CN102677121A - Preparation of multi-stage pore structure layer on surface of medical titanium by using one-step anodic oxidation method - Google Patents
Preparation of multi-stage pore structure layer on surface of medical titanium by using one-step anodic oxidation method Download PDFInfo
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- CN102677121A CN102677121A CN2012100947318A CN201210094731A CN102677121A CN 102677121 A CN102677121 A CN 102677121A CN 2012100947318 A CN2012100947318 A CN 2012100947318A CN 201210094731 A CN201210094731 A CN 201210094731A CN 102677121 A CN102677121 A CN 102677121A
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Abstract
The invention relates to a preparation of multi-stage pore structure layer on the surface of medical titanium by using a one-step anodic oxidation method. A process provided by the invention comprises the step of carrying out anodic oxidation on medical titanium in a sodium acetate or potassium acetate electrolyte under the direct-current step type constant current mode so as to obtain a crystal-form titanium dioxide layer with a micron/sub-micron composite multi-stage pore structure, wherein a large pore structure is composed of micro pit structures and has a diameter of 5-20 microns, and a small pore structure is a submicron-sized micropore structure densely distributed on a whole membrane and has a pore diameter of 50-500 nm. The process disclosed by the invention is simple, economic, green and environment-friendly, and expected to be used as a surface modification method for medical titanium in the field of orthopedics, dentistry or plastic surgery.
Description
Technical field
The present invention relates to a step anonizing medical titanium is carried out surface treatment, the hierarchical porous structure layer in that its surface preparation has micron/submicron is expected to be used in dentistry, orthopaedics, or the surface-treated field of plastic sugery titanium base implant.
Background technology
As everyone knows, natural bone healing and regenerated process are carried out being engulfed by osteoclast under the formed three-dimensional environment with micron order pit and submicron order raised structures.So the compound coarse or vesicular structure microscopic appearance of micron/submicron-scale is a kind of bionical texture, the titanium base implant with the compound coarse or vesicular structure microscopic appearance of micron/submicron-scale is successful Application clinically.But; Because the structure of micron order and submicron order size does not make in a step treatment process so easily simultaneously; So adopt the treatment process at least two steps usually; Add acid etching [Yang GL, Oral Surg Oral Med Oral Pathol Oral Radiol Endod 2008 such as sandblast; 106:516-24.], sandblast adds differential arc oxidation and handles [Chinese patent zl 200610123271.1, " bioactive film on titanium metal surface and sand blasting-micro arc oxidizing compounding process thereof ".], little processing of electrochemistry and acid etching [Zinger O, Differential regulation of osteoblasts by substrate microstructural features. Biomaterials 2005; 26:1837-47.], two go on foot anodize [Xie L, J. Biomed. Mater. Res. 2011; 98A:312-20.] etc.In the surface treatment method of numerous titanium base implants, anonizing is one of method of using always because anonizing can be on titanium implants surface even film forming, and do not receive the influence of its complex configuration.The sull that generates is porous normally; The aperture at several micron with interior or submicron order; The process of surface treatment of present commercial titanium abutment planting body TiUnite is anonizing, forms crateriform surface micropore structure, and the aperture mainly is distributed between the 0.5-3 micron; About 2 microns of thickness, sull mainly is made up of amorphous oxidation titanium and part anatase type titanium oxide.But it does not have micron/submicron compound porous structure.The process of surface treatment that another kind of commercial planting body SLA adopts is the sandblast aciding, forms the compound coarse structure of cellular micron/submicron, and acid etching forms about 1 micron acid etching hole structure, and forms the big bowl configurations about 10 microns.But, the sandblast acid etching can not form thicker titanium oxide layer.The residual a spot of grit blast of sandblasting meeting in addition, these grit blasts get into surrounding tissue in the back that implants, and can disturb normal bone integration process.And the acid etching process has H
2Get into the lattice of titanium material, cause hydrogen embrittlement, reduce its mechanical strength.
