CN105132880A - Method for modifying surface of titanium metal material and modified titanium metal material - Google Patents
Method for modifying surface of titanium metal material and modified titanium metal material Download PDFInfo
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- CN105132880A CN105132880A CN201510605289.4A CN201510605289A CN105132880A CN 105132880 A CN105132880 A CN 105132880A CN 201510605289 A CN201510605289 A CN 201510605289A CN 105132880 A CN105132880 A CN 105132880A
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Abstract
The invention provides a method for modifying the surface of a titanium metal material and a modified titanium metal material. According to the method, a plasma immersion ion implantation technique is adopted, and silver ions and nitrogen ions are implanted into the surface of the titanium metal material together to improve the biological activity of the medical titanium metal material. The silver ions exist in a nano form, titanium nitride is formed by nitrogen and titanium, and the antibacterial property of the titanium metal material is improved obviously through the synergistic effect between the silver ions and the titanium nitride, so that the titanium metal material has a good antibacterial ability to escherichia coli and staphylococcus aureus with antibacterial rates up to 100% and 99% respectively, and the requirements of antibacterial property, mechanical property and corrosion resistance property of the medical titanium metal material can be met.
Description
Technical field
The invention belongs to medical material tech field, be specifically related to the titanium metal material of a kind of method that surface modification is carried out to titanium metal material and the modification obtained.
Background technology
Surface modification (Surfacemodification) refers to and processes the surface of material and a kind of technology that its performance is changed, as carburizing (or nitriding), shot-peening, laser treatment, ion implantation, top coat method, anodic oxidation, chemical vapour deposition, physical vapor deposition etc.Wherein, plasma immersion and ion implantation (PIII) technology is the process for modifying surface that is a kind of novel, cheap, non-line-of-sight grown up in the last few years.This technology is by direct for workpiece to be implanted submergence in the plasma, and a series of negative potential pulse is applied relative to vacuum-chamber wall on workpiece, at this moment, just around workpiece, form a plasma sheath constantly expanded/bounce back, electronics at the flows by action of plasma sheath current potential to vacuum-chamber wall, and ion is under the effect of plasma sheath current potential, is accelerated from all directions and is injected into the surface of workpiece, thus realizing the surface modification of material.PIII technology has larger advantage to abnormal workpieces process and batch processing, and this technology has been widely used in the surface modification of the materials such as metal, pottery, semi-conductor and polymkeric substance now.
Titanium or titanium alloy is because having good mechanical property and biocompatibility and being widely used as the embedded material of orthopaedics and dentistry.But Long-term clinical is followed the tracks of and fundamental research finds, the biological activity of titanium or titanium alloy implantation material surface is still not ideal enough, causes implant Integrated implant ability more weak, is combined not strong with surrounding tissue.How to improve the biological activity of medical titanium metal material, improve the Integrated implant ability of implant, become one of focus of embedded material research.
Zinc, as one of required trace element of body vital movement, plays an important role to the hundreds of protein structure of maintenance and function.Zinc participates in various kinds of cell process in cell, such as DNA synthesis, enzymic activity and cell fission (TheJournalofNutrition2000,130:1500-1508.) etc.Research shows, zinc can reach by improving cell proliferation, alkaline phosphatase activities and collagen protein synthesis the effect (NutritionResearchandPractice2010,4:356-361.) promoting skeletonization.Therefore, zine ion Implanted Titanium and alloy surface thereof significantly can improve the biological activity (ActaBiomaterialia2010,6:962-968) of embedded material, thus promote propagation, the differentiation of cell.But the effect of zine ion to cell is mainly manifested in cell and material interactional later stage, the interaction (such as adhere to and sprawl) of cell in early days and between material is poor, need to improve.
Magnesium, as the important element of needed by human, is the cofactor of hundreds of enzyme system.To bioprocess such as protein synthesis, nucleotide metabolism that body weight for humans is wanted, there is positive effect.Magnesium is in cell growth process; be not only cell and energy support is provided; promote protein synthesis; and can promote cell proliferation and can have obvious promoter action to cell Attachment with sprawling, cell growth process is carried out positive protection and is prevented various influence factor to the damage of cell.Research shows, magnesium ion has vital role (Int.J.OralMaxillofac.Implants2005,20:349-359.) to bone remodeling.Magnesium ion injected bio-medical surface of metal titanium by ion implantation technique and can promote that cell is in the early stage response (Biomaterials2006,7:1728-1734.) of implant surfaces, improves the biological activity of embedded material.But magnesium ion is not very desirable to cell and the interaction in material later stage.
