CN100368027C - Hydrogen ion implantation process of raising bioactivity of nanometer titania coating - Google Patents
Hydrogen ion implantation process of raising bioactivity of nanometer titania coating Download PDFInfo
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- CN100368027C CN100368027C CNB2005100297432A CN200510029743A CN100368027C CN 100368027 C CN100368027 C CN 100368027C CN B2005100297432 A CNB2005100297432 A CN B2005100297432A CN 200510029743 A CN200510029743 A CN 200510029743A CN 100368027 C CN100368027 C CN 100368027C
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Abstract
The present invention relates to a hydrogen ion implantation method of enhancing the bioactivity of a nanometer titanium oxide coating, which is characterized in that a plasma immersion and implantation method is used for implanting hydrogen ions into a plasma spray nanometer titanium oxide coating, gas is introduced in a vacuum chamber in vacuum degree of 5*10<-6> to 10*10<-6> torr, the gas is ionized to form plasma through radio frequency discharge, a sample to be implanted is surrounded by the plasma, and positive ions in the plasma are implanted in the surface of the sample under the negative bias traction of a sample table. Results show that after the treated TiO2 coating is soaked in simulated body fluid for 14 days, bone-like apatites can be formed on the surface of the hydrogen ion implantation treated plasma spray nanometer TiO2 coating, which shows that the coating has good bioactivity.
Description
Technical field
The present invention relates to a kind of activation method of new bone substitution material, adopt hydrion to inject more precisely and make plasma spraying titania coating surface biologically active, belong to the medical bio field of ceramic coatings.
Background technology
Hydroxyapatite coating layer in plasma spraying is because its superior bioactive and biocompatibility have obtained extensive use clinically as artificial bone and artificial joint coating.But, hydroxyapatite coating layer in plasma spraying has two distinct disadvantage that limit its application, the one, low-crystallinity, low degree of crystallinity makes hydroxyapatite coating layer degraded easily in body fluid, reduced its service life [Fazan F, Marquis PM, Dissolution behavior of plasma-sprayed hydroxyapatite coatings, J.Mater.Sci.:Mater.Med.11 (2000) 787-92].The 2nd, and relatively low bond strength between the titanium alloy substrate, low bond strength can make the patient face danger [the Lamy D of disbonding, PierrcAC and Heimann RB, Hydroxyapatite coatings with a bond coat of biomedicalimplants by plasma projection, J.Mater.Res., 11 (1996) 680-686].Therefore, obtaining a kind of mechanical property and the biology performance excellent coating material of holding concurrently should be to make great efforts pursuing target.
In recent years, TiO
2The application of material in biological field obtains paying attention to gradually, and its biocompatibility has obtained confirming preferably.Recent research shows that in simulated body fluid, osteoid apatite can be at nano-TiO
2Powder [Kasuga T, Kondo H, Nogami M, Apatite formation on TiO
2Insimulated body fluid.J.Cryst.Growth 23 (2002) 5235-5240; M.Keshmiri and T.Troczynski, Apatite formation on TiO
2Anatase microspheres.J.Non-Cryst.Solids 324 (2003) 289-294] and by surperficial [the Uchida M that forms of the nano structure membrane of sol-gal process acquisition, Kim HM, Kokubo T, Fujibayashi S, Nakamura T.Structuraldependence of apatite formation on titania gels in a simulated body fluid.J.Biomed Mater Res.64A (2003) 164-170], this is a specific index of material biologically active.In addition, the TiO that has nanostructured
2Ceramic surface can promote osteoblastic seek connections with, grow and breed [Thomas J.Webster et al.Enhanced functions of osteoblasts onnanophase ceramics, Biomaterials 21 (2000) 1803-1810].This shows nanostructured TiO
2Might both have certain biological activity, have excellent biological compatibility again.This shows nanostructured TiO
2Behind the bone substitution material implant into body might and osseous tissue between form good synostosis.
Although the thin film of titanium oxide biologically active that above-mentioned sol-gal process obtains, with titanium alloy substrate relatively low bond strength limited it in clinical practice may.A large amount of documents confirms, plasma spraying TiO
2Coating has good corrosion resistance and abrasion resistance properties, and widely uses industrial, but does not see plasma spraying TiO
2The bioactivity research report of coating.Our early-stage Study confirms, plasma spraying TiO
2The bond strength of coating and titanium alloy substrate is 2～3 times of hydroxyapatite coating layer, yet this inert coatings can not be induced formation [Liu X, Ding C, the Plasma sprayed wollastonite/TiO of osteoid apatite in body fluid
2Composite coatings on titanium alloys.Biomaterials 23 (2002) 4065-4077].Therefore, if give plasma spraying TiO2 coating good biological activity, its combination property will be expected to be better than clinical hydroxyapatite coating layer commonly used.
