CN101555616A - 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
- Publication number
- CN101555616A CN101555616A CNA2009100115803A CN200910011580A CN101555616A CN 101555616 A CN101555616 A CN 101555616A CN A2009100115803 A CNA2009100115803 A CN A2009100115803A CN 200910011580 A CN200910011580 A CN 200910011580A CN 101555616 A CN101555616 A CN 101555616A
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- Prior art keywords
- nickel
- alloy
- coating
- electrolyte
- titanium
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- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Links
- 229910001000 nickel titanium Inorganic materials 0.000 title claims abstract description 38
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 239000011248 coating agent Substances 0.000 title claims abstract description 31
- 238000000576 coating method Methods 0.000 title claims abstract description 31
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 16
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 title abstract description 15
- 229910052588 hydroxylapatite Inorganic materials 0.000 title abstract description 14
- 238000000034 method Methods 0.000 title abstract description 14
- HZEWFHLRYVTOIW-UHFFFAOYSA-N [Ti].[Ni] Chemical compound [Ti].[Ni] HZEWFHLRYVTOIW-UHFFFAOYSA-N 0.000 title abstract 3
- 239000002131 composite material Substances 0.000 title abstract 3
- 239000000203 mixture Substances 0.000 claims abstract description 11
- 239000010935 stainless steel Substances 0.000 claims abstract description 8
- 229910001220 stainless steel Inorganic materials 0.000 claims abstract description 8
- 239000007864 aqueous solution Substances 0.000 claims abstract description 6
- 238000010438 heat treatment Methods 0.000 claims abstract description 3
- 229910045601 alloy Inorganic materials 0.000 claims description 35
- 239000000956 alloy Substances 0.000 claims description 35
- KHYBPSFKEHXSLX-UHFFFAOYSA-N iminotitanium Chemical compound [Ti]=N KHYBPSFKEHXSLX-UHFFFAOYSA-N 0.000 claims description 33
- 238000007254 oxidation reaction Methods 0.000 claims description 17
- 230000003647 oxidation Effects 0.000 claims description 16
- 238000007669 thermal treatment Methods 0.000 claims description 11
- 238000002360 preparation method Methods 0.000 claims description 10
- 239000008151 electrolyte solution Substances 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 5
- 239000012530 fluid Substances 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- 238000002791 soaking Methods 0.000 claims description 5
- -1 titanium dioxide compound Chemical class 0.000 claims description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- 238000013021 overheating Methods 0.000 claims description 2
- 239000011435 rock Substances 0.000 claims description 2
- 239000000758 substrate Substances 0.000 claims description 2
- 230000004071 biological effect Effects 0.000 abstract description 7
- 239000007943 implant Substances 0.000 abstract description 6
- 238000007745 plasma electrolytic oxidation reaction Methods 0.000 abstract description 3
- 239000003792 electrolyte Substances 0.000 abstract 5
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 abstract 1
- 150000001875 compounds Chemical class 0.000 description 7
- 210000000988 bone and bone Anatomy 0.000 description 5
- 230000000694 effects Effects 0.000 description 3
- 229910001069 Ti alloy Inorganic materials 0.000 description 2
- 230000008468 bone growth Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 210000001519 tissue Anatomy 0.000 description 2
- 201000010814 Synostosis Diseases 0.000 description 1
- 206010060872 Transplant failure Diseases 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 230000000975 bioactive effect Effects 0.000 description 1
- 230000031018 biological processes and functions Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 238000001727 in vivo Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 239000002207 metabolite Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 210000004409 osteocyte Anatomy 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
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- Materials For Medical Uses (AREA)
- Prostheses (AREA)
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 NaH 2PO4.2H2O, 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 by thermal treatment is in the method for Ni-Ti alloy surface preparation hydroxyapatite/titanium dioxide compound coating.
Background technology
Niti-shaped memorial alloy (NiTi) is widely used in the human body hard tissue implant owing to having shape memory effect and super-elasticity, but the Ni-Ti alloy bone implant material does not have biological activity, can not with human body bone forming synostosis, easily cause the implant afunction, make graft failure.Hydroxyapatite (HA) is the main inorganic components of body bone tissue, has excellent biological compatibility and bone guided, 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 dioxide in the titanium alloy surface preparation, promoting osteocyte to stick with the sorption of biological metabolite, the interface binding power effect that titanium dioxide improves coating and Ni-Ti alloy the biological action of hydroxyapatite, microvoid structure is dissolved in one, goes out hydroxyapatite/titanium dioxide 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 based on the porous coating of base metal oxide and with matrix and forms high-intensity metallurgical binding, but since in the Ni-Ti alloy atomic ratio of Ni and Ti near 50%, Ni is not a valve metal, its oxide film character instability can not directly be used 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 hydroxyapatite/titanium dioxide microporous coat, the present invention is by heat-treating in advance Ni-Ti alloy, and then adopts the differential arc oxidation method successfully to prepare hydroxyapatite/titanium dioxide micropore compound coating on Ni-Ti alloy.
Summary of the invention
The technical problem to be solved in the present invention 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 hydroxyapatite/titanium dioxide micropore compound coating at the thermal treatment of Ni-Ti alloy surface bonding and differential arc oxidization technique is provided.
