CN102181842A - Method for modifying titanium surface - Google Patents
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- CN102181842A CN102181842A CN 201110093356 CN201110093356A CN102181842A CN 102181842 A CN102181842 A CN 102181842A CN 201110093356 CN201110093356 CN 201110093356 CN 201110093356 A CN201110093356 A CN 201110093356A CN 102181842 A CN102181842 A CN 102181842A
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Abstract
The invention discloses a method for modifying titanium surface. The method comprises the following step of: performing tantalum ion implantation or plating on the titanium surface by using a plasma immersion ion implantation and deposition technology to obtain a tantalum and/or tantalum oxide modified layer. The titanium surface is modified, so that a high mechanical property of titanium can be preserved, the corrosion resistance and the bioactivity of a material can be improved, and high biocompatibility of the material can be kept; and the modified titanium surface which is subjected to tantalum ion implantation or plating is not required to be subjected to any aftertreatment, bone-like apatite can be induced to form and grow on the surface when the titanium surface is soaked in simulated body fluid, and an artificial bone substitutional material with high comprehensive performance can be obtained.
Description
Technical field
The present invention relates to a kind of method that surface of metal titanium is carried out modification, specifically, relate to a kind of method that plasma immersion ion injects and deposition technique carries out modification to surface of metal titanium of using, belong to the metal surface properties modification technical field.
Background technology
The bio-medical metallic substance is because its excellent mechanical property, easy processed-type and stability are obtaining application widely aspect osseous tissue and the joint reconstruction.The metallic substance of making implant at present comprises: 316L stainless steel, cochrome, titanium and alloy thereof etc., wherein titanium and alloy thereof obtain using the most widely owing to good mechanical property and biocompatibility.Yet metal implant material and device ubiquity do not have biological activity, combine clinical use problems such as not good with osseous tissue, this may cause implant to come off and the surrounding tissue necrosis.How making the metal implant biologically active, is the key of present bio-medical metal surface properties modification.
In order to improve the various performances of titanium and alloy thereof, can start with from two aspects: the one, set about from material body, as develop the new titanium alloy of various excellent performances; The 2nd, start with from material surface, adopt various surface treatment methods that titanium and alloy thereof are carried out surface modification, thereby make it be more suitable for requirement in medical use.Titanium and alloy thereof are carried out surface modification, both kept its a series of qualities, make its over-all properties obtain to improve significantly again as body material.In the reaction process of physiological environment and implant material, material surface plays important effect.Physiological environment can be made corresponding reaction to the implant with different surfaces feature, mainly contain the interaction of physiological systems such as material and cell, tissue, blood, internal secretion and immunity, and be affine to material or repel according to the results of interaction decision.Therefore, regulate and control the structure and the composition on implant material surface, can effectively improve the implantation effect of material.
Plasma immersion ion injects and deposition (Plasma immersion ion implantation and deposition, PIII﹠amp; D) technology is a kind of novel surface modification technology that begins to occur the beginning of the nineties in twentieth century, and it is to utilize high-octane ion implantation realization surface modification under room temperature or lesser temps.Compare with other process for modifying surface, plasma immersion ion injects and has unique advantage: ion implantation process is the thermal nonequilibrium process, is not subjected to the restriction of metallurgy rule, can be with among the acceleration of ions injecting material; Ion implantation process is a chilling process, can the atarting material internal structure, the variation of composition and outer shape; In addition, PIII﹠amp; The D technology has high reaction activity and omnibearing characteristics, can carry out uniform ion injection and deposition to heterotypic material effectively, be fit to have the injection process of the biomedical material of complicated shape, overcome the shortcoming that the conventional ion implantttion technique can only be carried out " sight line injection ".Metallic substance is carried out the ion implantation mechanical property that can improve material, as hardness, wear resistance, solidity to corrosion etc., all significant to the safety in utilization and the work-ing life of metal implant material.Simultaneously, by injecting the biological activity that some element can effectively improve metal implant material, also be the hot issue of technical field of biological material.Discovering in recent years adopted PIII﹠amp; The D technology is injected the biological activity and biocompatibility (the Surface ﹠amp that can significantly improve material as elements such as calcium, phosphorus and sodium to the surface of titanium and alloy thereof; Coatings Technology 2004,186 (1-2): 227-233.).But, because low, the high reaction activity of fusing point of materials such as calcium, phosphorus and sodium will obtain very difficulty of stable ion implantation modification technology.
