CN101497988A - Method for plating tantalum on TiNi alloy surface - Google Patents
Method for plating tantalum on TiNi alloy surface Download PDFInfo
- Publication number
- CN101497988A CN101497988A CNA2009100713493A CN200910071349A CN101497988A CN 101497988 A CN101497988 A CN 101497988A CN A2009100713493 A CNA2009100713493 A CN A2009100713493A CN 200910071349 A CN200910071349 A CN 200910071349A CN 101497988 A CN101497988 A CN 101497988A
- Authority
- CN
- China
- Prior art keywords
- tini alloy
- tantalum
- alloy surface
- tini
- surface plating
- Prior art date
- 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.)
- Pending
Links
Images
Landscapes
- Physical Vapour Deposition (AREA)
Abstract
The invention relates to a method for plating tantalum on the surface of TiNi alloy. The method solves the problem that the corrosion resistance property is poor when the TiNi alloy is implanted into the human body for a long time. The method comprises the follow steps: firstly, the TiNi alloy is mechanically polished, ultrasonically cleaned and dried; secondly, the sputter cleaning is carried out; thirdly, tantalum ions are used for bombarding the TiNi alloy which is then deposited and cooled to room temperature; and fourthly, the tantalum-plated TiNi alloy is just obtained after vacuum annealing. The tantalum-plated TiNi alloy prepared by the method has good corrosion resistance property, restricts Ni ions from dissolving out simultaneously and improves the biocompatibility. The invention has simple production process and convenient operation.
Description
Technical field
The present invention relates to a kind of method of alloy surface plating tantalum.
Background technology
The TiNi alloy is because of having excellent shape memory and superelastic properties, and good solidity to corrosion and biocompatibility obtain to use widely at biomedical sector, and prospect is very wide.One of medical use that the TiNi alloy has development potentiality most is an angiocarpy bracket, and the TiNi alloy bracket is easily realized self-expanding and permanent resilient support, and it is simple, easily fixing to have an operation, advantage such as posts, reactive force is even with vessel wall.The corrosive nature of biomaterial and biocompatibility depend primarily on the surface property of material.Why the TiNi alloy has preferably, and erosion resistance and biocompatibility are because the spontaneous TiO that forms one deck densification in its surface
2Passive film, but the oxide thickness of this spontaneous formation is thin, only about 2～20nm, and be easy to come off.Behind the long-term implant into body of TiNi alloy; the local corrosion of passivation layer can take place under this complex environment of blood of human body; and the process of its healing is very slow; thereby behind the long-term implant into body of TiNi alloy bracket; easily there are inflammation, teratogenesis and carcinogenic potentially dangerous because of the stripping of Ni ion; how to improve corrosion resistance, it is the research emphasis and the development trend of TiNi alloy biomedical applications that maximum amplitude reduces the stripping of Ni ion.
Summary of the invention
The present invention seeks to plant the problem of corrosion resistance difference in human body for a long time, and provide a kind of TiNi alloy surface to plate the method for tantalum in order to have solved existing TiNi alloy.
The method of TiNi alloy surface plating tantalum realizes according to the following steps: one, with the mechanical polishing of TiNi alloy, put into acetone ultrasonic cleaning 20～60min again, dry up then; Two, the TiNi alloy after drying up is put into the multi-arc ion plating film machine, and being evacuated to multi-arc ion plating film machine pressure is 10
-4～10
-5Pa, feeding argon gas to furnace pressure again is 0.2～0.3Pa, adds the negative bias of 800～1100V at the TiNi alloy, carries out sputter clean, reaches 300～400 ℃ to the TiNi alloy; Three, be that 70～80A, negative bias are that the TiNi alloy of handling through step 2 with the tantalum ion bombardment under the condition of 100～500V also deposits at arc stream, depositing time is 30～160min, is cooled to room temperature then; Four, vacuum annealing 30～90min under 800～1000 ℃ of conditions promptly gets the TiNi alloy that plates tantalum.