Plasma spraying nanostructured titania coating is a kind of new coating of development in recent years, is expected to obtain to have the coating material of nano effect.And, be easy to practicability, thereby plasma spraying nanostructured titania coating has obtained the extensive attention of electronics, chemical industry and biological field because plasma spray coating process is simple.But pre-stage test confirms that plasma spraying routine and nanostructured titania coating all lack biological activity, and in simulated body fluid, osteoid apatite can not form at coating surface.
The hydrion injection technique is widely used in the semicon industry.During often being injected in the silica-base material, hydrogen, also is used to make SOI (silicon materials above the insulator) material with the optics and the electrology characteristic of defective with the change silica-base material.In our previous work, once hydrogen was injected into and improved its biological activity in the monocrystalline silicon piece, and sure effect [Xuanyong Liu, Ricky K.Y.Fu, RayW.Y.Poon have been obtained, Peng Chen, Paul K.Chu, Chuanxian Ding, Biomimetic Growth ofApatite on Hydrogen Implanted Silicon, Biomaterials, 25/25 (2004) 5575-5581].Therefore, the method for intending in the present invention adopting hydrion to inject is improved the surface characteristic of plasma spraying nano-titanium oxide coating layer, thereby improves the biological activity of plasma spraying nano-titanium oxide coating layer.
Summary of the invention
The present invention is based on hydrogen plasma and injects and can change the material surface characteristic and propose, purpose is to provide a kind of hydrion to inject the method that improves bioactivity of nanometer titania coating, the present invention be utilize plasma spraying technology with the nano-titanium oxide powder deposition on the medical metal matrix, and adopt hydrogen plasma immersion ion injection technique to improve the biological activity and the biocompatibility of plasma spraying nano-titanium oxide coating layer, to develop novel biological activity bone substitution material.
Specific embodiment is as follows:
With particle diameter is nano oxidized titanium powder below the 100nm, forms aggregate particle size and be about micron-sized spherical powder behind mist projection granulating.Adopt plasma spraying technology, the nano-titanium oxide powder deposition after the pelletize on the medical metal matrix, is prepared titania coating.Under the optimized parameters (seeing Table 1) titanium dioxide powder is being sprayed on the medical metal matrix that cleans with sandblast.The cleaning of metallic matrix and sandblast are technology commonly used in the general Plasma Spraying Process Using, and its technological parameter need not at this detailed description, and one of ordinary skill in the art all can be grasped and be known.
Table 1 spray parameters
| Plasma gas Ar | 40slpm * | Powder carrier gas Ar | 3.5slpm |
| Plasma gas H 2 | 10slpm | Powder feeding rate | 7g/mm |
| Spray distance | 100mm | Electric current | 600A |
*Slpm: standard liter/min
Principal crystalline phase be the nano oxidized titanium powder of anatase after the plasma flame high-temperature fusion, high speed deposition forms coating to titanium alloy-based surface after the condensation cured.In this process, the partial oxidation titanium undergoes phase transition, and is phase-changed into the rutile phase from anatase.Studies show that, prepare the coating principal crystalline phase and be the rutile phase (Fig. 1: the titania coating coating XRD figure), coating surface by particle diameter for to form (Fig. 2) less than the nano-particle of 50nm.The coating surface reason different with inner phase composition and structure is the difference of its thermal history, and coating inside can be subjected to the heating of follow-up melt always, and anatase can progressively change into stable rutile phase mutually.The melt of coating surface does not have follow-up melt heating and directly is cooled to room temperature, and therefore metastable anatase can remain mutually, and crystal grain also keeps nanostructured.
