CN103877618B - A kind of method preparing argentiferous titanium deoxid film in medical titanium or titanium alloy surface - Google Patents
A kind of method preparing argentiferous titanium deoxid film in medical titanium or titanium alloy surface Download PDFInfo
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- CN103877618B CN103877618B CN201410102541.5A CN201410102541A CN103877618B CN 103877618 B CN103877618 B CN 103877618B CN 201410102541 A CN201410102541 A CN 201410102541A CN 103877618 B CN103877618 B CN 103877618B
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Abstract
The invention provides a kind of method preparing argentiferous titanium deoxid film in medical titanium or titanium alloy surface, comprise the steps: 1) adopt 180 ~ No. 1200 sand paper to polish step by step medical titanium or titanium alloy, then use deionized water, dehydrated alcohol, acetone ultrasonic cleaning respectively, dry; 2) silver nitrate solution is added in the liner of water heating kettle, then liner is put into water heating kettle, then titanium or titanium alloy sample are put into water heating kettle, make titanium or titanium alloy sample remain on below liquid level of solution, setting reaction temperature is 150-200 DEG C, and the response time is 16-24h; 3) question response terminates, and after water heating kettle temperature is down to room temperature, takes out water heating kettle, after the product washing in water heating kettle, drier, namely obtain argentiferous titanium deoxid film in medical titanium or titanium alloy surface.The advantages such as the present invention has that simple process, treatment temperature are low, with low cost, clean environment firendly, practical, the surface modification that can be used for porous titanium material.
Description
[technical field]
The invention belongs to biomedical materials field, be specifically related to a kind of method preparing argentiferous titanium deoxid film in medical titanium or titanium alloy surface.
[background technology]
In medical metal material, titanium and its alloys, because having the price of excellent corrosion resistance, intensity, toughness and relative moderate, is widely used in sclerous tissues's implants such as manufacturing bone fishplate bar, artificial joint, Dental Implant.But the elastic modelling quantity (about 110GPa) of titanium is much higher than biological bone (1-30GPa), and titanium implants can cause " stress shielding " phenomenon, is unfavorable for the healing of osseous tissue.The approach reducing the elastic modelling quantity of titanium has two: one to be alloying, develop the beta type or nearly beta Type Titanium Alloy that have compared with low elastic modulus, the such as TLM titanium alloy (Ti-25Nb-3Zr-2Sn-3Mo) of Xibei Inst. of Non-Ferrous Metals exploitation, elastic modelling quantity can be reduced to about 60GPa; Two is porous process, and void size about tens is to hundreds of micron, and make the elastic modelling quantity of POROUS TITANIUM or porous titanium alloy more close to biological bone, loose structure is also conducive to implant and osseous tissue forms firmly interface cohesion.
In order to improve biocompatibility and the synosteosis performance of titanium or titanium alloy, need to carry out surface modification to it.Adopt physics or chemistry, electrochemical method at coating or thin film such as titanium or titanium alloy surface-coated or growth in situ calcium phosphate, diamond like carbon, titanium dioxide, the surface propertys such as the corrosion resistance of titanium or titanium alloy, biocompatibility, wearability can be improved, obtain better bone and implant effect.Wherein, coating of titanium dioxide or thin film are proved to be has excellent corrosion resistance and biocompatibility, and has the characteristics such as photocatalysis, photic hydrophilic, antibiotic property.
Surgical implant, antibacterial can cause infection in the adhesion of material surface and breeding, and the antibacterial boundary layer of formation directly affects the success or failure of implant surgery.The method solving implant infection problems applies argentiferous, the antimicrobial coating of cupric and load antibacterials molecule at implant surfaces.Silver is considered to a kind of effective anti-biotic material for a long time, and it has the antibacterial activity of wide spectrum and has lower toxicity to cell.Silver is also for improving the anti-microbial property of coating of titanium dioxide or thin film.The method preparing argentiferous titanium oxide film layer has: (1) magnetron sputtering method is (as MusilJ, etal.Two-functionaldirectcurrentsputteredsilver-containi ngtitaniumdioxidethinfilms.NanoscaleResLett, 2009,4:313).The method belongs to physical vapour deposition (PVD), needs expensive vacuum equipment to carry out plated film, and there is sight line sex chromosome mosaicism, is difficult to form uniform rete on complex-shaped matrix (as implant) surface.(2) sol-gel process is (as AkgunBA, etal.Effectofsilverincorporationoncrystallizationandmicr ostructuralpropertiesofsol-gelderivedtitaniathinfilmsong lass.JSol-GelSciTechn, 2011,58:277).The method is easy to operation, and the rete all property covered is good, but relates to high-temperature sintering process, cannot be applied to some microstructures to heat sensitive titanium alloy (as TLM alloy, Ti-Ni alloy).(3) micro-arc oxidation (as ZhangPetal.AntibacterialTiO2coatingincorporatingsilverna noparticlesbymicroarcoxidationandionimplantation.JNanoma ter, 2013:542878).The method adopts electrolyte plasma discharge to carry out surface treatment to titanium or titanium alloy, can obtain that thickness is comparatively large, the titanium oxide film layer of rough surface porous, but relates to environmental issue, is difficult to the surface modification for POROUS TITANIUM.(4) ultraviolet lighting reducing process (as ZhaoLZ, etal.Antibacterialnano-structuredtitaniacoatingincorpora tedwithsilvernanoparticles.Biomater, 2011,32:5706).The Argent grain of the method reduction is gathered in Titanium base surface, is easy to come off.