Rare earth element tantalum (tantalum) lifeless matter toxicity, and have good fracture toughness property, erosion resistance and wear resisting property, therefore be used as the embedded material of plastic surgery and dentistry.The oxide skin that tantalum surface forms naturally makes it have biocompatibility and biological activity.There is the investigator to find, inject tantalum ion at titanium alloy surface, thereby the hardness that can increase titanium alloy surface improved wear resistance of titanium alloy (Rare Metal Materials and Engineering 2008,37 (3): 556-560.).
Summary of the invention
The present invention provides a kind of method that surface of metal titanium is carried out modification, to fill up the blank of prior art in order to solve the not difficult problem of biologically active of the titanium metal implant that exists in the prior art.
A kind of method that surface of metal titanium is carried out modification provided by the invention comprises the steps:
Use plasma immersion ion injection and deposition technique to carry out tantalum ion and inject or plated film, obtain to contain the modified layer of tantalum and/or tantalum pentoxide in surface of metal titanium.
Use plasma immersion ion injection and deposition technique when surface of metal titanium is carried out tantalum ion injection or plated film, the tantalum metal is a negative electrode.
The processing parameter that uses plasma immersion ion injection and deposition technique to carry out the tantalum ion injection in surface of metal titanium is: injecting voltage is 15～30kV, and pulse-repetition is 8Hz, and pulsewidth is 200～600 μ s, and injection length is 60～120 minutes; Preferred injection technology parameter is: injecting voltage is 30kV, and pulse-repetition is 8Hz, and pulsewidth is 450 μ s, and injection length is 60～120 minutes.
Use the processing parameter that plasma immersion ion injects and deposition technique carries out the tantalum ion plated film in surface of metal titanium to be: pulsed voltage is 450～550V, pulse-repetition is 7Hz, pulsewidth is 1000～4000 μ s, and dutycycle is 15%, and the plated film time is 60～120 minutes; Preferred coating process parameter is: pulsed voltage is 450V, and pulse-repetition is 7Hz, and pulsewidth is 2000 μ s, and dutycycle is 15%, and the plated film time is 60～120 minutes.
Use plasma immersion ion to inject and deposition technique while aerating oxygen when surface of metal titanium is carried out the tantalum ion plated film; The oxygen flow that feeds is recommended as 1～50 standard ml/min.
Above-mentioned titanium metal is the biomedical titanium metallic substance, refers to through the pretreated bio-medical titanium metal material of oxalic acid solution especially.
After modification of the present invention was handled, there was not tangible upper layer separation surface in the titanium surface, and the tantalum ion of injection/plated film is difficult for stripping, can solve the dissolving of traditional biological coating and peel off problem.Because titanium and tantalum atom size differ less than 8%, the unlimited solid solution of the β-Ti of tantalum and body-centered cubic structure, with the limited solid solution of the α-Ti of close-packed hexagonal structure, therefore between upper layer after modification of the present invention is handled and the titanium substrate very high bonding strength is arranged, especially tantalum injects sample, wherein the existence form of tantalum be the part solid solution in the titanium matrix, form the titanium tantalum alloy.In addition, the erosion resistance and the wear resisting property of tantalum and oxide compound thereof are very good, and can be arranged in vivo very long work-ing life.Limit major cause that the tantalum metal uses clinically before and be its density big, cost an arm and a leg and lack biological activity.Handle by modification of the present invention, form very thin tantalum and the oxide skin thereof of one deck, both can keep the good mechanical property of titanium metal, can improve the erosion resistance and the biological activity of material again, and can keep its excellent biological compatibility in surface of metal titanium.Therefore, adopt method of modifying of the present invention, will obtain a kind of artificial bone replacement material of high comprehensive performance.