Coatings prepared is carried out hydrion inject in plasma immersion ion injection device (Plasma Immersion IonImplantation), the equipment sketch map is seen Fig. 3.Its operation principle is as follows: under certain vacuum gas is introduced vacuum chamber, allow gas ionization form plasma by radio-frequency discharge, plasma surrounds sample fully, and under the back bias voltage traction of sample platform, the cation in the plasma is injected into the sample top layer.Ion implantation parameter of the present invention is: earlier the vacuum chamber basic pressure is evacuated to 5～10 * 10
-6Torr, with Ar ion pair sample surfaces bombardment 5～10 minutes, charging into hydrogen to pressure then was 3～8 * 10 earlier
-4, the injection bias voltage that imposes on sample target platform is 20～40kV, and the voltage pulsewidth is 30～50 microseconds, and pulse frequency is 100～300Hz, adopts radio frequency ionization hydrogen simultaneously, and radio-frequency power is 800～1400W, the hydrion injection length is 60～180 minutes.
The hydrion of the described plasma spraying nano-titanium oxide coating layer that carries out in the plasma immersion injection device injects, be under certain vacuum, gas to be introduced vacuum chamber, make gas ionization form plasma by radio-frequency discharge, plasma surrounds pre-injected sample fully, under the back bias voltage traction of sample platform, the cation in the plasma is injected into the sample top layer.
Describedly the plasma spraying nano-titanium oxide coating layer is carried out hydrion inject in the plasma immersion ion injection device; Its injection parameter is: earlier the vacuum chamber basic pressure is evacuated to 8 * 10
-6Torr, with Ar ion pair sample surfaces bombardment 10 minutes, charging into hydrogen to pressure then was 6 * 10 earlier
-4, the injection bias voltage that imposes on sample target platform is 30kV, and the voltage pulsewidth is 200 microseconds, and pulse frequency is 50Hz, adopts radio frequency ionization hydrogen simultaneously, and radio-frequency power is 1000W, the hydrion injection length is 120 minutes.
Describedly the plasma spraying nano-titanium oxide coating layer is carried out hydrion inject in the plasma immersion ion injection device; Its injection parameter is earlier the vacuum chamber basic pressure to be evacuated to 8 * 10
-6Torr, with Ar ion pair sample surfaces bombardment 5 minutes, charging into hydrogen to pressure then was 6 * 10 earlier
-4, the injection bias voltage that imposes on sample target platform is 40kV, and the voltage pulsewidth is 30 microseconds, and pulse frequency is 50Hz, adopts radio frequency ionization hydrogen simultaneously, and radio-frequency power is 1400W, the hydrion injection length is 120 minutes.
To handle the back coating is immersed in the simulated body fluid, studies confirm that, after soaking certain hour, osteoid apatite can form on the plasma spraying nano-titanium oxide coating layer surface that hydrion injects after handling, and this plasma spraying nano-titanium oxide coating layer that shows that hydrion injects after handling has good biological activity.
Description of drawings
The XRD figure of Fig. 1 plasma spraying nano-titanium oxide coating layer
R represents rutile among the figure, and A represents anatase
Fig. 2 plasma spraying nano-titanium oxide coating layer surface topography: (a) low power (1000 *) image, (b) high power (50000 *) image
Fig. 3 plasma immersion ion injects sketch map
The submergence of Fig. 4 hydrogen plasma is injected nano-titanium oxide coating layer and is immersed in 14 days rear surface patterns (a) of simulated body fluid and cross section pattern (b).
The untreated plasma spraying titania coating of Fig. 5 is immersed in the surface topography after 14 days in the simulated body fluid
The specific embodiment
Further illustrate characteristics of the present invention and effect below by embodiment.Limit the present invention absolutely not.
Embodiment 1: with particle diameter is the nano oxidized titanium powder of P25 (anatase content is about 80%) about 30nm, forms aggregate particle size and be about micron-sized spherical powder behind mist projection granulating.Adopt plasma spraying technology, the nano-titanium oxide powder deposition after the pelletize on titanium alloy substrate, is prepared titania coating, concrete spray parameters sees Table 1.
The titania coating of preparation is used acetone ultrasonic cleaning 5 minutes, carry out hydrion then and inject in the plasma immersion ion injection device, use Ar ion pair sample surfaces bombardment 5 minutes before injecting earlier, injection parameter sees Table 2.To handle the back coating and be immersed in the simulated body fluid, and soak after 14 days, osteoid apatite can form on the plasma spraying nano-titanium oxide coating layer surface that hydrion injects after handling, and sees Fig. 4.This plasma spraying nano-titanium oxide coating layer that shows that hydrion injects after handling has good biological activity.Under the identical soaking conditions, do not find have osteoid apatite to form through the coating surface of hydrion injection processing, its surface topography is preceding consistent with immersion, sees Fig. 5.
