/L sodium hydroxide, 1～4g/L nanometer hydroxyapatite, all the other are deionized water.
Wherein, the median size of described nanometer hydroxyapatite is 5-100nm.
Wherein, described medical magnesium alloy is pure Mg, Mg-Al-Zn, Mg-Zn-Ca, ZE41A, AE21 magnesiumalloy.
Wherein, concrete steps are following:
(1) with Mg alloy surface polishing light, deoils with absolute ethyl alcohol;
(2) fixedly immerse in the electrolytic solution behind the magnesiumalloy with copper electrode, carry out differential arc oxidation and handle;
(3) the composite ceramics rete after the growth cleans successively, dries through deionized water and absolute ethyl alcohol.
Wherein, mao power source adopts the constant pressure type pulse power, and its parameter is: forward on load voltage scope 200～320V, range of frequency 500～1500Hz, dutycycle 30～60%, oxidization time 10～30min.
The present invention has the following advantages:
1, the differential arc oxidization technique that the present invention adopted does not have particular requirement to shape, the size of magnesium or magnesiumalloy, and the electrolytic solution of employing does not contain the chemical element to environment and human body harmful.
2, adopt phosphoric acid salt and silicate electrolytic solution can prepare the ceramic film that has both than high anti-corrosion and good biocompatibility; And through in electrolytic solution, adding nano-hydroapatite particles; Have high anti-corrosion and a good bioactive pore self-sealing composite ceramics rete in that medical magnesium alloy surface in situ growth is a kind of; Then can further improve the biological activity and the corrosion resistance of ceramic layer, be widely used in the medical osseous tissue of human body.
Embodiment
Further specify technical solution of the present invention below in conjunction with specific embodiment, these embodiment can not be interpreted as it is the restriction to technical scheme.
Embodiment 1:
The first step: preparing electrolyte 10L adds it in electrolyzer behind the thorough mixing, adopts the mechanical stirring mode to keep electrolytic solution unrestricted flow; The component of every liter of electrolytic solution is: the 10g/L water glass, and the 15g/L sodium phosphate, 2g/L sodium hydroxide, nanometer hydroxyapatite 1g/L, all the other are deionized water; Wherein, the median size of nanometer hydroxyapatite is 5nm; The pH value of electrolytic solution is 8;
Second step: carry out the growth of composite ceramic film layer on microarc oxidation equipment provided, the pure magnesium of material selection, its surface is fixed on after sand papering, oil removing, cleaning, drying treatment on the copper electrode as anode, and the stainless steel electrolytic groove is a negative electrode; Adopt constant voltage control condition to carry out differential arc oxidation, its significant parameter is: forward on load voltage scope is 200V, and range of frequency is 500Hz, and dutycycle is 30%, and oxidization time is 10min;
The 3rd step: have the pure magnesium material of composite ceramics rete to clean successively, dry growth through deionized water and absolute ethyl alcohol.
Embodiment 2:
The first step: preparing electrolyte 10L adds it in electrolyzer behind the thorough mixing, adopts the pneumatic blending mode to keep electrolytic solution unrestricted flow; The component of every liter of electrolytic solution is: the 12g/L water glass, and the 16g/L sodium phosphate, 2g/L sodium hydroxide, nanometer hydroxyapatite 2g/L, all the other are deionized water; Wherein, the median size of nanometer hydroxyapatite is 20nm; The pH value of electrolytic solution is 10;
Second step: carry out the growth of composite ceramic film layer on microarc oxidation equipment provided, magnesiumalloy is selected AZ31 for use, and its surface is fixed on after sand papering, oil removing, cleaning, drying treatment on the copper electrode as anode, and the stainless steel electrolytic groove is a negative electrode; Adopt constant voltage control condition to carry out differential arc oxidation, its significant parameter is: forward on load voltage scope is 240V, and range of frequency is 750Hz, and dutycycle is 40%, and oxidization time is 15min;
The 3rd step: have the AZ31 material of composite ceramics rete to clean successively, dry growth through deionized water and absolute ethyl alcohol.
