CN103877618A - Method of preparing silver-bearing titanium dioxide thin film on surface of medical titanium or titanium alloy - Google Patents
Method of preparing silver-bearing titanium dioxide thin film on surface of medical titanium or titanium alloy Download PDFInfo
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- CN103877618A CN103877618A CN201410102541.5A CN201410102541A CN103877618A CN 103877618 A CN103877618 A CN 103877618A CN 201410102541 A CN201410102541 A CN 201410102541A CN 103877618 A CN103877618 A CN 103877618A
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Abstract
The invention provides a method of preparing a silver-bearing titanium dioxide thin film on the surface of medical titanium or a titanium alloy. The method comprises the following steps: 1) gradually polishing medical titanium or titanium alloy by #180-1200 abrasive paper, and respectively ultrasonic cleaning by deionized water, absolute ethyl alcohol and acetone, and airing; 2) adding a silver nitrate solution into a liner of a hydrothermal kettle, and then, placing the liner in the hydrothermal kettle, and then, placing a titanium or titanium alloy sample in the hydrothermal kettle to maintain the titanium or titanium alloy sample below the liquid level of the solution, and setting the reaction temperature at 150-200 DEG C and the reaction time is 16-24 hours; and 3) after reaction, after cooling the hydrothermal kettle to room temperature, taking out the hydrothermal kettle, and after washing the product in the hydrothermal kettle, and then drying to obtain the silver-bearing titanium dioxide thin film on the surface of medical titanium or titanium alloy. The method provided by the invention has the advantages of simple process, low treatment temperature, low cost, cleanness and environmental protection and strong practicality, and can be used for surface modification of porous titanium materials and the like.
Description
[technical field]
The invention belongs to biomedical materials field, be specifically related to a kind of method of preparing argentiferous titanium deoxid film at medical titanium or titanium alloy surface.
[background technology]
In medical metal material, titanium because having good corrosion resistance, intensity, toughness and relative cheap price, is widely used in sclerous tissues's implants such as manufacturing bone fishplate bar, artificial joint, Dental Implant with titanium alloy.But the elastic modelling quantity (about 110GPa) of titanium is much higher than biological bone (1-30GPa), titanium implants can cause " stress shielding " phenomenon, is unfavorable for the healing of osseous tissue.The approach that reduces the elastic modelling quantity of titanium has two: the one, and alloying, exploitation has compared with the beta type of low elastic modulus or nearly beta Type Titanium Alloy, the for example 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; The 2nd, porous processing, void size approximately tens, to hundreds of micron, makes the elastic modelling quantity of POROUS TITANIUM or porous titanium alloy more approach biological bone, and loose structure is also conducive to implant and forms firmly interface with osseous tissue and be combined.
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 property such as corrosion resistance, biocompatibility, wearability that can improve titanium or titanium alloy, obtains better bone and implants effect.Wherein, coating of titanium dioxide or thin film are proved to be has good corrosion resistance and biocompatibility, and has the characteristics such as photocatalysis, photic hydrophilic, antibiotic property.
Surgical implant, antibacterial can cause infection in adhesion and the breeding of material surface, the antibacterial boundary layer of formation directly affects the success or failure of implant surgery.The method that solves implant infection problems applies antimicrobial coating and the load antibacterials molecule of argentiferous, cupric at implant surfaces.Silver is considered to a kind of effectively anti-biotic material for a long time, and it has the antibacterial activity of wide spectrum and cell is had to lower toxicity.Silver is also for improving the anti-microbial property of coating of titanium dioxide or thin film.The method of preparing argentiferous titanium oxide film layer has: (1) magnetron sputtering method is (as Musil J, et al.Two-functional direct current sputtered silver-containing titanium dioxide thin films.Nanoscale Res Lett, 2009,4:313).The method belongs to physical vapour deposition (PVD), needs expensive vacuum equipment carry out plated film, and exists and look linear problem, is difficult to form on complex-shaped matrix (as implant) surface uniform rete.(2) sol-gel process is (as Akgun BA, et al.Effect of silver incorporation on crystallization and microstructural properties of sol-gel derived titania thin films on glass.J Sol-Gel Sci Techn, 2011,58:277).The method easy operating, 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 Zhang P et al.Antibacterial TiO2coating incorporating silver nanoparticles by microarc oxidation and ion implantation.J Nanomater, 2013:542878).The method adopts electrolyte plasma discharge to carry out surface treatment to titanium or titanium alloy, can obtain that thickness is 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 Zhao LZ, et al.Antibacterial nano-structured titania coating incorporated with silver nanoparticles.Biomater, 2011,32:5706).The silver-colored particle aggregation of the method reduction, in titanio 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 of preparing argentiferous titanium deoxid film at medical titanium or titanium alloy surface, this thin film is conducive to improve anti-microbial property and the biocompatibility of medical titanium material.