Technical solution of the present invention is that Ni-Ti alloy is cleaned back thermal treatment in electric furnace, Heating temperature is 400～650 ℃, soaking time 0.5～2h, furnace cooling, then the Ni-Ti alloy after Overheating Treatment is suspended in the electrolytic solution as anode, negative electrode is the stainless steel electrolytic liquid bath or is suspended on the interior stainless steel substrates of electrolytic solution, adopt the bipolar pulse power supply, direct impulse voltage is 300～650V, negative-going pulse voltage is 0～100V, pulse-repetition is 200～800Hz, dutycycle is 8%～30% to carry out differential arc oxidation, the working fluid temperature is 0～40 ℃, treatment time 0～10min, 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 by Ni-Ti alloy being carried out the titania coating of preoxidation thermal treatment formation one deck densification, and then carry out differential arc oxidation, having solved Ni-Ti alloy is not valve metal, be difficult to directly carry out the problem that differential arc oxidation is handled, go out hydroxyapatite/titanium dioxide 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 the specific 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, 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, 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, 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.
Present embodiment can form the titanium dioxide 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, 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.
Present embodiment can form hydroxyapatite/titanium dioxide 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, adopt 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, 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.
Present embodiment can form hydroxyapatite/titanium dioxide 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 dioxide 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 Overheating Treatment is suspended in the electrolytic solution as anode, negative electrode is the stainless steel electrolytic liquid bath or is suspended on the interior stainless steel substrates of electrolytic solution, adopt the bipolar pulse power supply, direct impulse voltage is 300～650V, negative-going pulse voltage is 0～100V, pulse-repetition is 200～800Hz, dutycycle is 8%～30% to carry out differential arc oxidation, the working fluid temperature is 0～40 ℃, treatment time 0～10min, 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 |
|---|---|---|---|
| CN2009100115803A CN101555616B (en) | 2009-05-13 | 2009-05-13 | Method for preparing hydroxyapatite/titanium dioxide composite coating on nickel-titanium surface |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009100115803A CN101555616B (en) | 2009-05-13 | 2009-05-13 | Method for preparing hydroxyapatite/titanium dioxide composite coating on nickel-titanium surface |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101555616A true CN101555616A (en) | 2009-10-14 |
| CN101555616B CN101555616B (en) | 2012-11-07 |
Family
ID=41173890
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2009100115803A Expired - Fee Related CN101555616B (en) | 2009-05-13 | 2009-05-13 | Method for preparing hydroxyapatite/titanium dioxide composite coating on nickel-titanium surface |
Country Status (1)
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|---|---|
| CN (1) | CN101555616B (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN102605411A (en) * | 2012-03-31 | 2012-07-25 | 大连理工大学 | Preparation process of pleated hole-slot shaped titanium dioxide thin film with super wetting ability |
| CN102747403A (en) * | 2012-07-03 | 2012-10-24 | 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 |
| 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 |
| CN105671612A (en) * | 2015-08-21 | 2016-06-15 | 北京大学第三医院 | Porous metal implant with micro-arc oxidation coating and preparation method |
| CN106673693A (en) * | 2016-12-23 | 2017-05-17 | 江南大学 | Preparation method of novel bioceramic porous material |
| CN109487323A (en) * | 2018-12-20 | 2019-03-19 | 大连理工大学 | A kind of electrolyte in surface of metal titanium differential arc oxidation preparation perforated membrane containing biological active elements |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4019723B2 (en) * | 2001-02-23 | 2007-12-12 | 株式会社デンソー | Electrolytic phosphate chemical treatment method |
| KR100856156B1 (en) * | 2004-06-28 | 2008-09-03 | 인사이트 코포레이션 | 3-aminocyclopentanecarboxamides as modulators of chemokine receptors |
| EP2084310A1 (en) * | 2006-10-05 | 2009-08-05 | Boston Scientific Limited | Polymer-free coatings for medical devices formed by plasma electrolytic deposition |
| CN1974876B (en) * | 2006-11-02 | 2010-07-07 | 华南理工大学 | Bioactive film on titanium metal surface and its sand blasting-micro arc oxidizing compounding process |
| CN100572610C (en) * | 2007-02-10 | 2009-12-23 | 青岛科技大学 | The plasma micro-arc oxidation legal system is equipped with the method for hydroxyl apatite bioceramic film |
| CN101138650B (en) * | 2007-10-24 | 2010-11-03 | 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 |
-
2009
- 2009-05-13 CN CN2009100115803A patent/CN101555616B/en not_active Expired - Fee Related
Cited By (10)
| 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 |
| CN102605411A (en) * | 2012-03-31 | 2012-07-25 | 大连理工大学 | Preparation process of pleated hole-slot shaped titanium dioxide thin film with super wetting ability |
| 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 |
| CN102747403A (en) * | 2012-07-03 | 2012-10-24 | 淮阴工学院 | Method of preparing magnesium-doped hydroxyapatite/titania active film on surface of medical titanium alloy |
| 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 |
| CN105671612A (en) * | 2015-08-21 | 2016-06-15 | 北京大学第三医院 | Porous metal implant with micro-arc oxidation coating and preparation method |
| CN106673693A (en) * | 2016-12-23 | 2017-05-17 | 江南大学 | Preparation method of novel bioceramic porous material |
| CN109487323A (en) * | 2018-12-20 | 2019-03-19 | 大连理工大学 | A kind of electrolyte in surface of metal titanium differential arc oxidation preparation perforated membrane containing biological active elements |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101555616B (en) | 2012-11-07 |
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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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