CN101555616B - Method for preparing hydroxyapatite/titanium dioxide composite coating on nickel-titanium surface - Google Patents
Method for preparing hydroxyapatite/titanium dioxide composite coating on nickel-titanium surface Download PDFInfo
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- CN101555616B CN101555616B CN2009100115803A CN200910011580A CN101555616B CN 101555616 B CN101555616 B CN 101555616B CN 2009100115803 A CN2009100115803 A CN 2009100115803A CN 200910011580 A CN200910011580 A CN 200910011580A CN 101555616 B CN101555616 B CN 101555616B
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Abstract
A method for preparing a hydroxyapatite/titanium dioxide composite coating on a nickel-titanium surface relates to a method for preparing a hydroxyapatite/titanium dioxide porous composite coating on the nickel-titanium surface. The method is characterized in that the nickel-titanium alloy is heat treated in a furnace with the heating temperature of 400-650 DEG C and the holding time of 0.5-2h, later cooled along with the furnace, and then suspended in electrolyte as an anode for micro-arc oxidation; the cathode is a stainless electrolyte tank or a stainless steel sheet which is suspended in the electrolyte; a bipolar pulse power supply is adopted, with the positive pulse voltage of 300-650V, the negative pulse voltage of 0-100V, the pulse frequency of 200-800Hz, the duty cycle of 8 percent to 30 percent, the electrolyte temperature of 0-40 DEG C, the processing time of 0-10min, the electrolyte composition of aqueous solution of (CH3COO)2Ca.H2O and NaH2PO4.2H2O, the composition ratio of 0.025-0.2mol/L of Ca, and 0.025-0.2mol/L of PO. The coating prepared by the invention effectively improves the biological activity and coating strength of the nickel-titanium alloy, and is suitable to be used in the field of human body hard tissue implant and lumen stent.
Description
Technical field
The invention belongs to the Materials Science and Engineering technical field; The preparation method who relates to a kind of Ni-Ti alloy bioactive coating on surface, particularly a kind of method that combines with differential arc oxidation through thermal treatment is in the method for Ni-Ti alloy surface preparation Win 40350/titanium oxide compound coating.
Background technology
Niti-shaped memorial alloy (NiTi) is widely used in the human body hard tissue implant owing to having SME and super-elasticity; But the Ni-Ti alloy bone implant material does not have biological activity; Can not with human body bone forming synostosis, be prone to cause the implant afunction, make graft failure.Win 40350 (HA) is the main inorganic components of body bone tissue, has excellent biological compatibility and bone guided property, and the coating that contains HA in the Ni-Ti alloy surface preparation has bigger effect for improving its implant bone forming ability.But the fragility of HA is big, toughness is low, intensity difference, and big with the difference of thermal expansion coefficient of titanium alloy, thus the coating of the pure HA composition of metallic surface intensity is low in vivo, a little less than the coating bonding force, be easy to come off.The present invention is in order to overcome the defective of simple hydroxyapatite coating layer; The micropore compound coating that contains HA and titanium oxide in the titanium alloy surface preparation; Promoting osteocyte to stick with the sorption of biological metabolite, the interface binding power effect that titanium oxide improves coating and Ni-Ti alloy the biological action of Win 40350, microvoid structure is dissolved in one, goes out Win 40350/titanium oxide micropore compound coating in the Ni-Ti alloy surface preparation.
Differential arc oxidation method (MAO) is a kind of metallic surface microporous oxide coating production; This method can prepare with the base metal oxide to be main porous coating and to form high-intensity metallurgical binding with matrix; But since in the Ni-Ti alloy atomic ratio of Ni and Ti near 50%; Ni is not a valve metal, and its sull character is unstable, can not directly use micro-arc oxidation process at the NiTi alloy surface and prepare coating.At present domestic and international still useless differential arc oxidation method is at the report of Ni-Ti alloy surface preparation Win 40350/titanium oxide microporous coat; The present invention is through heat-treating Ni-Ti alloy in advance, and then adopts the differential arc oxidation method on Ni-Ti alloy, successfully to prepare Win 40350/titanium oxide micropore compound coating.
Summary of the invention
The technical problem that the present invention will solve is to improve the biological activity on Ni-Ti alloy surface, improves the biocompatibility of its implant and tissue.A kind of method for preparing Win 40350/titanium oxide micropore compound coating at the thermal treatment of Ni-Ti alloy surface bonding and differential arc oxidization technique is provided.
