CN102425000A - Method for preparing biologically active titanium dioxide film on NiTi alloy surface - Google Patents
Method for preparing biologically active titanium dioxide film on NiTi alloy surface Download PDFInfo
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- CN102425000A CN102425000A CN2011103878211A CN201110387821A CN102425000A CN 102425000 A CN102425000 A CN 102425000A CN 2011103878211 A CN2011103878211 A CN 2011103878211A CN 201110387821 A CN201110387821 A CN 201110387821A CN 102425000 A CN102425000 A CN 102425000A
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Abstract
The invention relates to a method for preparing a biologically active titanium dioxide film on a NiTi alloy surface, relating to a method for modification of a medical NiTi alloy surface and solving the technical problems of harsh conditions for micro-arc oxidation of the NiTi alloy with concentrated phosphoric acid as electrolyte in the prior art. In the method for preparing the biologically active titanium dioxide film on the NiTi alloy surface, concentrated sulfuric acid with the mass concentration being 98 percent is used as electrolyte, NiTi alloy is used as an anode, and a stainless steel tank is used as a cathode for micro-arc oxidation to obtained the biologically active titanium dioxide film on the NiTi alloy surface, or alkali treatment is carried out after micro-arc oxidation. By adopting the method, the titanium oxide film with a nanoscale porous structure and good biocompatibility can be prepared on the NiTi alloy surface, and the film and a substrate have high bonding strength of more than 45MPa. Moreover, the method is simple and can be used in clinical areas such as orthopedic surgery, department of stomatology, cardiovascular department, gynecology and the like.
Description
Technical field
The present invention relates to the medical NiTi alloy surface modifying method, particularly relate to its surface biological activatory method.
Background technology
NiTi shape memory alloy (SMA) has unique SME and super-elasticity, excellent biological compatibility, solidity to corrosion and mechanical property; It is a kind of ideal bio-medical material; Be widely used in biomedical materials field, be applied to clinical fields such as orthopedics, Stomatological Department, cardiology department, gynaecology at present.Compare with other medical metal materials; The Young's modulus of NiTi shape memory alloy and human body hard tissue are the most approaching; This advantage has improved the mechanical compatibility of it and skeleton; Can alleviate the stress-shielding effect of traditional metal materials after implantation, avoid causing skeleton bulking and implant obscission, the comfort level behind the raising corrective surgery.But the NiTi alloy itself is a kind of bio-inert material, behind the implant into body, is difficult to form synostosis with tissue, does not have bone conductibility.Therefore, how to improve the erosion resistance of NiTi alloy, realize surface bioactiveization, improve an urgent demand that medical biological safety of NiTi alloy and consistency are its clinical application.
Bioactive film kind in the preparation of NiTi alloy surface is a lot of at present, wherein modal CaP film and the titanium dioxide film of comprising.Contained Ca, the P composition of CaP rete is easy to take place degraded and absorbs in the human body environment, the physical strength of itself is relatively poor in addition, and the bonding force between rete and the matrix is not strong, comes off easily behind the implant into body.Titanium oxide has good anti-corrosion and blood compatibility, in the human body environment stability better and have a good biological activity, the thin film of titanium oxide that therefore prepares biologically active at the NiTi alloy surface becomes one of optimal method of the present NiTi of improvement alloy surface biological activity.The method for preparing thin film of titanium oxide at the NiTi alloy surface has technology such as galvanic deposit, laser coating, sol-gel, chemical treatment and thermooxidizing; But aforesaid method all exists weak point separately, and is relatively poor such as the bonding force of technological rete for preparing such as sol-gel, galvanic deposit and matrix.The rete of technology such as chemical treatment, thermooxidizing preparation is thinner, and is not corrosion-resistant behind the long-term implant into body.