The TiNi alloy of the plating tantalum that the inventive method makes soaked in the simulated body fluid of 0.9%NaCl after 49 days, and the Ni ion amount of separating out of the TiNi alloy of plating tantalum is 0.28 μ gcm
-2, do not plate that the Ni ionic amount of separating out is 8.4 μ gcm in the TiNi alloy of tantalum
-2With the TiNi alloy phase ratio that does not plate tantalum, the TiNi alloy Ni ion amount of separating out of plating tantalum has descended 30 times, shows that the plating tantalum can effectively suppress the Ni ion and separate out, and improves the biocompatibility of TiNi alloy.
Description of drawings
Fig. 1 is being plunderred the X ray diffracting spectrum of angle when being 1 ° for a short time for embodiment 36 step 3 make product; Fig. 2 is being plunderred the X ray diffracting spectrum of angle when being 3 ° for a short time for embodiment 36 step 3 make product; Fig. 3 is being plunderred the X ray diffracting spectrum of angle when being 5 ° for a short time for embodiment 36 step 3 make product; Fig. 4 makes the X ray diffracting spectrum of product for embodiment 36; Fig. 5 makes the plating tantalum TiNi alloy layer scratch test figure of product for embodiment 36; Fig. 6 does not plate the circulation electrokinetic potential anodic polarization curves of the TiNi alloy of tantalum for prior art; Fig. 7 makes the circulation electrokinetic potential anodic polarization curves of product for embodiment 36; Fig. 8 for the Ni ion amount of separating out with the soak time change curve, among the figure-the Ni ion amount of separating out of TiNi alloy that ■-expression prior art is not plated tantalum is with the soak time change curve ,-●-expression embodiment 36 makes the Ni ion amount of separating out of product with the soak time change curve.
Embodiment
Technical solution of the present invention is not limited to following cited embodiment, also comprises the arbitrary combination between each embodiment.
Embodiment one: the method for present embodiment TiNi alloy surface plating tantalum realizes according to the following steps: one, with the mechanical polishing of TiNi alloy, put into acetone ultrasonic cleaning 20～60min again, dry up then; Two, the TiNi alloy after drying up is put into the multi-arc ion plating film machine, and being evacuated to multi-arc ion plating film machine pressure is 10
-4～10
-5Pa, feeding argon gas to furnace pressure again is 0.2～0.3Pa, adds the negative bias of 800～1100V at the TiNi alloy, carries out sputter clean, reaches 300～400 ℃ to the TiNi alloy; Three, be that 70～80A, negative bias are that the TiNi alloy of handling through step 2 with the tantalum ion bombardment under the condition of 100～500V also deposits at arc stream, depositing time is 30～160min, is cooled to room temperature then; Four, vacuum annealing 30～90min under 800～1000 ℃ of conditions promptly gets the TiNi alloy that plates tantalum.
Embodiment two: that present embodiment and embodiment one are different is ultrasonic cleaning 30～50min in the step 1.Other is identical with embodiment one.
Embodiment three: that present embodiment and embodiment one are different is ultrasonic cleaning 40min in the step 1.Other is identical with embodiment one.
Embodiment four: that present embodiment and embodiment one are different is ultrasonic cleaning 20min in the step 1.Other is identical with embodiment one.
Embodiment five: that present embodiment and embodiment one are different is ultrasonic cleaning 60min in the step 1.Other is identical with embodiment one.
Embodiment six: what present embodiment was different with embodiment one or two is to be evacuated to 10-5Pa in the step 2.Other is identical with embodiment one or two.
Embodiment seven: what present embodiment was different with embodiment one or two is to be evacuated to 10-in the step 2
4Pa.Other is identical with embodiment one or two.
Embodiment eight: what present embodiment was different with embodiment one or two is to be evacuated to 5 * 10 in the step 2
-4Pa.Other is identical with embodiment one or two.
Embodiment nine: what present embodiment and embodiment six were different is to feed argon gas to 0.25Pa in step 2.Other is identical with embodiment six.
Embodiment ten: what present embodiment and embodiment six were different is to feed argon gas to 0.2Pa in step 2.Other is identical with embodiment six.