For achieving the above object, the present invention adopts following technical scheme:
A method of preparing argentiferous titanium deoxid film at medical titanium or titanium alloy surface, comprises the steps:
1) adopt 180～No. 1200 sand paper to polish step by step medical titanium or titanium alloy, then use respectively deionized water, dehydrated alcohol, acetone ultrasonic cleaning, 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, titanium or titanium alloy sample are remained on below liquid level of solution, setting reaction temperature is 160-200 ℃, and the response time is 16-24h;
3) question response finishes, and water heating kettle temperature is down to after room temperature, takes out water heating kettle, by after the product washing in water heating kettle, drier, obtain argentiferous titanium deoxid film in medical titanium or titanium alloy surface.
The present invention further improves and is: in step 1), adopt 180,500,800, No. 1200 sand paper to polish step by step medical titanium or titanium alloy.
The present invention further improves and is: step 2) in, the concentration of silver nitrate solution is 10-20mmol/L.
The present invention further improves and is: the filling rate of silver nitrate solution in water heating kettle liner is 70-80%.
The present invention further improves and is: the liner of water heating kettle adopts polytetrafluoroethyllining lining.
The present invention further improves and is: medical titanium or the titanium alloy surface of argentiferous titanium deoxid film prepared by step 4) carry out ultraviolet lighting, to reduce its water contact angle.
With respect to prior art, a kind of method of preparing argentiferous titanium deoxid film at 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, form argentiferous titanium deoxid film at material surface, to improve anti-microbial property and the biocompatibility of titanium or titanium alloy sample.
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 the hydrothermal treatment consists in the embodiment of the present invention 1;
Fig. 2 is the surface topography map of the pure titanium sample of the 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.
[specific embodiment]
Below in conjunction with the drawings and the specific embodiments, the present invention is described in further detail.
Embodiment 1:
Adopt silver nitrate solution hydrothermal treatment consists 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, is added in teflon-lined water heating kettle, filling rate 70%, and titanium sheet is put in water heating kettle.Airtight and 200 ℃ at hydrothermal treatment consists 12 hours.Reaction finishes rear taking-up sample, embathes several times with pure water, dries stand-by.As shown in Figure 1, pure titanium has formed 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 the biocompatibility that hydrophilic is conducive to improve material.
Embodiment 2:
Adopt silver nitrate solution hydrothermal treatment consists 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, is added in teflon-lined water heating kettle, filling rate 70%, and titanium sheet is put in water heating kettle.Airtight and 150 ℃ at hydrothermal treatment consists 24 hours.Reaction finishes rear taking-up sample, embathes several times with pure water, dries stand-by.As shown in Figure 2, pure titanium through hydrothermal treatment consists rear surface formed 30-50nm granule and wide about 50nm, reach the acicular crystal of 600nm.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 respectively acetone, ethanol and pure water ultrasonic cleaning 5min.The silver nitrate solution of preparation 10mmolL, is added in teflon-lined water heating kettle, filling rate 80%, and titanium alloy sheet is put in water heating kettle.Airtight and 200 ℃ at hydrothermal treatment consists 12 hours.Reaction finishes rear taking-up sample, embathes several times with pure water, dries stand-by.As shown in Figure 3, titanium alloy T LM through hydrothermal treatment consists rear surface formed about 50nm granule and wide about 150nm, reach the rhomboidan of 400nm.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 the biocompatibility that hydrophilic is conducive to improve material.