The differential arc oxidation method be a kind of in the metallic surface technology of growth in situ ceramic membrane; Can form metallurgical binding between the rete of this technology preparation and the matrix; Has very high bonding strength; The rete of preparation itself has vesicular structure in addition, is specially adapted to the surface treatment of medical embedded material, has been widely used in the surface-treated of medical titanium or titanium alloy at present.Contain a large amount of nickel in the NiTi alloy; The category that does not belong to valve metal; Therefore the electrolyte system that is fit to NiTi alloy differential arc oxidation only has several kinds, and studying carefully more at present is in the aluminate electrolyte system, the NiTi alloy to be carried out differential arc oxidation Processing of Preparation aluminum oxide rete.But the biological activity of aluminum oxide is not as titanium oxide.And prepare titanium oxide layer at the NiTi alloy surface is a difficult point.At Preparation and properties of titanium oxide film on NiTi alloy by micro-arcoxidation (Applied Surface Science; 257 (2011); To be electrolytic solution carry out the method for differential arc oxidation to the NiTi alloy to disclosed employing SPA 5576-5580), and this method at first SPA will be passed through freezing treatment, secondly in treating processes; Electrolyte temperature will continue to remain on low-temperature condition, and condition is very harsh; Adopting SPA simultaneously is that electrolytic solution is when carrying out differential arc oxidation to the NiTi alloy; The differential arc oxidation initial stage; Can the NiTi alloy surface need form one deck decision differential arc oxidation through anodic oxidation realize passive film smoothly; Early stage, the formation of passive film will be experienced a very growth process, in the treatment time that has prolonged greatly, therefore was unfavorable for large-scale industrial application.
Summary of the invention
The present invention be to solve existing with SPA do electrolytic solution to the NiTi alloy with the harsh technical problem of differential arc oxidation law part, and the preparation method of NiTi alloy surface biological activity titanium oxide layer is provided.
The preparation method of NiTi alloy surface biological activity titanium oxide layer of the present invention carries out according to the following steps: with mass concentration is that 98% the vitriol oil is an electrolytic solution; With the NiTi alloy is that positive pole, stainless steel tank are negative pole, is that 0 ℃~10 ℃, current density are 1A/dm at electrolyte temperature
2~20A/dm
2, voltage is differential arc oxidation 2min~10min under the condition of 50V~70V, obtains NiTi alloy surface biological activity titanium oxide layer.
The preparation method of NiTi alloy surface biological activity titanium oxide layer of the present invention can also carry out according to the following steps: with mass concentration is that 98% the vitriol oil is an electrolytic solution; With the NiTi alloy is that positive pole, stainless steel tank are negative pole, is that 0 ℃~10 ℃, current density are 1A/dm at electrolyte temperature
2~20A/dm
2, voltage is differential arc oxidation 2min~10min under the condition of 50V~70V; NiTi alloy after again differential arc oxidation being handled is immersed in sodium hydroxide solution immersion 5h~10h that concentration is 0.5mol/L~2.5mol/L, obtains NiTi alloy surface biological activity titanium oxide layer.
The present invention has through employing that to cause the inactive vitriol oil by force be that electrolytic solution carries out differential arc oxidation to the NiTi alloy; The preparatory passivation layer that utilizes the vitriol oil to form at the NiTi alloy surface; This is the essential condition that can decision later stage spark discharge realize; Also be the prerequisite that can the decision differential arc oxidation be realized smoothly, simplified greatly the NiTi alloy is carried out the technology that differential arc oxidation prepares titanium oxide layer.Titanium oxide layer has better biocompatibility, and rete has nano level vesicular structure in addition, can induce Win 40350 to deposit at surperficial forming core, improves the biological activity of NiTi alloy.The NiTi alloy that process this method is handled is behind implant into body, and NiTi alloy embedded material can directly form synostosis with people's bone, shortens the time of operation healing greatly, alleviates patient's misery, has enlarged the range of application of medical NiTi alloy.In addition, this rete and matrix have higher binding strength greater than 45MPa, can satisfy requirements for clinical application.
Description of drawings
Fig. 1 is the stereoscan photograph of the NiTi alloy surface bioactive film of test one preparation;
Fig. 2 is that the NiTi alloy surface bioactive film of test one preparation soaks the stereoscan photograph after 28 days in simulated body fluid;
Fig. 3 is that the NiTi alloy surface bioactive film of test one preparation soaks the X-ray diffraction spectrogram after 28 days in simulated body fluid.
Fig. 4 is that the NiTi alloy surface bioactive film of test one preparation soaks the stereoscan photograph after 14 days in simulated body fluid.