Anodised processing condition or parameter (electrolytic solution, electric source modes, loading mode, voltage, current density, oxidization time etc.) have very big influence to the performance of sull.Document shows, when application acetic acid is made electrolytic solution, adopts the staged constant current mode; Because the special field of acetate ion causes solvency action; Can form bigger pore structure on the sull surface, can generate groove or bowl configurations [Xie L, the J Biomed Mater Res 2011 of 20-30 micron; 98A:312-20.].In addition, research shows, the formation of submicron order vesicular structure depend on electrical spark phenomenon in the anode oxidation process effect [Li LH, Biomaterials 2004; 25:2867 – 75].In the anodic oxidation of acetic acid electrolytic solution, do not see the generation of electrical spark, and at sulfuric acid, sodium sulfate, certain down visible electrical spark of voltage conditions produces [Cui XY, Dent Mater 2009 in the phosphoric acid electrolyte; 25:80-86.]. this is that its aqueous solution has higher specific conductivity, thereby helps to reduce voltage breakdown because these electrolytic solution are strong electrolytes.But, can not form the groove or the bowl configurations of bigger micron-scale at the acid ion of these electrolytic solution.
The deficiency that for a change existing method exists at preparation micron/submicron compound porous structure, we propose a kind of novel thinking and technology, prepare the compound porous sull of micron/submicron through single stage method at the medical titanium implant surfaces.We adopt sodium-acetate or Potassium ethanoate as electrolytic solution; And employing staged constant current mode; Pit effect through acetate ion in the electrolytic solution obtains the micron order bowl configurations, because sodium-acetate or Potassium ethanoate are strong electrolytes, its aqueous solution specific conductivity significantly improves than acetic acid electrolytic solution simultaneously; Voltage breakdown reduces; Can in anodised process, produce electrical spark, thereby obtain the vesicular structure of submicron, and sull crystallization under the electrical spark effect is fixed and improved its stability and film substrate bond strength.The relative amorphous oxide film of crystal formation sull has better biological activity, can improve the bone of titanium implants and integrate performance.
Summary of the invention
The object of the invention has been to provide the method for an a kind of easy step anonizing at medical titanium surface preparation hierarchical porous structure layer.
Concrete process step is:
(1) pre-treatment of titanium-based metal material process mechanical grinding, oil removing and ultrasonic cleaning before anodize; In anodic oxidation device, be anode with the titanium; With stainless steel or titanium is negative electrode; In 10 ~ 40 ℃ electrolytic solution, carry out anodize, keep in the anode oxidation process stirring, stirring velocity is 800 r/min ~ 1000 r/min.The electrolytic solution that adopts during anodic oxidation is 1 ~ 3M sodium-acetate or Potassium ethanoate.
What (2) adopt is direct current staged constant current mode, and the initial current density on titanium components surface is from 5 mA/cm
2Beginning progressively is elevated to 50 mA/cm
2, up-flow step journey is 5 mA/cm
2, and at each current density value maintenance 2 ~ 4 min.
(3) through after the anodize, sample is with carrying out ultrasonic cleaning in the 1 M dilution heat of sulfuric acid, to remove the particle that is deposited on the surface in the anode oxidation process.
Through above process step, can have the crystal formation titanium dioxide layer of micron/submicron compound porous structure in the surface of metal titanium preparation.Micron-sized structure is the micron bowl configurations, 2 ~ 20 microns in aperture, and small structure is that densification is distributed in submicron order microvoid structure on the whole film, the aperture is between 50 ~ 500 nanometers.
The ingenious characteristics of having utilized anodic oxidation spark discharge mechanism and acetate electrolytic solution of the present invention successfully make the crystal formation oxidation titanium film with micron/submicron compound porous structure with a step anonizing.The traditional two-step treatment process obtains titanium-based surface hierarchical porous structure layer relatively, and a step anonizing is easy and simple to handle, simple economy.
Specific embodiments
Below in conjunction with the specific examples that the contriver provides, the technology of being invented is done further to set forth in detail.Need to prove that the present invention is not limited to these embodiment,, in the category that the present invention provides, carry out the interpolation and the replacement of technical characterictic, all belong to protection scope of the present invention for those skilled in the art.