Embodiment 11: what present embodiment and embodiment six were different is to feed argon gas to 0.3Pa in step 2.Other is identical with embodiment six.
Embodiment 12: what present embodiment and embodiment one, two or nine were different is the negative bias that adds 900～1000V in the step 2 at the TiNi alloy.Other is identical with embodiment one, two or nine.
Embodiment 13: what present embodiment and embodiment one, two or nine were different is the negative bias that adds 1100V in the step 2 at the TiNi alloy.Other is identical with embodiment one, two or nine.
Embodiment 14: what present embodiment and embodiment one, two or nine were different is the negative bias that adds 950V in the step 2 at the TiNi alloy.Other is identical with embodiment one, two or nine.
Embodiment 15: what present embodiment and embodiment one, two or nine were different is the negative bias that adds 800V in the step 2 at the TiNi alloy.Other is identical with embodiment one, two or nine.
Embodiment 16: present embodiment and embodiment 12 are different is to reach 320～380 ℃ to the TiNi alloy in the step 2.Other is identical with embodiment 12.
Embodiment 17: present embodiment and embodiment 12 are different is to reach 350 ℃ to the TiNi alloy in the step 2.Other is identical with embodiment 12.
Embodiment 18: present embodiment and embodiment 12 are different is to reach 300 ℃ to the TiNi alloy in the step 2.Other is identical with embodiment 12.
Embodiment 19: present embodiment and embodiment 12 are different is to reach 400 ℃ to the TiNi alloy in the step 2.Other is identical with embodiment 12.
Embodiment 20: what present embodiment and embodiment one, two, nine or 16 were different is that negative bias is 200～400V in the step 3.Other is identical with embodiment one, two, nine or 16.
Embodiment 21: what present embodiment and embodiment one, two, nine or 16 were different is that negative bias is 300V in the step 3.Other is identical with embodiment one, two, nine or 16.
Embodiment 22: what present embodiment and embodiment one, two, nine or 16 were different is that negative bias is 100V in the step 3.Other is identical with embodiment one, two, nine or 16.
Embodiment 23: what present embodiment and embodiment one, two, nine or 16 were different is that negative bias is 500V in the step 3.Other is identical with embodiment one, two, nine or 16.
Embodiment 24: what present embodiment and embodiment 20 were different is that depositing time is 50～150min in the step 3.Other is identical with embodiment 20.
Embodiment 25: what present embodiment and embodiment 20 were different is that depositing time is 100min in the step 3.Other is identical with embodiment 20.
Embodiment 26: what present embodiment and embodiment 20 were different is that depositing time is 30min in the step 3.Other is identical with embodiment 20.
Embodiment 27: what present embodiment and embodiment 20 were different is that depositing time is 160min in the step 3.Other is identical with embodiment 20.
Embodiment 28: what present embodiment and embodiment one, two, nine, 16 or 24 were different is that vacuum annealing temperature is 850～950 ℃ in the step 4.Other is identical with embodiment one, two, nine, 16 or 24.
Embodiment 29: present embodiment and embodiment one, two, nine, 16 or 24 are different be in the step 4 in the step 4 vacuum annealing temperature be 800 ℃.Other is identical with embodiment one, two, nine, 16 or 24.
Embodiment 30: present embodiment and embodiment one, two, nine, 16 or 24 are different be in the step 4 in the step 4 vacuum annealing temperature be 1000 ℃.Other is identical with embodiment one, two, nine, 16 or 24.
The embodiment hentriaconta-: present embodiment and embodiment one, two, nine, 16 or 24 are different be in the step 4 in the step 4 vacuum annealing temperature be 900 ℃.Other is identical with embodiment one, two, nine, 16 or 24.
Embodiment 32: present embodiment and embodiment 28 are different be in the step 4 vacuum annealing time be 40～80min.Other is identical with embodiment 28.
Embodiment 33: present embodiment and embodiment 28 are different be in the step 4 vacuum annealing time be 30min.Other is identical with embodiment 28.
Embodiment 34: present embodiment and embodiment 28 are different be in the step 4 vacuum annealing time be 90min.Other is identical with embodiment 28.