Embodiment
Embodiment one: the preparation method of the NiTi alloy surface biological activity titanium oxide layer of this embodiment carries out according to the following steps: with mass concentration is that 98% the vitriol oil is an electrolytic solution; With the NiTi alloy is that positive pole, stainless steel tank are negative pole, is that 0 ℃~10 ℃, current density are 1A/dm at electrolyte temperature
2~20A/dm
2, voltage is differential arc oxidation 2min~10min under the condition of 50V~70V, obtains NiTi alloy surface biological activity titanium oxide layer.
This embodiment has through employing that to cause the inactive vitriol oil by force be that electrolytic solution carries out differential arc oxidation to the NiTi alloy; The preparatory passivation layer that utilizes the vitriol oil to form at the NiTi alloy surface; This is the essential condition that can decision later stage spark discharge realize; Also be the prerequisite that can the decision differential arc oxidation be realized smoothly, simplified greatly the NiTi alloy is carried out the technology that differential arc oxidation prepares titanium oxide layer.Titanium oxide layer has better biocompatibility, and rete has nano level vesicular structure in addition, can induce Win 40350 to deposit at surperficial forming core, improves the biological activity of NiTi alloy.The NiTi alloy that process this method is handled is behind implant into body, and NiTi alloy embedded material can directly form synostosis with people's bone, shortens the time of operation healing greatly, alleviates patient's misery, has enlarged the range of application of medical NiTi alloy.In addition, this rete and matrix have higher binding strength greater than 45MPa, can satisfy requirements for clinical application.
Embodiment two: this embodiment and embodiment one are different is to be that positive pole, stainless steel tank are negative pole with the NiTi alloy, is that 2 ℃~8 ℃, current density are 5A/dm at electrolyte temperature
2~18A/dm
2, voltage is differential arc oxidation 3min~8min under the condition of 55V~65V.Other is identical with embodiment one.
Embodiment three: this embodiment and embodiment one are different is to be that positive pole, stainless steel tank are negative pole with the NiTi alloy, is that 4 ℃, current density are 12A/dm at electrolyte temperature
2, voltage is differential arc oxidation 6min under the condition of 60V.Other is identical with embodiment one.
Embodiment four: the preparation method of the NiTi alloy surface biological activity titanium oxide layer of this embodiment carries out according to the following steps: with mass concentration is that 98% the vitriol oil is an electrolytic solution; With the NiTi alloy is that positive pole, stainless steel tank are negative pole, is that 0 ℃~10 ℃, current density are 1A/dm at electrolyte temperature
2~20A/dm
2, voltage is differential arc oxidation 2min~10min under the condition of 50V~70V; NiTi alloy after again differential arc oxidation being handled is immersed in sodium hydroxide solution immersion 5h~10h that concentration is 0.5mol/L~2.5mol/L.Obtain NiTi alloy surface biological activity titanium oxide layer.
In this embodiment, the NiTi alloy after differential arc oxidation is handled passes through alkali treatment again, can form a large amount of Ti-OH groups at film surface, further improves the ability that rete induces Win 40350 to generate, thereby improves the biological activity of rete greatly.
Embodiment five: this embodiment and embodiment four are different is to be that positive pole, stainless steel tank are negative pole with the NiTi alloy, is that 2 ℃~8 ℃, current density are 5A/dm at electrolyte temperature
2~18A/dm
2, voltage is differential arc oxidation 3min~8min under the condition of 55V~65V.Other is identical with embodiment four.
Embodiment six: this embodiment is different with embodiment four or five is to be that positive pole, stainless steel tank are negative pole with the NiTi alloy, is that 4 ℃, current density are 12A/dm at electrolyte temperature
2, voltage is differential arc oxidation 6min under the condition of 60V.Other is identical with embodiment four or five.
Embodiment seven: what this embodiment was different with one of embodiment four to six is: the NiTi alloy after differential arc oxidation is handled is immersed in sodium hydroxide solution immersion 5h~10h that concentration is 0.5mol/L~2.5mol/L.Other is identical with one of embodiment four to six.