Technical scheme of the present invention is that Ni-Ti alloy is cleaned back thermal treatment in electric furnace, and Heating temperature is 400～650 ℃, soaking time 0.5～2h; Furnace cooling; Then the Ni-Ti alloy after bakingout process is suspended in the electrolytic solution as anode, negative electrode is the stainless steel electrolytic liquid bath or is suspended on the stainless steel substrates in the electrolytic solution, adopts the bipolar pulse power supply; Direct impulse voltage is that 300～650V, negative-going pulse voltage are that 0～100V, pulse-repetition are that 200～800Hz, dutycycle are 8%～30% to carry out differential arc oxidation; The working fluid temperature is 0～40 ℃, treatment time 0～10min, and the electrolytic solution that differential arc oxidation adopts is (CH
3COO)
2CaH
2O and NaH
2PO
42H
2The aqueous solution of O, composition proportion is Ca 0.025-0.2mol/L, contains P 0.025-0.2mol/L.
Effect of the present invention and benefit are to form the fine and close titania coating of one deck through Ni-Ti alloy being carried out preoxidation thermal treatment; And then carry out differential arc oxidation; Having solved Ni-Ti alloy is not valve metal, is difficult to directly carry out the problem that differential arc oxidation is handled, and goes out Win 40350/titanium oxide micropore compound coating in the Ni-Ti alloy surface preparation; The coating of the inventive method preparation can effectively be improved the biological activity of coating, and improves the intensity of coating and the interface bond strength of coating and matrix.
Embodiment
Be described in detail embodiment of the present invention below in conjunction with technical scheme.
Embodiment 1:
The Ni-Ti alloy workpiece is put in the electric furnace heat-treats, thermal treatment temp is at 400 ℃, soaking time 2h; Furnace cooling is suspended to the Ni-Ti alloy after the thermal treatment in the electrolytic solution as anode then, and negative electrode is the stainless steel electrolytic liquid bath; Adopt the bipolar pulse power supply, direct impulse voltage is that 550V, negative-going pulse voltage are that 50V, pulse-repetition are that 500Hz, dutycycle are 20% to carry out differential arc oxidation, and the working fluid temperature is 10 ℃; Treatment time 1min, the bath composition that differential arc oxidation adopts is (CH
3COO)
2CaH
2O and NaH
2PO
42H
2The aqueous solution of O, composition proportion are Ca 0.1mol/L, P 0.1mol/L.
This embodiment can form the titanium oxide microporous coat that contains Ca, P on the Ni-Ti alloy surface, and coating and Ni-Ti alloy bonding strength are difficult for peeling off, coming off greater than 30MPa, have good biological activity.
Embodiment 2:
The Ni-Ti alloy workpiece is put in the electric furnace heat-treats, thermal treatment temp is at 550 ℃, soaking time 1h; Furnace cooling is suspended to the Ni-Ti alloy after the thermal treatment in the electrolytic solution as anode then, and negative electrode is the stainless steel electrolytic liquid bath; Adopt the bipolar pulse power supply, direct impulse voltage is that 500V, negative-going pulse voltage are that 50V, pulse-repetition are that 500Hz, dutycycle are 15% to carry out differential arc oxidation, and the working fluid temperature is 10 ℃; Treatment time 3min, the bath composition that differential arc oxidation adopts is (CH
3COO)
2CaH
2O and NaH
2PO
42H
2The aqueous solution of O, composition proportion are Ca 0.1mol/L, P 0.1mol/L.
This embodiment can form Win 40350/titanium oxide micropore compound coating on the Ni-Ti alloy surface, and coating and Ni-Ti alloy bonding strength are difficult for peeling off, coming off greater than 30MPa, have good biological activity, promote new bone growth.
Embodiment 3:
The Ni-Ti alloy workpiece is put in the electric furnace heat-treats, thermal treatment temp is at 650 ℃, soaking time 0.5h; Furnace cooling; Then the Ni-Ti alloy after the thermal treatment is suspended in the electrolytic solution as anode, negative electrode is the stainless steel electrolytic liquid bath, adopts the bipolar pulse power supply; Direct impulse voltage is that 450V, negative-going pulse voltage are that 50V, pulse-repetition are that 500Hz, dutycycle are 10% to carry out differential arc oxidation; The working fluid temperature is 10 ℃, treatment time 5min, and the bath composition that differential arc oxidation adopts is (CH
3COO)
2CaH
2O and NaH
2PO
42H
2The aqueous solution of O, composition proportion are Ca 0.1mol/L, P 0.1mol/L.
This embodiment can form Win 40350/titanium oxide micropore compound coating on the Ni-Ti alloy surface, and coating and Ni-Ti alloy bonding strength are difficult for peeling off, coming off greater than 30MPa, have good biological activity, promote new bone growth.