Table 2 hydrion injection parameter
| Basic pressure (Torr.) | 8×10 -6 | Pulsewidth (μ s) | 30 |
| H 2Pressure (Torr.) | 6×10 -4 | Pulse frequency (Hz) | 100 |
| Injecting voltage (kV) | 20 | Radio-frequency power (W) | 1000 |
| Injection length (min) | 120 |
Embodiment 2: with particle diameter is the nano oxidized titanium powder of P25 (anatase content is about 80%) about 30nm, forms aggregate particle size and be about micron-sized spherical powder behind mist projection granulating.Adopt plasma spraying technology, the nano-titanium oxide powder deposition after the pelletize on titanium alloy substrate, is prepared titania coating, concrete spray parameters sees Table 1.
The titania coating of preparation is used acetone ultrasonic cleaning 5 minutes, carry out hydrion then and inject in the plasma immersion ion injection device, use Ar ion pair sample surfaces bombardment 10 minutes before injecting earlier, injection parameter sees Table 3.To handle the back coating is immersed in the simulated body fluid, studies confirm that, soak after 14 days, osteoid apatite can form on the plasma spraying nano-titanium oxide coating layer surface that hydrion injects after handling, and this plasma spraying nano-titanium oxide coating layer that shows that hydrion injects after handling has good biological activity.
Table 3 hydrion injection parameter
| Basic pressure (Torr.) | 8×10 -6 | Pulsewidth (μ s) | 200 |
| H 2Pressure (Torr.) | 8×10 -4 | Pulse frequency (Hz) | 50 |
| Injecting voltage (kV) | 30 | Radio-frequency power (W) | 1000 |
| Injection length (min) | 120 |
Embodiment 3: with particle diameter is the nano oxidized titanium powder of P25 (anatase content is about 80%) about 30nm, and forming aggregate particle size behind mist projection granulating is micron-sized spherical powder.Adopt plasma spraying technology, the nano-titanium oxide powder deposition after the pelletize on titanium alloy substrate, is prepared titania coating, concrete spray parameters sees Table 1.
The titania coating of preparation is used acetone ultrasonic cleaning 5 minutes, carry out hydrion then and inject in the plasma immersion ion injection device, use Ar ion pair sample surfaces bombardment 10 minutes before injecting earlier, injection parameter sees Table 4.To handle the back coating is immersed in the simulated body fluid, studies confirm that, soak after 14 days, osteoid apatite can form on the plasma spraying nano-titanium oxide coating layer surface that hydrion injects after handling, and this plasma spraying nano-titanium oxide coating layer that shows that hydrion injects after handling has good biological activity.
Table 4 hydrion injection parameter
| Basic pressure (Torr.) | 8×10 -6 | Pulsewidth (μ s) | 30 |
| H 2Pressure (Torr.) | 6×10 -4 | Pulse frequency (Hz) | 100 |
| Injecting voltage (kV) | 40 | Radio-frequency power (W) | 1400 |
| Injection length (min) | 120 |
Claims (5)
1. a hydrion injects the method that improves the plasma spraying bioactivity of nanometer titania coating, it is characterized in that using plasma submergence method for implanting article on plasma spraying nano-titanium oxide coating layer carries out hydrion and injects, injection parameter is earlier the vacuum chamber basic pressure to be evacuated to 5～10 * 10
-6Torr, with Ar ion pair sample surfaces bombardment 5～10 minutes, charging into hydrogen to pressure then was 3～8 * 10 earlier
-4, the injection bias voltage that imposes on sample target platform is 20～40kV, and the voltage pulsewidth is 30～50 microseconds, and pulse frequency is 100～300Hz, adopts radio frequency ionization hydrogen simultaneously, and radio-frequency power is 800～1400W, the hydrion injection length is 60～180 minutes.
2. inject the method that improves the plasma spraying bioactivity of nanometer titania coating by the described hydrion of claim 1, the hydrion that it is characterized in that the described plasma spraying nano-titanium oxide coating layer that carries out in the plasma immersion injection device injects, be under certain vacuum, gas to be introduced vacuum chamber, make gas ionization form plasma by radio-frequency discharge, plasma surrounds pre-injected sample fully, under the back bias voltage traction of sample platform, the cation in the plasma is injected into the sample top layer.