Embodiment eight: what this embodiment was different with one of embodiment four to seven is: the NiTi alloy after differential arc oxidation is handled is immersed in the sodium hydroxide solution immersion 8h that concentration is 1.5mol/L.Other is identical with one of embodiment four to seven.
The present invention adopts following verification experimental verification beneficial effect of the present invention:
Test one: the preparation method of the NiTi alloy surface bioactive film of this test one carries out according to the following steps: with mass concentration is that 98% vitriol oil is an electrolytic solution; With the NiTi alloy is that positive pole, stainless steel tank are negative pole, is that 10 ℃, current density are 10A/dm at electrolyte temperature
2, voltage is differential arc oxidation 5min under the condition of 60V, obtains NiTi alloy surface biological activity titanium oxide layer.
NiTi alloy in this test one is specially medical NiTi alloy, and wherein the atomic percent of Ni is 50.8at.%, and the atomic percent of Ti is 49.2at.%.
The stereoscan photograph of the NiTi alloy surface biological activity titanium oxide layer of this test one preparation is as shown in Figure 1, and as can beappreciated from fig. 1 rete has the porous pattern, and the aperture is between 100nm~300nm.
The NiTi alloy surface biological activity titanium oxide layer of test one preparation is placed in the simulated body fluid soaked 28 days; Every other day change simulated body fluid one time; It is as shown in Figure 2 to soak after 28 days the stereoscan photograph of NiTi alloy surface bioactive film, and as can beappreciated from fig. 2 film surface has been induced a large amount of spherical settling of generation to cover.
The X-ray diffraction spectrogram that soaks NiTi alloy surface biological activity titanium oxide layer after 28 days is as shown in Figure 3; In the collection of illustrative plates of Fig. 3 ◆ be the diffraction peak of Win 40350; ■ is the diffraction peak of NiTi alloy substrate; Do not have its their diffraction peak, hence one can see that induces the settling of generation to be mainly Win 40350.
The preparatory passivation layer that this test utilizes the vitriol oil to form at the NiTi alloy surface; Make the NiTi alloy carry out differential arc oxidation smoothly; And condition is content with very little, and simple, obtains the nanometer porous oxidation titanium film with better biocompatibility; Can induce Win 40350 to deposit, improve the biological activity of NiTi alloy at surperficial forming core.
The rete and the high base strength of this test preparation are 48.2MPa, and bonding strength is high, can satisfy requirements for clinical application.
Test two: the preparation method of the NiTi alloy surface bioactive film of this test can also carry out according to the following steps: with mass concentration is that 98% the vitriol oil is an electrolytic solution; With the NiTi alloy is that positive pole, stainless steel tank are negative pole, is that 8 ℃, current density are 15A/dm at electrolyte temperature
2, voltage is differential arc oxidation 8min under the condition of 58V, and then the NiTi alloy after handling differential arc oxidation to be immersed in concentration be that the sodium hydroxide solution of 2mol/L soaks 10h, obtain NiTi alloy surface biological activity titanium oxide layer.
The stereoscan photograph that the NiTi alloy surface biological activity titanium oxide layer of this test preparation soaked in simulated body fluid after 14 days is as shown in Figure 4; As can be seen from Figure 4 only 14 days film surfaces have been induced a large amount of settling of generation to cover; Compare with the rete before the alkaline purification, the rete biological activity after the alkaline purification improves greatly.
The preparatory passivation layer that this test utilizes the vitriol oil to form at the NiTi alloy surface; Make the NiTi alloy carry out differential arc oxidation smoothly, and condition is content with very little, and simple; Carry out alkaline purification behind the differential arc oxidation again; Obtain nanometer porous oxidation titanium film, can induce Win 40350 to deposit, improve the biological activity of NiTi alloy at surperficial forming core with better biocompatibility.
The rete and the high base strength of this test preparation are 47.6MPa, and bonding strength is high, can satisfy requirements for clinical application.
Claims (8)
1.NiTi the preparation method of alloy surface biological activity titanium oxide layer; The preparation method who it is characterized in that NiTi alloy surface biological activity titanium oxide layer carries out according to the following steps: with mass concentration is that 98% the vitriol oil is an electrolytic solution; With the NiTi alloy is that positive pole, stainless steel tank are negative pole, is that 0 ℃~10 ℃, current density are 1A/dm at electrolyte temperature
2~20A/dm
2, voltage is differential arc oxidation 2min~10min under the condition of 50V~70V, obtains NiTi alloy surface biological activity titanium oxide layer.