Embodiment 1:The pure titanium sheet (TA2) that is of a size of 10 * 10 * 1 mm is used 400# successively, 600#, and 800# abrasive paper for metallograph sanding and polishing, and then use acetone, and absolute ethyl alcohol, deionized water is ultrasonic cleaning 5 min respectively; In 1 M sodium-acetate electrolytic solution, sample is carried out anodize, adopt slowly equal fast up-flow pattern of direct current, promptly from 5 mA/cm
2Be raised to 50 mA/cm
2Under each current density condition, keep 2 min, the step journey is 5 mA/cm
2, be total to anodic oxidation 20 min.After the ultrasonic cleaning, scanning electron microscopic observation can be seen a micron bowl configurations under the low power, and pit diameter is about the 5-20 micron, can see under the high power that densification is distributed in the submicron order microvoid structure on whole surface, and the aperture is about the 50-500 nanometer.X-ray diffraction analysis shows that surface film oxide contains anatase titanium dioxide and rutile titanium dioxide crystalline phase.
Embodiment 2:The pure titanium sheet (TA2) that is of a size of 7.8 * 7.8 * 1 mm is used 400# successively, 600#, and 800# abrasive paper for metallograph sanding and polishing, and then use acetone, and absolute ethyl alcohol, deionized water is ultrasonic cleaning 5 min respectively; In 3 M sodium-acetate electrolytic solution, sample is carried out anodize, adopt slowly equal fast up-flow pattern of direct current, promptly from 5 mA/cm
2Be raised to 50 mA/cm
2Under each current density condition, keep 3 min, the step journey is 5 mA/cm
2, be total to anodic oxidation 30 min.After the ultrasonic cleaning, scanning electron microscopic observation can be seen a micron bowl configurations under the low power, and the pit aperture is about the 8-20 micron, can see under the high power that densification is distributed in the submicron order microvoid structure on whole surface, and the aperture is about the 50-600 nanometer.X-ray diffraction analysis shows that surface film oxide contains anatase titanium dioxide and rutile titanium dioxide crystalline phase.
Embodiment 3:Diameter is that the pure titanium sheet (TA2) of 15 mm is used 400# successively, 600#, and 800# abrasive paper for metallograph sanding and polishing, and then use acetone, and absolute ethyl alcohol, deionized water is ultrasonic cleaning 5 min respectively; In the 2 M Potassium ethanoate mixed electrolytic solutions, sample is carried out anodize, adopt slowly equal fast up-flow pattern of direct current, promptly from 5 mA/cm
2Be raised to 50 mA/cm
2Under each current density condition, keep 2 min, the step journey is 5 mA/cm
2, be total to anodic oxidation 20 min.After the ultrasonic cleaning, ESEM is observed down, can see a micron bowl configurations under the low power, and pit diameter is about the 5-20 micron, can see under the high power that densification is distributed in the submicron order microvoid structure on whole surface, and the aperture is about the 50-500 micron.X-ray diffraction analysis shows that surface film oxide contains anatase titanium dioxide and rutile titanium dioxide crystalline phase.
Claims (3)
1. a step anonizing is at medical titanium surface preparation hierarchical porous structure layer; It is characterized in that comprising the steps and processing condition: the pre-treatment of titanium or titanium alloy process mechanical grinding, oil removing and ultrasonic cleaning before anodize; In anodic oxidation device, be anode with medical titanium or titanium alloy; With stainless steel or titanium is negative electrode, in 10 ~ 40 ℃ electrolyte system, carries out anodize, and the electrolytic solution of employing is 1-3 M sodium-acetate or Potassium ethanoate; Keep in the anode oxidation process stirring, stirring velocity is 800 r/min ~ 1000 r/min.
2. go on foot anonizing at medical titanium surface preparation hierarchical porous structure layer according to right 1 described, it is characterized in that: what adopt during anodic oxidation is direct current staged constant current mode, and anodic current density is from 5 mA/cm
2Beginning progressively is elevated to 50 mA/cm
2, up-flow step journey is 5 mA/cm
2, and at each current density value maintenance 2 ~ 4 min.