Compared with prior art, the present invention has following beneficial effect:
1, the inventive method carries out that tantalum ion injects or there is not tangible upper layer separation surface in the surface of metal titanium of plated film, and the tantalum ion of injection or plated film is difficult for stripping, does not have the dissolving of coating and peels off problem; Both can keep the good mechanical property of titanium metal, and can improve the erosion resistance and the biological activity of material again, and can keep its excellent biological compatibility;
2, the tantalum ion that obtains after process modification of the present invention is handled injects or the surface of metal titanium of plated film need not to pass through any aftertreatment again, be immersed in and bring out formation and the growth of osteoid apatite in the simulated body fluid, can obtain a kind of artificial bone replacement material of high comprehensive performance on the surface.
Description of drawings
Fig. 1 is transmission electron microscope (TEM) photo of pretreated surface of metal titanium.
Fig. 2 a is the XPS collection of illustrative plates of the surface of metal titanium injected of the tantalum ion that obtains after modification of the present invention is handled.
Fig. 2 b is the XPS collection of illustrative plates of the surface of metal titanium of the tantalum ion plated film that obtains after modification of the present invention is handled.
Fig. 3 is the electrokinetic potential polarization curve of the titanium metal material that obtains after modification of the present invention is handled, and among the figure: 1 be pure titanium, 2 surface of metal titanium for the tantalum ion injection, and 3 is the surface of metal titanium of tantalum ion plated film, 4 is the surface of metal titanium of tantalum oxide plated film.
Fig. 4 a is that pretreated titanium metal material soaks the surface topography map after 28 days in simulated body fluid.
Fig. 4 b is the surface topography map of titanium metal material after simulated body fluid soaks 28 days that the tantalum ion that obtains after modification of the present invention is handled injects.
Fig. 4 c is the surface topography map the titanium metal material of the tantalum ion plated film through obtaining after the modification processing of the present invention soaks 28 days in simulated body fluid after.
Fig. 4 d is the surface topography map the titanium metal material of the tantalum oxide plated film through obtaining after the modification processing of the present invention soaks 28 days in simulated body fluid after.
Fig. 5 is the XRD figure spectrum the titanium metal material through obtaining after the modification processing of the present invention soaks 28 days in simulated body fluid after, among the figure: 1 surface of metal titanium for the tantalum ion injection, 2 is the surface of metal titanium of tantalum ion plated film, 3 is the surface of metal titanium of tantalum oxide plated film.
Specific implementation method
The present invention is described in further detail and completely below in conjunction with embodiment, but do not limit content of the present invention.
In 5% oxalic acid solution, 100 ℃ of pre-treatment 2 hours to be removing surperficial natural oxidizing layer with pure titanium, and obtain the clean surface with even roughness degree (seeing shown in Figure 1).
Adopt PIII﹠amp; The D technology is a negative electrode with the High-purity Tantalum metal, and tantalum ion is flow into pretreated medical titanium surface, obtains titanium tantalum surface alloy layer.Concrete injection parameter is shown in Table 1.The surperficial XPS collection of illustrative plates that obtains under this injection parameter sees that shown in Fig. 2 a, there is the existence of tantalum element on the show sample surface as a result.Scanning electron microscopic observation is found the surface topography no significant difference of tantalum before and after injecting, and reason may be that tantalum and titanium metal form alloy easily, and tantalum ion has certain energy in the injection process, can enter in the lattice of titanium metal and form sosoloid.
The titanium sample that tantalum ion injects is surveyed its electrokinetic potential polarization curve at physiological saline (0.9%NaCl solution), and wherein sample is a working electrode, and the utmost point and reference electrode are respectively Graphite Electrodes and saturated calomel electrode.Driven potential polarization curve can find out that than pure titanium surface, the corrosion potential generation forward that tantalum injects the rear surface moves (seeing shown in Figure 3).This explanation tantalum injects the erosion resistance of sample is enhanced.Scanning electron microscopic observation finds that also osteoid apatite can form on the titanium surface of injecting through tantalum, shown in Fig. 4 b; The result of XRD confirms that also the titanium surface that tantalum injects has phosphatic rock to generate after soaking simulated body fluid, as shown in Figure 5.Simultaneous test confirms that in simulated body fluid, osteoid apatite can not be only forming through pretreated pure titanium metal surface, shown in Fig. 4 a.This shows that tantalum injects erosion resistance and the biological activity that can improve the bio-medical titanium metal.