2. the preparation method of NiTi alloy surface biological activity titanium oxide layer according to claim 1 is characterized in that with the NiTi alloy being that positive pole, stainless steel tank are negative pole, is that 2 ℃~8 ℃, current density are 5A/dm at electrolyte temperature
2~18A/dm
2, voltage is differential arc oxidation 3min~8min under the condition of 55V~65V.
3. the preparation method of NiTi alloy surface biological activity titanium oxide layer according to claim 1 is characterized in that with the NiTi alloy being that positive pole, stainless steel tank are negative pole, is that 4 ℃, current density are 12A/dm at electrolyte temperature
2, voltage is differential arc oxidation 6min under the condition of 60V.
4.NiTi the preparation method of alloy surface biological activity titanium oxide layer; The preparation method who it is characterized in that NiTi alloy surface biological activity titanium oxide layer carries out according to the following steps: with mass concentration is that 98% the vitriol oil is an electrolytic solution; With the NiTi alloy is that positive pole, stainless steel tank are negative pole, is that 0 ℃~10 ℃, current density are 1A/dm at electrolyte temperature
2~20A/dm
2, voltage is differential arc oxidation 2min~10min under the condition of 50V~70V; NiTi alloy after again differential arc oxidation being handled is immersed in sodium hydroxide solution immersion 5h~10h that concentration is 0.5mol/L~2.5mol/L, obtains NiTi alloy surface biological activity titanium oxide layer.
5. the preparation method of NiTi alloy surface biological activity titanium oxide layer according to claim 4 is characterized in that with the NiTi alloy being that positive pole, stainless steel tank are negative pole, is that 2 ℃~8 ℃, current density are 5A/dm at electrolyte temperature
2~18A/dm
2, voltage is differential arc oxidation 3min~8min under the condition of 55V~65V.
6. the preparation method of NiTi alloy surface biological activity titanium oxide layer according to claim 4 is characterized in that with the NiTi alloy being that positive pole, stainless steel tank are negative pole, is that 4 ℃, current density are 12A/dm at electrolyte temperature
2, voltage is differential arc oxidation 6min under the condition of 60V.
7. according to the preparation method of claim 4,5 or 6 described NiTi alloy surface biological activity titanium oxide layers, it is characterized in that the NiTi alloy after the differential arc oxidation processing is immersed in sodium hydroxide solution immersion 5h~10h that concentration is 0.5mol/L~2.5mol/L.
8. according to the preparation method of claim 4,5 or 6 described NiTi alloy surface biological activity titanium oxide layers, it is characterized in that the NiTi alloy after the differential arc oxidation processing is immersed in the sodium hydroxide solution immersion 8h that concentration is 1.5mol/L.
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CN104309055B (en) * | 2013-10-31 | 2018-03-27 | 比亚迪股份有限公司 | The manufacture method and metal-resin composite of metal-resin composite |
EP3391915A3 (en) * | 2017-03-30 | 2019-01-02 | Biomet Manufacturing, LLC | Methods of modifying the porous surface of implants |
EP3636294A1 (en) | 2018-10-08 | 2020-04-15 | Jozef Stefan Institute | Method for treatment medical devices made from nickel - titanium (niti) alloys |
CN113368315A (en) * | 2021-06-09 | 2021-09-10 | 河北工业大学 | Medical nickel-titanium alloy material with temperature-sensitive hydrogel coating and preparation method and application thereof |
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CN104309055B (en) * | 2013-10-31 | 2018-03-27 | 比亚迪股份有限公司 | The manufacture method and metal-resin composite of metal-resin composite |
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CN113368315A (en) * | 2021-06-09 | 2021-09-10 | 河北工业大学 | Medical nickel-titanium alloy material with temperature-sensitive hydrogel coating and preparation method and application thereof |
CN113368315B (en) * | 2021-06-09 | 2022-04-19 | 河北工业大学 | Medical nickel-titanium alloy material with temperature-sensitive hydrogel coating and preparation method and application thereof |
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