3. inject the method that improves the plasma spraying bioactivity of nanometer titania coating by the described hydrion of claim 1, it is characterized in that the plasma spraying nano-titanium oxide coating layer is carried out hydrion to be injected in the plasma immersion ion injection device; Its injection parameter is earlier the vacuum chamber basic pressure to be evacuated to 8 * 10
-6Torr, with Ar ion pair sample surfaces bombardment 5 minutes, charging into hydrogen to pressure then was 6 * 10 earlier
-4, the injection bias voltage that imposes on sample target platform is 20kV, and the voltage pulsewidth is 30 microseconds, and pulse frequency is 100Hz, adopts radio frequency ionization hydrogen simultaneously, and radio-frequency power is 1000W, the hydrion injection length is 120 minutes.
4. a hydrion injects the method that improves the plasma spraying bioactivity of nanometer titania coating, it is characterized in that the plasma spraying nano-titanium oxide coating layer is carried out hydrion in the plasma immersion ion injection device inject; Its injection parameter is: earlier the vacuum chamber basic pressure is evacuated to 8 * 10
-6Torr, with Ar ion pair sample surfaces bombardment 10 minutes, charging into hydrogen to pressure then was 6 * 10 earlier
-4, the injection bias voltage that imposes on sample target platform is 30kV, and the voltage pulsewidth is 200 microseconds, and pulse frequency is 50Hz, adopts radio frequency ionization hydrogen simultaneously, and radio-frequency power is 1000W, the hydrion injection length is 120 minutes.
5. a hydrion injects the method that improves the plasma spraying bioactivity of nanometer titania coating, it is characterized in that the plasma spraying nano-titanium oxide coating layer is carried out hydrion in the plasma immersion ion injection device inject; Its injection parameter is earlier the vacuum chamber basic pressure to be evacuated to 8 * 10
-6Torr, with Ar ion pair sample surfaces bombardment 5 minutes, charging into hydrogen to pressure then was 6 * 10 earlier
-4, the injection bias voltage that imposes on sample target platform is 40kV, and the voltage pulsewidth is 30 microseconds, and pulse frequency is 50Hz, adopts radio frequency ionization hydrogen simultaneously, and radio-frequency power is 1400W, the hydrion injection length is 120 minutes.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101554583B (en) * | 2009-06-02 | 2011-01-05 | 北京师范大学 | Titania thin films with submicron pore structure and preparation method thereof |
| CN102191454B (en) * | 2011-04-26 | 2012-12-05 | 中国科学院上海硅酸盐研究所 | Surface modification method for medical titanium metal material |
| CN104576305A (en) * | 2013-10-23 | 2015-04-29 | 中微半导体设备(上海)有限公司 | Self-cleaning vacuum treatment chamber |
| CN110180020B (en) * | 2019-05-29 | 2021-01-12 | 中国科学院上海硅酸盐研究所 | Nitrogen-doped titanium oxide coating and preparation method and application thereof |
| CN110180034B (en) * | 2019-05-29 | 2020-07-21 | 中国科学院上海硅酸盐研究所 | Reduced titanium oxide coating and preparation method and application thereof |
| CN111910155B (en) * | 2020-06-30 | 2022-05-31 | 北京航空航天大学合肥创新研究院 | Film material modification method and modified film material |
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| CN1611554A (en) * | 2003-10-28 | 2005-05-04 | 北京立高高新技术研究所 | Multifunctional coating and its preparing method |
| CN1651604A (en) * | 2005-01-07 | 2005-08-10 | 中国科学院上海硅酸盐研究所 | Method of preparing nano-titanium oxide coating layer having bioactivity |
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| CN1611554A (en) * | 2003-10-28 | 2005-05-04 | 北京立高高新技术研究所 | Multifunctional coating and its preparing method |
| CN1651604A (en) * | 2005-01-07 | 2005-08-10 | 中国科学院上海硅酸盐研究所 | Method of preparing nano-titanium oxide coating layer having bioactivity |
Non-Patent Citations (2)
| Title |
|---|
| BIOMIMETIC GROWTH OF APATITE ONHYDROGEN-IMPLANTED SILICON. LIU,XUANYONG ETAL.BIOMATERIALS,Vol.25 No.25. 2004 * |
| 离子溅射及其在工业上的应用. 左耀珠.电工电能新技术，第1期. 1982 * |
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