[summary of the invention]
The object of the present invention is to provide a kind of short-cut method preparing argentiferous titanium deoxid film in medical titanium or titanium alloy surface, this thin film is conducive to the anti-microbial property and the biocompatibility that improve medical titanium material.
For achieving the above object, the present invention adopts following technical scheme:
Prepare a method for argentiferous titanium deoxid film in medical titanium or titanium alloy surface, comprise the steps:
1) adopt 180 ~ No. 1200 sand paper to polish step by step medical titanium or titanium alloy, then use deionized water, dehydrated alcohol, acetone ultrasonic cleaning respectively, dry;
2) silver nitrate solution is added in the liner of water heating kettle, then liner is put into water heating kettle, then titanium or titanium alloy sample are put into water heating kettle, make titanium or titanium alloy sample remain on below liquid level of solution, setting reaction temperature is 160-200 DEG C, and the response time is 16-24h;
3) question response terminates, and after water heating kettle temperature is down to room temperature, takes out water heating kettle, after the product washing in water heating kettle, drier, namely obtain argentiferous titanium deoxid film in medical titanium or titanium alloy surface.
The present invention improves further and is: in step 1), adopts 180,500,800, No. 1200 sand paper to polish step by step medical titanium or titanium alloy.
The present invention improves further and is: step 2) in, the concentration of silver nitrate solution is 10-20mmol/L.
The present invention improves further and is: the filling rate of silver nitrate solution in water heating kettle liner is 70-80%.
The present invention improves further and is: the liner of water heating kettle adopts polytetrafluoroethyllining lining.
The present invention improves further and is: carry out ultraviolet lighting, to reduce its water contact angle to the medical titanium of argentiferous titanium deoxid film prepared by step 4) or titanium alloy surface.
Relative to prior art, a kind of method preparing argentiferous titanium deoxid film in medical titanium or titanium alloy surface of the present invention, the method adopts silver nitrate solution to carry out hydrothermal treatment consists to titanium or titanium alloy sample, argentiferous titanium deoxid film is formed, to improve anti-microbial property and the biocompatibility of titanium or titanium alloy sample at material surface.
The advantages such as the present invention has that simple process, treatment temperature are lower, with low cost, clean environment firendly, practical, the surface modification that can be used for porous titanium material.
[accompanying drawing explanation]
Fig. 1 is the surface topography map of the pure titanium sample of hydrothermal treatment consists in the embodiment of the present invention 1;
Fig. 2 is the surface topography map of the pure titanium sample of hydrothermal treatment consists in the embodiment of the present invention 2;
Fig. 3 is the surface topography map of the hydrothermal treatment consists titanium alloy T LM sample in the embodiment of the present invention 3;
Fig. 4 is the surface topography map of the hydrothermal treatment consists Nitinol sample in the embodiment of the present invention 4.
[detailed description of the invention]
Below in conjunction with the drawings and the specific embodiments, the present invention is described in further detail.
Embodiment 1:
Silver nitrate solution hydrothermal treatment consists is adopted to prepare argentiferous titanium dioxide nano-film on pure titanium surface
Adopt the pure titanium sheet of thickness 1.2mm, size 10 × 10mm
2, polish step by step with 180,500,800, No. 1200 sand paper, with acetone, ethanol and pure water ultrasonic cleaning 10min respectively.The silver nitrate solution of preparation 10mmol/L, be added in teflon-lined water heating kettle, filling rate 70%, titanium sheet is put in water heating kettle.Airtight and 200 DEG C at hydrothermal treatment consists 12 hours.Reaction terminates rear taking-up sample, embathes several times, dry stand-by with pure water.As shown in Figure 1, pure titanium defines the granule of 50-130nm through hydrothermal treatment consists rear surface.X-ray photoelectron spectroscopy detection is to silver element.This sample is through ultraviolet lighting after 60 minutes, and water contact angle is reduced to 7.9 degree from 98.3 degree.Improve hydrophilic and be conducive to the biocompatibility improving material.
Embodiment 2:
Silver nitrate solution hydrothermal treatment consists is adopted to prepare argentiferous titanium dioxide nano-film on pure titanium surface
Adopt the pure titanium sheet of thickness 1.2mm, size 10 × 10mm
2, polish step by step with 180,500,800, No. 1200 sand paper, with acetone, ethanol and pure water ultrasonic cleaning 10min respectively.The silver nitrate solution of preparation 20mmol/L, be added in teflon-lined water heating kettle, filling rate 70%, titanium sheet is put in water heating kettle.Airtight and 150 DEG C at hydrothermal treatment consists 24 hours.Reaction terminates rear taking-up sample, embathes several times, dry stand-by with pure water.As shown in Figure 2, pure titanium defines the granule of 30-50nm and wide about 50nm, reaches the acicular crystal of 600nm through hydrothermal treatment consists rear surface.Electron spectrum detects silver element.