Embodiment 35: present embodiment and embodiment 28 are different be in the step 4 vacuum annealing time be 60min.Other is identical with embodiment 28.
Embodiment 36: the method for present embodiment TiNi alloy surface plating tantalum realizes according to the following steps: one, with the mechanical polishing of TiNi alloy, put into acetone ultrasonic cleaning 20min again, dry up then; Two, the TiNi alloy after drying up is put into the multi-arc ion plating film machine, and being evacuated to furnace pressure is 10
-5Pa, feeding argon gas to furnace pressure again is 0.25Pa, adds the negative bias of 1100V at the TiNi alloy, carries out sputter clean, reaches 350 ℃ to the TiNi alloy; Three, be that 75A, negative bias are that the TiNi alloy of handling through step 2 with the tantalum ion bombardment under the condition of 300V also deposits at arc stream, depositing time is 100min, is cooled to room temperature then; Four, vacuum annealing 60min under 900 ℃ of conditions promptly gets the TiNi alloy that plates tantalum.
The present embodiment step 3 makes product and is plunderring the X ray diffracting spectrum of angle when being 1 ° for a short time as shown in Figure 1, as can be seen from Figure 1 the product that makes of present embodiment step 3 ° located to occur broad in 2 θ=42 and the very weak peak of intensity, illustrate that tantalum coating top layer is a non-crystalline state; The present embodiment step 3 makes product and is plunderring the X ray diffracting spectrum of angle when being 3 ° for a short time as shown in Figure 2, the present embodiment step 3 makes product and is plunderring the X ray diffracting spectrum of angle when being 5 ° for a short time as shown in Figure 3, from Fig. 1, Fig. 2 and Fig. 3 as can be seen the product that makes of present embodiment step 3 along with the increase of plunderring the angle for a short time, also promptly institute's coating degree of depth that penetrates increases, (212) corresponding to β-Ta have appearred, (111) and (510) diffraction peak, and these diffraction peaks grow becomes sharp with the increase of grazing angle, this shows that adopt that multi-arc ion coating obtains on the TiNi alloy is the β-Ta of amorphous.
The X ray diffracting spectrum that present embodiment makes product as shown in Figure 4, the diffraction peak of representative α-Ta and TiNi alloy has only appearred in the X ray diffracting spectrum of the product that makes of present embodiment as can be seen from Figure 4, the diffraction peak of β-Ta phase does not occur, show annealed processing, the sedimentary β of TiNi alloy surface-Ta fundamental transformation is α-Ta, the thermostability of α-Ta and chemical stability all are better than β-Ta, and that form at the TiNi alloy surface is β-Ta.Adopt suitable thermal treatment to make β-Ta change α-Ta into, help improving coating performance.
The plating tantalum TiNi alloy layer scratch test figure that present embodiment makes product as shown in Figure 5, the critical load value that do not obtain in adding load scope of the product that makes of present embodiment shows that coating and matrix bond are good as can be seen from Figure 5.
Prior art do not plate tantalum the TiNi alloy circulation electrokinetic potential anodic polarization curves as shown in Figure 6, the circulation electrokinetic potential anodic polarization curves that present embodiment makes product as shown in Figure 7, the circulation electrokinetic potential anodic polarization curves that does not plate the TiNi alloy of tantalum as can be seen from Figures 6 and 7 has bigger flyback hysteresis loop, the hysteresis loop that present embodiment makes product disappears substantially, the reverse scanning curve overlaps substantially with the forward scan curve, illustrate that pitting attack has taken place the TiNi alloy surface that does not plate tantalum, and the self-reparing capability of passive film is relatively poor, and present embodiment makes product not origination point corrosion in the simulated body fluid of 0.9%NaCl, even because physical abuse has been destroyed the oxide film of plating tantalum surface, this oxide film also can be very fast be repaired voluntarily, and promptly present embodiment makes product and has good anti-pitting attack performance.