Table 1 tantalum injection parameter
| Injecting voltage | 30kV |
| Pulse-repetition | 8Hz |
| Pulsewidth | 450μs |
| Injection length | 90 minutes |
In 5% oxalic acid solution, 100 ℃ of pre-treatment 2 hours to be removing surperficial natural oxidizing layer with pure titanium, and obtain the clean surface with even roughness degree.
Adopt PIII﹠amp; The D technology is a negative electrode with the High-purity Tantalum metal, and the tantalum ion plated film in pretreated medical titanium surface, is obtained to have the nano level upper layer of tantalum and oxide compound thereof.Concrete filming parameter is shown in Table 2.The surperficial XPS collection of illustrative plates that obtains under this filming parameter sees shown in Fig. 2 b that the show sample outermost surface is tantalum and oxide compound thereof as a result.Scanning electron microscopic observation is found the surface topography no significant difference before and after the tantalum plated film, and reason may be that the tantalum film that obtains under this experiment condition is a Nano grade, is not enough to cover fully the micron projection on pre-treatment medical titanium surface.
Its electrokinetic potential polarization curve is surveyed on the titanium surface of tantalum plated film in physiological saline, found that than pure titanium surface, the corrosion potential of tantalum plated film rear surface produces forward and moves (seeing shown in Figure 3).This explanation tantalum plated film is enhanced the erosion resistance of sample, and is better than the sample that tantalum injects, and this is because tantalum is stronger than the passivation ability of titanium, the corrosion resistant oxide skin of easier formation.Scanning electron microscopic observation finds that osteoid apatite can form on the titanium surface through the tantalum plated film, shown in Fig. 4 c; The result of XRD has also confirmed the phosphatic rock generation, as shown in Figure 5.This shows that the tantalum plated film can improve the erosion resistance and the biological activity of bio-medical titanium metal.
Table 2 tantalum filming parameter
| Pulsed voltage | ?450V |
| Pulse-repetition | ?7Hz |
| Pulsewidth | ?2000μs |
| Dutycycle | ?15％ |
| The plated film time | 90 minutes |
Embodiment 3
In 5% oxalic acid solution, 100 ℃ of pre-treatment 2 hours to be removing surperficial natural oxidizing layer with pure titanium, and obtain the clean surface with even roughness degree.
Adopt PIII﹠amp; The D technology is a negative electrode with the High-purity Tantalum metal, and to the vacuum chamber aerating oxygen, the tantalum ion plated film in pretreated medical titanium surface, is obtained the nano level upper layer of tantalum oxide.Concrete tantalum oxide filming parameter is shown in Table 3.Scanning electron microscopic observation is found the surface topography no significant difference before and after the plated film, and reason may be that the tantalum-oxide film that obtains under this experiment condition is a Nano grade, is not enough to cover fully the micron projection on pre-treatment medical titanium surface.
Its electrokinetic potential polarization curve is surveyed on the titanium surface of tantalum oxide plated film in physiological saline, found that than pure titanium surface, the corrosion potential of tantalum oxide plated film rear surface produces forward and moves (seeing shown in Figure 3).This explanation tantalum oxide plated film is enhanced the erosion resistance of sample, and injects and the tantalum plated film be an optimum than tantalum, and this is the result of the corrosion resistance nature of tantalum oxide excellence.Scanning electron microscopic observation finds that osteoid apatite can form on the titanium surface through tantalum oxide tantalum plated film, shown in Fig. 4 d; The result of XRD has also confirmed the phosphatic rock generation, as shown in Figure 5.This shows that the tantalum oxide plated film can improve the erosion resistance and the biological activity of bio-medical titanium metal.