Patent CN104726836A discloses the titanium metal material of a kind of method of carrying out surface modification to titanium metal material and the modification obtained, and its method is that zine ion and magnesium ion are injected into titanium metal material surface thus improve the biological activity of medical titanium metal material by using plasma immersion ion implantttion technique altogether.Although this invention makes the corrosion resistance nature of titanium metal material be improved, its anti-microbial property is unsatisfactory.
Summary of the invention
For the problem that the anti-microbial property of Modified Titanium metallic substance in prior art is undesirable, the invention provides a kind of method of titanium metal material being carried out to surface modification newly, method of the present invention is that silver ions and Nitrogen ion are injected into titanium metal material surface by using plasma immersion ion implantttion technique altogether, obtain the titanium metal material of the modification of the silver-colored nitrogen of common note, thus the anti-microbial property of medical titanium metal material can be improved.
First aspect, the invention provides a kind of method of titanium metal material being carried out to surface modification, and silver ions and Nitrogen ion are injected into titanium metal material surface by using plasma immersion ion implantttion technique altogether.
Wherein, described common injection refers to that the silver cathode of excitation pulse simultaneously vacuum arc plasma source carries out plasma immersion and ion implantation.
In the present invention, silver ions exists with nano shape, and nitrogen then forms titanium nitride with titanium, and the two synergy not only improves the anti-microbial property of titanium metal material significantly, further improves corrosion resistance and the hardness of titanium metal material.
In the present invention, the processing parameter of described plasma immersion ion implantation technique is preferably: vacuum chamber temperature is 40 ~ 50 DEG C, and background vacuum is 3 × 10
-3~ 4 × 10
-3pa, injecting voltage is-10 ~-40kV, and frequency is 5 ~ 9Hz, and pulsewidth is 50 ~ 450 μ s, and nitrogen flow is 10 ~ 20sccm, and injection length is 0.5 ~ 2.0h altogether.
Wherein, vacuum chamber temperature can be 40 DEG C, 42 DEG C, 44 DEG C, 46 DEG C, 48 DEG C or 50 DEG C etc.; Nitrogen flow can be 10sccm, 12sccm, 14sccm, 16sccm, 18sccm or 20sccm etc.; Injection length can be 0.5h, 1h, 1.5h or 2h etc. altogether.
In the present invention, described zinc negative electrode is preferably fine silver negative electrode.
In the present invention, described titanium metal material be pure titanium as the pure titanium after sandblasting acid treatment, or titanium alloy.
Another object of the present invention is to the titanium metal material of the modification providing a kind of method of the present invention to obtain, wherein, the titanium metal material surface of described modification is injected with silver ions and Nitrogen ion simultaneously, and namely titanium metal material of the present invention is the titanium metal material of the silver-colored nitrogen modification of common note.
The titanium metal material of described modification be pure titanium as the pure titanium after sandblasting acid treatment, or titanium alloy.
Positive progressive effect of the present invention is: the present invention adopts PIII technology silver ions and Nitrogen ion to be injected into altogether titanium metal material surface to carry out surface modification and obtain the titanium metal material of modification, wherein silver ions exists with nano shape, nitrogen then forms titanium nitride with titanium, the two synergy improves the anti-microbial property of titanium metal material significantly, to intestinal bacteria and streptococcus aureus, all there is good antibacterial ability, its antibiotic rate can reach 100% and 99% respectively, the germ resistance needed for medical titanium metal material can be met, the requirement of mechanical property and corrosion resistance nature.