Embodiment 4:
Adopt silver nitrate solution hydrothermal treatment consists Nitinol 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 respectively acetone, ethanol and pure water ultrasonic cleaning 5min.The silver nitrate solution of preparation 10mmol/L, is added in teflon-lined water heating kettle, filling rate 80%, and Nitinol sheet is put in water heating kettle.Airtight and 200 ℃ at hydrothermal treatment consists 12 hours.Reaction finishes rear taking-up sample, embathes several times with pure water, dries stand-by.As shown in Figure 4, titanium alloy T LM through hydrothermal treatment consists rear surface formed about 60nm granule and wide about 80nm, reach the rhomboidan of 400nm.Backscattered electron image shows that the sparse white particle of specimen surface is silver-colored granule.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 the biocompatibility that hydrophilic is conducive to improve 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 only limits to this; for general technical staff of the technical field of the invention; without departing from the inventive concept of the premise; can also make some simple deduction or replace, all should be considered as belonging to the present invention and determine scope of patent protection by submitted to claims.
Claims (6)
1. a method of preparing argentiferous titanium deoxid film at medical titanium or titanium alloy surface, is characterized in that, comprises the steps:
1) adopt 180～No. 1200 sand paper to polish step by step medical titanium or titanium alloy, then use respectively deionized water, dehydrated alcohol, acetone ultrasonic cleaning, 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, titanium or titanium alloy sample are remained on below liquid level of solution, setting reaction temperature is 150-200 ℃, and the response time is 16-24h;
3) question response finishes, and water heating kettle temperature is down to after room temperature, takes out water heating kettle, by after the product washing in water heating kettle, drier, obtain argentiferous titanium deoxid film in medical titanium or titanium alloy surface.
2. a kind of method of preparing argentiferous titanium deoxid film at medical titanium or titanium alloy surface according to claim 1, is characterized in that, in step 1), adopts 180,500,800, No. 1200 sand paper to polish step by step medical titanium or titanium alloy.
3. a kind of method of preparing argentiferous titanium deoxid film at medical titanium or titanium alloy surface according to claim 1, is characterized in that step 2) in, the concentration of silver nitrate solution is 10-20mmol/L.
4. a kind of method of preparing argentiferous titanium deoxid film at medical titanium or titanium alloy surface according to claim 1, is characterized in that, the filling rate of silver nitrate solution in water heating kettle liner is 70-80%.
5. a kind of method of preparing argentiferous titanium deoxid film at medical titanium or titanium alloy surface according to claim 1, is characterized in that, the liner of water heating kettle adopts polytetrafluoroethyllining lining.
6. a kind of method of preparing argentiferous titanium deoxid film at medical titanium or titanium alloy surface according to claim 1, it is characterized in that, medical titanium or the titanium alloy surface of argentiferous titanium deoxid film prepared by step 4) carry out ultraviolet lighting, to reduce its water contact angle.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN106752113A (en) * | 2016-12-14 | 2017-05-31 | 浙江恒逸高新材料有限公司 | A kind of preparation method of modifying titanium dioxide and application |
| 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 |
| CN110129785A (en) * | 2019-06-12 | 2019-08-16 | 重庆理工大学 | A kind of surface treatment method of TiNb alloy |
-
2014
- 2014-03-19 CN CN201410102541.5A patent/CN103877618B/en not_active Expired - Fee Related
Non-Patent Citations (1)
| Title |
|---|
| 刘钟馨等: "钛基底上纳米柱阵列薄膜的制备与表征", 《广东化工》, no. 06, 31 December 2009 (2009-12-31), pages 11 - 13 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN106752113A (en) * | 2016-12-14 | 2017-05-31 | 浙江恒逸高新材料有限公司 | A kind of preparation method of modifying titanium dioxide and application |
| 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 |
| CN110129785A (en) * | 2019-06-12 | 2019-08-16 | 重庆理工大学 | A kind of surface treatment method of TiNb alloy |
| CN110129785B (en) * | 2019-06-12 | 2021-03-23 | 重庆理工大学 | Surface treatment method of TiNb alloy |
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