Embodiment 3:
Adopt silver nitrate solution hydrothermal treatment consists titanium alloy T LM(Ti-25Nb-3Zr-2Sn-3Mo) prepare argentiferous titanium dioxide nano-film
Adopt the titanium alloy T LM sheet of thickness 0.6mm, size 10 × 10mm
2, polish step by step with 180,500,800, No. 1200 sand paper, use acetone, ethanol and pure water ultrasonic cleaning 5min respectively.The silver nitrate solution of preparation 10mmolL, be added in teflon-lined water heating kettle, filling rate 80%, titanium alloy sheet is put in water heating kettle.Airtight and 200 DEG C at hydrothermal treatment consists 12 hours.Reaction terminates rear taking-up sample, embathes several times, dry stand-by with pure water.As shown in Figure 3, titanium alloy T LM defines the granule of about 50nm and wide about 150nm, reaches the rhomboidan of 400nm through hydrothermal treatment consists rear surface.Electron spectrum detects silver element.This sample is through ultraviolet lighting after 60 minutes, and water contact angle is reduced to 6.5 degree from 108.5 degree.Improve hydrophilic and be conducive to the biocompatibility improving material.
Embodiment 4:
Silver nitrate solution hydrothermal treatment consists Nitinol is adopted to prepare argentiferous titanium dioxide nano-film
Adopt the Nitinol sheet of thickness 2.0mm, size 10 × 10mm
2, polish step by step with 180,500,800, No. 1200 sand paper, use acetone, ethanol and pure water ultrasonic cleaning 5min respectively.The silver nitrate solution of preparation 10mmol/L, be added in teflon-lined water heating kettle, filling rate 80%, Nitinol sheet is put in water heating kettle.Airtight and 200 DEG C at hydrothermal treatment consists 12 hours.Reaction terminates rear taking-up sample, embathes several times, dry stand-by with pure water.As shown in Figure 4, titanium alloy T LM defines the granule of about 60nm and wide about 80nm, reaches the rhomboidan of 400nm through hydrothermal treatment consists rear surface.Backscattered electron image shows that the sparse white particle of specimen surface is Argent grain.X-ray diffraction detects the diffraction maximum of titanium dioxide and silver-colored simple substance.This sample is through ultraviolet lighting after 60 minutes, and water contact angle is reduced to 24.7 degree from 98.8 degree.Improve hydrophilic and be conducive to the biocompatibility improving material.
Above content is in conjunction with concrete preferred implementation further description made for the present invention; can not assert that the specific embodiment of the present invention is only limitted to this; for general technical staff of the technical field of the invention; without departing from the inventive concept of the premise; some simple deduction or replace can also be made, all should be considered as belonging to the present invention by submitted to claims determination scope of patent protection.
Claims (2)
1. prepare a method for argentiferous titanium deoxid film in medical titanium or titanium alloy surface, it is characterized in that, comprise the steps:
1) adopt 180,500,800, No. 1200 sand paper to polish step by step medical titanium or titanium alloy, then use deionized water, dehydrated alcohol, acetone ultrasonic cleaning respectively, dry;
2) silver nitrate solution is added in the liner of water heating kettle, then liner is put into water heating kettle, again titanium or titanium alloy sample are put into water heating kettle, make titanium or titanium alloy sample remain on below liquid level of solution, setting reaction temperature is 150-200 DEG C, and the response time is 16-24h, wherein, the concentration of silver nitrate solution is 10-20mmol/L, and the liner of water heating kettle adopts polytetrafluoroethyllining lining, and the filling rate of silver nitrate solution in water heating kettle liner is 70-80%;
3) question response terminates, and after water heating kettle temperature is down to room temperature, takes out water heating kettle, after the product pure water in water heating kettle, drier, namely obtain argentiferous titanium deoxid film in medical titanium or titanium alloy surface.
2. a kind of method preparing argentiferous titanium deoxid film in medical titanium or titanium alloy surface according to claim 1, it is characterized in that, to step 3) medical titanium of argentiferous titanium deoxid film prepared or titanium alloy surface carry out ultraviolet lighting, to reduce its water contact angle.
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| CN105803428A (en) * | 2016-05-10 | 2016-07-27 | 浙江大学 | Method for preparing zinc-doped nanometer structure with bacteriostatic action on surface of porous pure titanium |
| CN106752113B (en) * | 2016-12-14 | 2019-02-19 | 浙江恒逸高新材料有限公司 | A kind of preparation method and application of modifying titanium dioxide |
| CN107212907A (en) * | 2017-06-20 | 2017-09-29 | 上海形状记忆合金材料有限公司 | A kind of nanometer film plugging device and preparation method thereof |
| CN110129785B (en) * | 2019-06-12 | 2021-03-23 | 重庆理工大学 | Surface treatment method of TiNb alloy |
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