Claims (1)
1. the preparation method of Ni-Ti alloy surface hydroxyl phosphatic rock/titanium oxide compound coating; It is characterized in that: with Ni-Ti alloy thermal treatment in electric furnace, Heating temperature is 400～650 ℃, soaking time 0.5～2h; Furnace cooling; Then the Ni-Ti alloy after bakingout process is suspended in the electrolytic solution as anode, negative electrode is the stainless steel electrolytic liquid bath or is suspended on the stainless steel substrates in the electrolytic solution, adopts the bipolar pulse power supply; Direct impulse voltage is that 300～650V, negative-going pulse voltage are that 0～100V, pulse-repetition are that 200～800Hz, dutycycle are 8%～30% to carry out differential arc oxidation; The working fluid temperature is 0～40 ℃, treatment time 1～10min, and the electrolytic solution that differential arc oxidation adopts is (CH
3COO)
2CaH
2O and NaH
2PO
42H
2The aqueous solution of O, composition proportion is Ca 0.025～0.2mol/L, contains P 0.025～0.2mol/L.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN2009100115803A CN101555616B (en) | 2009-05-13 | 2009-05-13 | Method for preparing hydroxyapatite/titanium dioxide composite coating on nickel-titanium surface |
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|---|---|---|---|
| CN2009100115803A CN101555616B (en) | 2009-05-13 | 2009-05-13 | Method for preparing hydroxyapatite/titanium dioxide composite coating on nickel-titanium surface |
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| CN101555616A CN101555616A (en) | 2009-10-14 |
| CN101555616B true CN101555616B (en) | 2012-11-07 |
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Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI480026B (en) * | 2010-01-14 | 2015-04-11 | Univ Nat Taipei Technology | Bio-implant having screw body selectively formed with nanoporous in spiral groove and method of making the same |
| CN102560595A (en) * | 2012-01-05 | 2012-07-11 | 哈尔滨工业大学 | Process for preparing composite coating of hydroxyapatite and porous titanium dioxide on biomedical titanium metal surface |
| CN102605411B (en) * | 2012-03-31 | 2014-08-13 | 大连理工大学 | Preparation process of pleated hole-slot shaped titanium dioxide thin film with super wetting ability |
| CN102747403B (en) * | 2012-07-03 | 2014-10-29 | 淮阴工学院 | Method of preparing magnesium-doped hydroxyapatite/titania active film on surface of medical titanium alloy |
| CN103083099A (en) * | 2013-01-29 | 2013-05-08 | 哈尔滨工业大学 | Root of tooth implant matrix containing silicon, calcium, phosphorus and sodium micro-arc oxidation coating and preparation method thereof |
| CN105671612B (en) * | 2015-08-21 | 2017-12-29 | 北京大学第三医院 | Porous metal implants and preparation method with differential arc oxidation coating |
| CN106673693A (en) * | 2016-12-23 | 2017-05-17 | 江南大学 | Preparation method of novel bioceramic porous material |
| CN109487323B (en) * | 2018-12-20 | 2020-12-11 | 大连理工大学 | Electrolyte for preparing porous membrane containing bioactive elements on titanium metal surface by micro-arc oxidation |
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| WO2006004684A2 (en) * | 2004-06-28 | 2006-01-12 | Incyte Corporation | 3-aminocyclopentanecarboxamides as modulators of chemokine receptors |
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| CN101054708A (en) * | 2007-02-10 | 2007-10-17 | 青岛科技大学 | Method of preparing hydroxyl apatite bioceramic film by plasma micro-arc oxidization method |
| CN101138650A (en) * | 2007-10-24 | 2008-03-12 | 常州天力生物涂层技术有限公司 | Galvano-chemistry bioactivation processing method of stephanoporate titanium bead sintered coating |
| US20080086195A1 (en) * | 2006-10-05 | 2008-04-10 | Boston Scientific Scimed, Inc. | Polymer-Free Coatings For Medical Devices Formed By Plasma Electrolytic Deposition |
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2009
- 2009-05-13 CN CN2009100115803A patent/CN101555616B/en not_active Expired - Fee Related
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1381616A (en) * | 2001-02-23 | 2002-11-27 | 株式会社电装 | Electrolytic phosphate chemical treatment method |
| WO2006004684A2 (en) * | 2004-06-28 | 2006-01-12 | Incyte Corporation | 3-aminocyclopentanecarboxamides as modulators of chemokine receptors |
| US20080086195A1 (en) * | 2006-10-05 | 2008-04-10 | Boston Scientific Scimed, Inc. | Polymer-Free Coatings For Medical Devices Formed By Plasma Electrolytic Deposition |
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| CN101555616A (en) | 2009-10-14 |
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Inventor after: Zhao Hong Inventor after: Guan Shaoxuan Inventor after: Ge Zhendong Inventor after: Tian Cuicui Inventor after: Qi Min Inventor after: Yang Dazhi Inventor before: Zhao Hong Inventor before: Guan Shaoxuan Inventor before: Ge Zhendong Inventor before: Tian Cui Inventor before: Qi Min Inventor before: Yang Dazhi |
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Free format text: CORRECT: INVENTOR; FROM: ZHAO HONG GUAN SHAOXUAN GE ZHENDONG TIAN CUI QI MIN YANG DAZHI TO: ZHAO HONG GUAN SHAOXUAN GE ZHENDONG TIAN CUICUI QI MIN YANG DAZHI |
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