The Ni ion amount of separating out with the soak time change curve as shown in Figure 8, do not plate of the increase of the TiNi alloy of tantalum as can be seen from Figure 8 along with soak time, the Ni ionic amount of separating out increases when beginning to some extent, change very little in time through the amount of separating out behind the certain hour, soak after 49 days in the simulated body fluid of 0.9%NaCl, the Ni ion amount of separating out that present embodiment makes product is 0.28 μ gcm
-2, do not plate that the Ni ionic amount of separating out is 8.4 μ gcm in the TiNi alloy of tantalum
-2With the TiNi alloy phase ratio that does not plate tantalum, the Ni ion amount of separating out that present embodiment makes product has descended 30 times, shows that the plating tantalum can effectively suppress the Ni ion and separate out, and improves the biocompatibility of TiNi alloy.
Claims (10)
1, the method for TiNi alloy surface plating tantalum is characterized in that the method for TiNi alloy surface plating tantalum realizes according to the following steps: one, with the mechanical polishing of TiNi alloy, put into acetone ultrasonic cleaning 20～60min again, dry up then; Two, the TiNi alloy after drying up is put into the multi-arc ion plating film machine, and being evacuated to multi-arc ion plating film machine pressure is 10
-4～10
-5Pa, feeding argon gas to furnace pressure again is 0.2～0.3Pa, adds the negative bias of 800～1100V at the TiNi alloy, carries out sputter clean, reaches 300～400 ℃ to the TiNi alloy; Three, be that 70～80A, negative bias are that the TiNi alloy of handling through step 2 with the tantalum ion bombardment under the condition of 100～500V also deposits at arc stream, depositing time is 30～160min, is cooled to room temperature then; Four, vacuum annealing 30～90min under 800～1000 ℃ of conditions promptly gets the TiNi alloy that plates tantalum.
2, the method for TiNi alloy surface plating tantalum according to claim 1 is characterized in that ultrasonic cleaning 30～50min in the step 1.
3, the method for TiNi alloy surface plating tantalum according to claim 1 and 2 is characterized in that being evacuated to 10 in the step 2
-5Pa.
4, the method for TiNi alloy surface plating tantalum according to claim 3 is characterized in that feeding in the step 2 argon gas to 0.25Pa.
5,, it is characterized in that adding at the TiNi alloy in the step 2 negative bias of 900～1000V according to the method for claim 1,2 or 4 described TiNi alloy surface plating tantalums.
6, the method for TiNi alloy surface according to claim 5 plating tantalum is characterized in that in the step 2 reaching 320～380 ℃ to the TiNi alloy.
7, according to the method for claim 1,2,4 or 6 described TiNi alloy surface plating tantalums, it is characterized in that negative bias is 200～400V in the step 3.
8, the method for TiNi alloy surface plating tantalum according to claim 7 is characterized in that depositing time is 50～150min in the step 3.
9, according to the method for claim 1,2,4,6 or 8 described TiNi alloy surface plating tantalums, it is characterized in that vacuum annealing temperature is 850～950 ℃ in the step 4.