Embodiment
Embodiment 1
The pure titanium sheet of 10mm × 10mm × 1mm will be of a size of through nitration mixture (HF:HNO
3: H
2o=1:5:4, volume ratio) clean 10min after, use alcohol, deionized water and ultrapure water ultrasonic cleaning clean successively, clean 10 ~ 20min, seasoning is stand-by at every turn.Using plasma immersion ion injects (PIII) technology and silver and Nitrogen ion is injected into altogether pure titanium surface, and its processing parameter is: vacuum chamber temperature is 45 DEG C, and background vacuum is 3 × 10
-3~ 4 × 10
-3pa, injecting voltage is 30kV, and frequency is 7Hz, and pulsewidth is 50 ~ 450 μ s, and nitrogen flow is 15sccm, and injection length is 1h altogether.
The titanium metal material of obtained surface modification all has good antibacterial ability to intestinal bacteria and streptococcus aureus, and its antibiotic rate can reach 100% and 99.6% respectively.
Embodiment 2:
The pure titanium sheet of 10mm × 10mm × 1mm will be of a size of through nitration mixture (HF:HNO
3: H
2o=1:5:4, volume ratio) clean 10min after, use alcohol, deionized water and ultrapure water ultrasonic cleaning clean successively, clean 10 ~ 20min, seasoning is stand-by at every turn.Using plasma immersion ion injects (PIII) technology and silver and Nitrogen ion is injected into altogether pure titanium surface, and its processing parameter is: vacuum chamber temperature is 40 DEG C, and background vacuum is 3 × 10
-3~ 4 × 10
-3pa, injecting voltage is 10kV, and frequency is 9Hz, and pulsewidth is 50 ~ 450 μ s, and nitrogen flow is 20sccm, and injection length is 2h altogether.
The titanium metal material of obtained surface modification all has good antibacterial ability to intestinal bacteria and streptococcus aureus, and its antibiotic rate can reach 100% and 99.3% respectively.
Embodiment 3:
The pure titanium sheet of 10mm × 10mm × 1mm will be of a size of through nitration mixture (HF:HNO
3: H
2o=1:5:4, volume ratio) clean 10min after, use alcohol, deionized water and ultrapure water ultrasonic cleaning clean successively, clean 10 ~ 20min, seasoning is stand-by at every turn.Using plasma immersion ion injects (PIII) technology and silver and Nitrogen ion is injected into altogether pure titanium surface, and its processing parameter is: vacuum chamber temperature is 50 DEG C, and background vacuum is 3 × 10
-3~ 4 × 10
-3pa, injecting voltage is 40kV, and frequency is 5Hz, and pulsewidth is 50 ~ 450 μ s, and nitrogen flow is 10sccm, and injection length is 0.5h altogether.
The titanium metal material of obtained surface modification all has good antibacterial ability to intestinal bacteria and streptococcus aureus, and its antibiotic rate can reach 100% and 99.5% respectively.
Comparative example 1:
Embodiment 1 in patent CN104726836A, the antibiotic rate of titanium metal material to intestinal bacteria and streptococcus aureus of obtained surface modification is respectively 85% and 79%.
Comparative example 2:
Using plasma immersion ion implantttion technique is only surperficial to titanium metal material by silver ion implantation, and the antibiotic rate of titanium metal material to intestinal bacteria and streptococcus aureus of obtained surface modification is respectively 81% and 80%
Comparative example 3:
Using plasma immersion ion implantttion technique is only surperficial to titanium metal material by N~+ implantation, and the antibiotic rate of titanium metal material to intestinal bacteria and streptococcus aureus of obtained surface modification is respectively 75% and 71%
The result of integrated embodiment 1-3 and comparative example 1-3 can be found out, the present invention adopts PIII technology silver ions and Nitrogen ion to be injected into altogether titanium metal material surface to carry out surface modification and obtain the titanium metal material of common note zinc-magnesium modification, ion exists with nano shape, nitrogen then forms titanium nitride with titanium, the two synergy not only improves the anti-microbial property of titanium metal material significantly, to intestinal bacteria and streptococcus aureus, all there is good antibacterial ability, its antibiotic rate can reach 100% and 99% respectively, the germ resistance needed for medical titanium metal material can be met, the requirement of mechanical property and corrosion resistance nature.
Claims (7)
1. titanium metal material is carried out to a method for surface modification, it is characterized in that, silver ions and Nitrogen ion are injected into titanium metal material surface by using plasma immersion ion implantttion technique altogether.