Embodiment 3:
The first step: preparing electrolyte 10L adds it in electrolyzer behind the thorough mixing, adopts the mechanical stirring mode to keep electrolytic solution unrestricted flow; The component of every liter of electrolytic solution is: the 12g/L water glass, and the 17.5g/L sodium phosphate, 4g/L sodium hydroxide, nanometer hydroxyapatite 3g/L, all the other are deionized water; Wherein, the median size of nanometer hydroxyapatite is 50nm; The pH value of electrolytic solution is 12;
Second step: carry out the growth of composite ceramic film layer on microarc oxidation equipment provided, magnesiumalloy is selected ZE41 for use, and its surface is fixed on after sand papering, oil removing, cleaning, drying treatment on the copper electrode as anode, and the stainless steel electrolytic groove is a negative electrode; Adopt constant voltage control condition to carry out the arc oxidizing process, its significant parameter is: forward on load voltage scope is 280V, and range of frequency is 1000Hz, and dutycycle is 50%, and oxidization time is 20min;
In the 3rd step, there is the ZE41 material of composite ceramics rete to clean successively, dry growth through deionized water and absolute ethyl alcohol.
Embodiment 4:
The first step: preparing electrolyte 10L adds it in electrolyzer behind the thorough mixing, adopts the pneumatic blending mode to keep electrolytic solution unrestricted flow; Every liter of electrolyte component is: the 15g/L water glass, and the 20g/L sodium phosphate, 4g/L sodium hydroxide, nanometer hydroxyapatite 4g/L, all the other are deionized water; Wherein, the median size of nanometer hydroxyapatite is 100nm; The pH value of electrolytic solution is 14;
Second step: carry out the growth of composite ceramic film layer on microarc oxidation equipment provided, magnesiumalloy is selected AE21 for use, and its surface is fixed on after sand papering, oil removing, cleaning, drying treatment on the copper electrode as anode, and the stainless steel electrolytic groove is a negative electrode; Adopt constant voltage control condition to carry out the arc oxidizing process, its significant parameter is: forward on load voltage scope is 320V, and range of frequency is 1500Hz, and dutycycle is 60%, and oxidization time is 30min;
In the 3rd step, there is the AE21 material of composite ceramics rete to clean successively, dry growth through deionized water and absolute ethyl alcohol.
Said embodiment of the present invention only be for clearly demonstrate that the present invention does for example, and be not to be qualification to embodiment of the present invention.Those of ordinary skill for affiliated field; Also can on the basis of above-mentioned explanation, make other multi-form variation or change; Here need not also can't give all embodiments exhaustive, and these belong to conspicuous variation or the change that spirit of the present invention amplified out and still are in protection scope of the present invention.
Claims (5)
1. improve the preparation method of the bioactive composite ceramics rete of medical magnesium alloy; It is characterized in that: this ceramic film adopts differential arc oxidization technique; Through in silicate/phosphate electrolytic solution, adding nano-hydroapatite particles, at medical magnesium alloy surface in situ growth pore self-sealing composite ceramics rete; Every liter of electrolytic solution is grouped into by following one-tenth: 10～15g/L water glass, and 15～20g/L sodium phosphate, 2～4g/L sodium hydroxide, 1～4g/L nanometer hydroxyapatite, all the other are deionized water.
2. the preparation method of the bioactive composite ceramics rete of raising medical magnesium alloy according to claim 1 is characterized in that: the median size of described nanometer hydroxyapatite is 5-100nm.
3. the preparation method of the bioactive composite ceramics rete of raising medical magnesium alloy according to claim 1 is characterized in that: described medical magnesium alloy is pure Mg, Mg-Al-Zn, Mg-Zn-Ca, ZE41A, AE21 magnesiumalloy.