10, the method for TiNi alloy surface plating tantalum according to claim 9 is characterized in that the vacuum annealing time is 40～80min in the step 4.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2009100713493A CN101497988A (en) | 2009-01-24 | 2009-01-24 | Method for plating tantalum on TiNi alloy surface |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2009100713493A CN101497988A (en) | 2009-01-24 | 2009-01-24 | Method for plating tantalum on TiNi alloy surface |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101497988A true CN101497988A (en) | 2009-08-05 |
Family
ID=40945257
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2009100713493A Pending CN101497988A (en) | 2009-01-24 | 2009-01-24 | Method for plating tantalum on TiNi alloy surface |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101497988A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102828157A (en) * | 2012-07-30 | 2012-12-19 | 北京航空航天大学 | Method for conducting surface modification on medical titanium nickel (TiNi) shape memory alloys through niobium (Nb) ion injection deposition |
| CN103014414A (en) * | 2013-01-04 | 2013-04-03 | 哈尔滨工程大学 | TiNi-base shape memory alloy containing components in graded distribution and preparation method thereof |
| CN104630730A (en) * | 2015-02-17 | 2015-05-20 | 哈尔滨工程大学 | Surface modification method of NiTi alloy martensitic root canal file |
| CN114012179A (en) * | 2021-10-19 | 2022-02-08 | 浙江骏业工具有限公司 | High-strength heat-resistant chip removal titanium film saw blade and processing technology thereof |
-
2009
- 2009-01-24 CN CNA2009100713493A patent/CN101497988A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102828157A (en) * | 2012-07-30 | 2012-12-19 | 北京航空航天大学 | Method for conducting surface modification on medical titanium nickel (TiNi) shape memory alloys through niobium (Nb) ion injection deposition |
| CN103014414A (en) * | 2013-01-04 | 2013-04-03 | 哈尔滨工程大学 | TiNi-base shape memory alloy containing components in graded distribution and preparation method thereof |
| CN103014414B (en) * | 2013-01-04 | 2014-08-20 | 哈尔滨工程大学 | TiNi-base shape memory alloy containing components in graded distribution and preparation method thereof |
| CN104630730A (en) * | 2015-02-17 | 2015-05-20 | 哈尔滨工程大学 | Surface modification method of NiTi alloy martensitic root canal file |
| CN114012179A (en) * | 2021-10-19 | 2022-02-08 | 浙江骏业工具有限公司 | High-strength heat-resistant chip removal titanium film saw blade and processing technology thereof |
| CN114012179B (en) * | 2021-10-19 | 2024-03-05 | 浙江骏业工具有限公司 | High-strength heat-resistant chip removal titanium film saw blade and processing technology thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103556148B (en) | A kind of surface modifying method of NiTi shape memory alloy | |
| CN101962769B (en) | Method for preparing hydrophobic film on surface of material | |
| CN101532122B (en) | Method for preparing diamond-like coating on surface of biological medical NiTi alloy | |
| CN101497988A (en) | Method for plating tantalum on TiNi alloy surface | |
| CN102618829B (en) | Medical magnesium alloy material with amorphous film and preparation method thereof | |
| Fang et al. | Enhanced adhesion and anticorrosion of silk fibroin coated biodegradable Mg-Zn-Ca alloy via a two-step plasma activation | |
| CN103031523B (en) | The preparation method of the cupric compound coating on a kind of metal parts of medicine equipment and medicine equipment | |
| CN104862649B (en) | A kind of preparation method of titanium alloy surface gradient Ni/TiN composite modified layers | |
| CN111441025B (en) | Corrosion-resistant high-entropy alloy film, preparation method and application thereof in seawater environment | |
| CN105925949A (en) | Method for preparing micro-nano porous structure on titanium or titanium alloy surface | |
| CN103924202A (en) | Metal support surface modification method | |
| Shanaghi et al. | Enhancement of mechanical properties and corrosion resistance of NiTi alloy by carbon plasma immersion ion implantation | |
| CN111926289B (en) | Preparation method of tantalum coating | |
| CN106756847A (en) | A kind of preparation method of witch culture DLC film | |
| CN109234784A (en) | A kind of preparation method of medical magnesium alloy composite material | |
| Wan et al. | Corrosion properties of oxygen plasma immersion ion implantation treated magnesium | |
| CN112522673B (en) | Biomedical magnesium alloy surface rare earth composite film and preparation method thereof | |
| CN103603026B (en) | A kind of method taken off completely except workpiece surface diamond-like carbon film | |
| CN108930023B (en) | Method for preparing tantalum biological coating on surface of magnesium alloy through magnetron sputtering | |
| CN103911593A (en) | Preparation method of titanium alloy surface Ag-doped TiO2 thin film | |
| CN106544628A (en) | A kind of preparation method containing deuterium foil target | |
| US8512859B2 (en) | Housing and method for making the same | |
| CN107881469A (en) | Diamond-like composite coating and preparation method thereof and purposes and coated tool | |
| JP2022092454A (en) | Blood compatibility medical titanium material, and production method of blood compatibility medical titanium material | |
| CN101230445A (en) | Method for improving developobility of TiNi alloy bracket under X-ray |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Open date: 20090805 |