3. go on foot anonizing at medical titanium surface preparation hierarchical porous structure layer according to right 1 described; It is characterized in that: film surface is hierarchical porous structure; Macroporous structure is made up of bowl configurations; 2 ~ 20 microns of diameters, small structure is distributed in the submicron order microvoid structure on the whole film for fine and close, and the aperture is between 50 ~ 500 nanometers.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103436937A (en) * | 2013-07-25 | 2013-12-11 | 四川大学 | Preparation method of double-layer titanium dioxide nanotube thin film with pear-shaped structure |
| CN103668390A (en) * | 2014-01-02 | 2014-03-26 | 四川大学 | Titanium or titanium-alloy material with micron-nano coarse-structure surface and preparation method thereof |
| RU2545887C2 (en) * | 2012-10-23 | 2015-04-10 | Общество с Ограниченной Ответственностью "Фабрика новых материалов" | Method of production of flexible nanoporous composite membrane with cellular structure of anode metal oxide or alloy |
| CN105496577A (en) * | 2015-12-10 | 2016-04-20 | 四川大学 | Titanium implant with bone resorption lacunae-like surface appearance and preparation method of titanium implant |
| CN105543934A (en) * | 2015-12-17 | 2016-05-04 | 大博医疗科技股份有限公司 | Medical titanium implant micro-arc oxidation film layer and preparation method |
| CN107551316A (en) * | 2017-09-11 | 2018-01-09 | 佘雨辰 | Imitation biochemistry mixes the preparation method of chlorine nanotube boundling pattern layer dentistry implant |
| CN108284562A (en) * | 2017-01-10 | 2018-07-17 | 优尔材料工业（深圳）有限公司 | The complex and preparation method thereof of zirconium-base amorphous alloy part and plastic part |
| CN110699733A (en) * | 2019-11-20 | 2020-01-17 | 中国计量大学 | Preparation method, product and application of titanium alloy porous oxide film |
| CN114592226A (en) * | 2022-03-08 | 2022-06-07 | 重庆臻宝实业有限公司 | Preparation process of high-density anode film suitable for Display Dry Etcher |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| RU2545887C2 (en) * | 2012-10-23 | 2015-04-10 | Общество с Ограниченной Ответственностью "Фабрика новых материалов" | Method of production of flexible nanoporous composite membrane with cellular structure of anode metal oxide or alloy |
| CN103436937A (en) * | 2013-07-25 | 2013-12-11 | 四川大学 | Preparation method of double-layer titanium dioxide nanotube thin film with pear-shaped structure |
| CN103668390A (en) * | 2014-01-02 | 2014-03-26 | 四川大学 | Titanium or titanium-alloy material with micron-nano coarse-structure surface and preparation method thereof |
| CN103668390B (en) * | 2014-01-02 | 2016-10-26 | 四川大学 | There is the titanium on micro-nano rough structure surface or titanium alloy material and preparation method |
| CN105496577A (en) * | 2015-12-10 | 2016-04-20 | 四川大学 | Titanium implant with bone resorption lacunae-like surface appearance and preparation method of titanium implant |
| CN105496577B (en) * | 2015-12-10 | 2018-07-27 | 四川大学 | Titanium implant and preparation method with similar Bone resoiption pit surface topography |
| CN105543934A (en) * | 2015-12-17 | 2016-05-04 | 大博医疗科技股份有限公司 | Medical titanium implant micro-arc oxidation film layer and preparation method |
| CN108284562A (en) * | 2017-01-10 | 2018-07-17 | 优尔材料工业（深圳）有限公司 | The complex and preparation method thereof of zirconium-base amorphous alloy part and plastic part |
| CN107551316A (en) * | 2017-09-11 | 2018-01-09 | 佘雨辰 | Imitation biochemistry mixes the preparation method of chlorine nanotube boundling pattern layer dentistry implant |
| CN110699733A (en) * | 2019-11-20 | 2020-01-17 | 中国计量大学 | Preparation method, product and application of titanium alloy porous oxide film |
| CN114592226A (en) * | 2022-03-08 | 2022-06-07 | 重庆臻宝实业有限公司 | Preparation process of high-density anode film suitable for Display Dry Etcher |
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Application publication date: 20120919 |