Table 3 tantalum oxide filming parameter
| Oxygen flow | ?50sccm* |
| Pulsed voltage | ?450V |
| Pulse-repetition | ?7Hz |
| Pulsewidth | ?2000μs |
| Dutycycle | ?15％ |
| The plated film time | 90 minutes |
* sccm: standard ml/min
Pretreated medical titanium metallic surface is biologically active not, through PIII﹠amp; The D technology carries out that the corrosion resistance nature and the biological activity of material all is improved behind the tantalum ion injection/film-coating modification.The major cause that corrosion resistance nature improves is that the metallic surface has formed fine and close oxide skin.The generation of tantalum oxide is the one of the main reasons that tantalum ion injection/plated film causes pure titanium corrosion resistance nature to improve.The tantalum ratio is easier to passivation, and tantalum ion injection/plated film has improved the passivation ability of pure titanium, and the oxide compound kind on pure titanium surface is more after the modification, contains the different valence state oxide compound of tantalum and titanium, more helps forming stable and fine and close surface passivation rete.On the other hand, the titanium surface after tantalum ion injects has generated corrosion-resistant titanium tantalum alloy layer, thereby improves the corrosion resistance nature of material.The pure titanium surface of bioactivity research discovery tantalum ion injection/film-coating modification all can induce hydroxyapatite to generate biologically active at the simulated body fluid environment.Reason may be that the tantalum/tantalum oxide of sample surfaces in the simulated body fluid environment can form tantalum hydroxyl (Ta-OH), and the tantalum hydroxyl has good biological activity according to the literature.On the other hand, there are some researches show that good wettability and high surface energy can promote bioactive raising.Contact angle test shows, the pure titanium surface contact angle of the relative primary of pure titanium of tantalum ion injection/film-coating modification all are and reduce trend, and surface wettability improves.
In sum, handle by modification of the present invention, form very thin tantalum and the oxide skin thereof of one deck, both can keep the good mechanical property of titanium metal in surface of metal titanium, the erosion resistance and the biological activity of material can be improved again, and its excellent biological compatibility can be kept.Therefore, adopt method of modifying of the present invention, will obtain a kind of artificial bone replacement material of high comprehensive performance.
Claims (10)
1. the method that surface of metal titanium is carried out modification is characterized in that: use plasma immersion ion injection and deposition technique to carry out tantalum ion in surface of metal titanium and inject or plated film, obtain to contain the modified layer of tantalum and/or tantalum pentoxide.
2. a kind of method that surface of metal titanium is carried out modification according to claim 1 is characterized in that: use plasma immersion ion injection and deposition technique when surface of metal titanium is carried out tantalum ion injection or plated film, the tantalum metal is a negative electrode.
3. a kind of method of surface of metal titanium being carried out modification according to claim 1, it is characterized in that, the processing parameter that uses plasma immersion ion injection and deposition technique to carry out the tantalum ion injection in surface of metal titanium is: injecting voltage is 15～30kV, pulse-repetition is 8Hz, pulsewidth is 200～600 μ s, and injection length is 60～120 minutes.
4. a kind of method that surface of metal titanium is carried out modification according to claim 3 is characterized in that, described injection technology parameter is: injecting voltage is 30kV, and pulse-repetition is 8Hz, and pulsewidth is 450 μ s, and injection length is 60～120 minutes.
5. a kind of method of surface of metal titanium being carried out modification according to claim 1, it is characterized in that, use the processing parameter that plasma immersion ion injects and deposition technique carries out the tantalum ion plated film in surface of metal titanium to be: pulsed voltage is 450～550V, pulse-repetition is 7Hz, pulsewidth is 1000～4000 μ s, dutycycle is 15%, and the plated film time is 60～120 minutes.
6. a kind of method that surface of metal titanium is carried out modification according to claim 5 is characterized in that, described coating process parameter is: pulsed voltage is 450V, pulse-repetition is 7Hz, pulsewidth is 2000 μ s, and dutycycle is 15%, and the plated film time is 60～120 minutes.