4. the preparation method of the bioactive composite ceramics rete of raising medical magnesium alloy according to claim 1 is characterized in that concrete steps are following:
(1) with Mg alloy surface polishing light, deoils with absolute ethyl alcohol;
(2) fixedly immerse in the electrolytic solution behind the magnesiumalloy with copper electrode, carry out differential arc oxidation and handle;
(3) the composite ceramics rete after the growth cleans successively, dries through deionized water and absolute ethyl alcohol.
5. the preparation method of the bioactive composite ceramics rete of raising medical magnesium alloy according to claim 4; It is characterized in that: mao power source adopts the constant pressure type pulse power; Its parameter is: forward on load voltage scope 200～320V; Range of frequency 500～1500Hz, dutycycle 30～60%, oxidization time 10～30min.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105274603A (en) * | 2015-11-27 | 2016-01-27 | 福州大学 | Compound modified coating of magnesium or magnesium alloy surface carbon-containing nano tube and preparation method of compound modified coating |
| CN106119750A (en) * | 2016-06-22 | 2016-11-16 | 浙江工业大学 | Laser-impact and differential arc oxidation are combined in Mg alloy surface and prepare biological coating method |
| CN107435160A (en) * | 2017-08-18 | 2017-12-05 | 山东省科学院新材料研究所 | A kind of short process making method of the anti-corrosion antimicrobial composite coating of magnesium alloy and titanium alloy |
| CN108950652A (en) * | 2018-08-17 | 2018-12-07 | 蔡文剑 | A kind of ceramic pan and preparation method thereof of differential of arc on metal surface oxidation |
| CN109023465A (en) * | 2018-08-17 | 2018-12-18 | 蔡文剑 | A kind of ceramic manual casing and preparation method thereof of differential of arc on metal surface oxidation |
| CN109440166A (en) * | 2018-12-19 | 2019-03-08 | 西安交通大学 | A kind of magnesium lithium alloy surface raising wear resistance and corrosion resistance micro-arc oxidation compound treatment method |
| CN110195248A (en) * | 2019-06-24 | 2019-09-03 | 哈尔滨工业大学 | A kind of metal material of modification and the method for modifying of metal surface |
| CN110528048A (en) * | 2019-08-30 | 2019-12-03 | 广东省新材料研究所 | A kind of titanium alloy implant Bio-surface active coating and preparation method thereof |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105274603A (en) * | 2015-11-27 | 2016-01-27 | 福州大学 | Compound modified coating of magnesium or magnesium alloy surface carbon-containing nano tube and preparation method of compound modified coating |
| CN106119750A (en) * | 2016-06-22 | 2016-11-16 | 浙江工业大学 | Laser-impact and differential arc oxidation are combined in Mg alloy surface and prepare biological coating method |
| CN107435160A (en) * | 2017-08-18 | 2017-12-05 | 山东省科学院新材料研究所 | A kind of short process making method of the anti-corrosion antimicrobial composite coating of magnesium alloy and titanium alloy |
| CN107435160B (en) * | 2017-08-18 | 2019-03-05 | 山东省科学院新材料研究所 | A kind of short flow process of magnesium alloy and the anti-corrosion antimicrobial composite coating of titanium alloy |
| CN108950652A (en) * | 2018-08-17 | 2018-12-07 | 蔡文剑 | A kind of ceramic pan and preparation method thereof of differential of arc on metal surface oxidation |
| CN109023465A (en) * | 2018-08-17 | 2018-12-18 | 蔡文剑 | A kind of ceramic manual casing and preparation method thereof of differential of arc on metal surface oxidation |
| CN109440166A (en) * | 2018-12-19 | 2019-03-08 | 西安交通大学 | A kind of magnesium lithium alloy surface raising wear resistance and corrosion resistance micro-arc oxidation compound treatment method |
| CN110195248A (en) * | 2019-06-24 | 2019-09-03 | 哈尔滨工业大学 | A kind of metal material of modification and the method for modifying of metal surface |
| CN110528048A (en) * | 2019-08-30 | 2019-12-03 | 广东省新材料研究所 | A kind of titanium alloy implant Bio-surface active coating and preparation method thereof |
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