2. the method for claim 1, is characterized in that, described common injection refers to that the silver cathode of excitation pulse simultaneously vacuum arc plasma source carries out plasma immersion and ion implantation.
3. method as claimed in claim 1 or 2, it is characterized in that: the processing parameter of described plasma immersion ion implantation technique is: vacuum chamber temperature is 40 ~ 50 DEG C, background vacuum is 3 × 10
-3~ 4 × 10
-3pa, injecting voltage is 10 ~ 40kV, and frequency is 5 ~ 9Hz, and pulsewidth is 50 ~ 450 μ s, and nitrogen flow is 10 ~ 20sccm, and injection length is 0.5 ~ 2.0h altogether.
4. method as claimed in claim 2, is characterized in that: described silver cathode is fine silver negative electrode.
5. the method as described in any one of claim 1-4, is characterized in that: described titanium metal material is pure titanium or titanium alloy.
6. a titanium metal material for the modification that the method described in any one of claim 1-5 obtains, is characterized in that, the titanium metal material surface of described modification is injected with silver ions and Nitrogen ion altogether.
7. the material as described in any one of claim 1-6, the titanium metal material of described modification is pure titanium or titanium alloy.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106175996A (en) * | 2016-06-30 | 2016-12-07 | 天津医科大学 | Surface has Invasive lumbar fusion device and the preparation method that rich silver nanoparticle multilayer film is modified |
| CN107773782A (en) * | 2016-08-24 | 2018-03-09 | 上海双申医疗器械股份有限公司 | It is a kind of to put forward high purity titanium and the method for titanium alloy surface cytocompatibility and biocidal property |
| CN108062001A (en) * | 2018-01-02 | 2018-05-22 | 京东方科技集团股份有限公司 | The patterning method of film layer, wire grating polarization structure and preparation method thereof |
| CN108385074A (en) * | 2018-03-22 | 2018-08-10 | 深圳大学 | A kind of nitrogen method for implanting and its modified cutter, mold |
| CN109023343A (en) * | 2018-07-07 | 2018-12-18 | 中国矿业大学 | A kind of processing method of medical titanium alloy antibacterial surface biological coating |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20080131479A1 (en) * | 2006-08-02 | 2008-06-05 | Jan Weber | Endoprosthesis with three-dimensional disintegration control |
| CN102191454A (en) * | 2011-04-26 | 2011-09-21 | 中国科学院上海硅酸盐研究所 | Surface modification method for medical titanium metal material |
| CN103526175A (en) * | 2013-11-06 | 2014-01-22 | 武汉科技大学 | Antibacterial hard stainless steel tool and preparation method thereof |
-
2015
- 2015-09-21 CN CN201510605289.4A patent/CN105132880A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20080131479A1 (en) * | 2006-08-02 | 2008-06-05 | Jan Weber | Endoprosthesis with three-dimensional disintegration control |
| CN102191454A (en) * | 2011-04-26 | 2011-09-21 | 中国科学院上海硅酸盐研究所 | Surface modification method for medical titanium metal material |
| CN103526175A (en) * | 2013-11-06 | 2014-01-22 | 武汉科技大学 | Antibacterial hard stainless steel tool and preparation method thereof |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106175996A (en) * | 2016-06-30 | 2016-12-07 | 天津医科大学 | Surface has Invasive lumbar fusion device and the preparation method that rich silver nanoparticle multilayer film is modified |
| CN107773782A (en) * | 2016-08-24 | 2018-03-09 | 上海双申医疗器械股份有限公司 | It is a kind of to put forward high purity titanium and the method for titanium alloy surface cytocompatibility and biocidal property |
| CN108062001A (en) * | 2018-01-02 | 2018-05-22 | 京东方科技集团股份有限公司 | The patterning method of film layer, wire grating polarization structure and preparation method thereof |
| CN108385074A (en) * | 2018-03-22 | 2018-08-10 | 深圳大学 | A kind of nitrogen method for implanting and its modified cutter, mold |
| CN109023343A (en) * | 2018-07-07 | 2018-12-18 | 中国矿业大学 | A kind of processing method of medical titanium alloy antibacterial surface biological coating |
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Application publication date: 20151209 |