7. according to claim 5 or 6 described a kind of methods that surface of metal titanium is carried out modification, it is characterized in that: while aerating oxygen when carrying out the tantalum plated film.
8. a kind of method that surface of metal titanium is carried out modification according to claim 7 is characterized in that: the oxygen flow of feeding is 1～50 standard ml/min.
9. a kind of method that surface of metal titanium is carried out modification according to claim 1 is characterized in that: described titanium metal is the biomedical titanium metallic substance.
10. a kind of method that surface of metal titanium is carried out modification according to claim 9 is characterized in that: described bio-medical titanium metal material is through the pretreated material of oxalic acid solution.
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| CN106435430A (en) * | 2016-12-13 | 2017-02-22 | 江西省科学院应用物理研究所 | Method for anti-oxygenic property of improving thermal spraying MCrAlY coating |
| CN106691609A (en) * | 2016-11-24 | 2017-05-24 | 北京华钽生物科技开发有限公司 | High-tissue-affinity corrosion-resisting implant tooth and manufacturing method thereof |
| CN106945382A (en) * | 2017-02-22 | 2017-07-14 | 华中科技大学 | A kind of preparation method of titanium/tantalum composite plate and products thereof |
| CN107708650A (en) * | 2015-07-13 | 2018-02-16 | 三仪股份有限公司 | Dental surface film formation powder comprising the apatite through burning till |
| RU2650221C1 (en) * | 2017-03-03 | 2018-04-11 | Федеральное государственное бюджетное образовательное учреждение высшего образования "Саратовский государственный технический университет имени Гагарина Ю.А." (СГТУ имени Гагарина Ю.А.) | Method for formation nanostructured oxide coating on technical titanium |
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| CN113073303A (en) * | 2021-03-26 | 2021-07-06 | 南京工程学院 | Biomedical pure magnesium surface functional structured ion implantation modified layer and preparation method and application thereof |
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| CN107708650A (en) * | 2015-07-13 | 2018-02-16 | 三仪股份有限公司 | Dental surface film formation powder comprising the apatite through burning till |
| CN106691609A (en) * | 2016-11-24 | 2017-05-24 | 北京华钽生物科技开发有限公司 | High-tissue-affinity corrosion-resisting implant tooth and manufacturing method thereof |
| CN106691609B (en) * | 2016-11-24 | 2022-04-15 | 北京华钽生物科技开发有限公司 | High-affinity tissue corrosion-resistant implant and manufacturing method thereof |
| CN106435430B (en) * | 2016-12-13 | 2019-02-05 | 江西省科学院应用物理研究所 | A method of improving thermal spraying MCrAlY coating antioxygenic property |
| CN106435430A (en) * | 2016-12-13 | 2017-02-22 | 江西省科学院应用物理研究所 | Method for anti-oxygenic property of improving thermal spraying MCrAlY coating |
| CN106945382B (en) * | 2017-02-22 | 2018-12-25 | 华中科技大学 | A kind of preparation method and products thereof of titanium/tantalum composite plate |
| CN106945382A (en) * | 2017-02-22 | 2017-07-14 | 华中科技大学 | A kind of preparation method of titanium/tantalum composite plate and products thereof |
| RU2650221C1 (en) * | 2017-03-03 | 2018-04-11 | Федеральное государственное бюджетное образовательное учреждение высшего образования "Саратовский государственный технический университет имени Гагарина Ю.А." (СГТУ имени Гагарина Ю.А.) | Method for formation nanostructured oxide coating on technical titanium |
| CN110230026A (en) * | 2019-06-26 | 2019-09-13 | 西安交通大学 | A method of improving niobium alloy surface oxidation-resistant ability |
| CN113073303A (en) * | 2021-03-26 | 2021-07-06 | 南京工程学院 | Biomedical pure magnesium surface functional structured ion implantation modified layer and preparation method and application thereof |
| CN113073303B (en) * | 2021-03-26 | 2021-11-16 | 南京工程学院 | Biomedical pure magnesium surface functional structured ion implantation modified layer and preparation method and application thereof |
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Application publication date: 20110914 |