CN103046056B - Method for preparing Ag-Ti-O antibacterial nanotube film on surface of titanium alloy - Google Patents
Method for preparing Ag-Ti-O antibacterial nanotube film on surface of titanium alloy Download PDFInfo
- Publication number
- CN103046056B CN103046056B CN201210559876.0A CN201210559876A CN103046056B CN 103046056 B CN103046056 B CN 103046056B CN 201210559876 A CN201210559876 A CN 201210559876A CN 103046056 B CN103046056 B CN 103046056B
- Authority
- CN
- China
- Prior art keywords
- vacuum chamber
- test specimen
- film
- titanium alloy
- treatment
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Abstract
The invention provides a method for preparing an Ag-Ti-O antibacterial nanotube film on the surface of a titanium alloy, and belongs to the technical field of nanotube film preparation. The method is characterized by including placing a preprocessed test piece on a sample stage of pulse DC magneto-controlled sputter coating equipment, and placing a plane TiAg alloy target opposite to the sample; feeding argon into a vacuum chamber, and sputter-cleaning the vacuum chamber and the preprocessed test piece; coating a TiAg alloy film layer on the surface of the test piece after the cleaning; and then performing anodic oxidation treatment on the alloy film layer to prepare the Ag-Ti-O nanotube film. The film prepared through the method is good in film-substrate cohesion, and has a long-acting antibacterial property and excellent biocompatibility.
Description
Technical field
The invention belongs to nano-tube film field of material preparation, relate to a kind of method of preparing the Ag-Ti-O nano-tube film of long-term antibacterial ability and good biocompatibility at titanium alloy surface.
Background technology
Titanium alloy relies on its excellent mechanical property and biocompatibility to be widely used as embedded material, as joint prosthesis, tooth implant, orthodontic wire etc.But, follow the postoperative infection sickness rate of titanium alloy higher, patient's rehabilitation is caused to very big harm, as increased medical expense, extend rehabilitation duration and causing various complication even dead.
In order to address the above problem, conventional method is that titanium alloy is carried out to surface modification treatment both at home and abroad at present, and conventional method has: (1) ion implantation, (2) antibacterials load method etc.Adopting ion implantation is some elements with anti-microbial property at material surface doping, as Ag, and Cu, Zn etc., the significantly anti-microbial property of strongthener, reduces the probability of occurrence infecting, but, this technological reaction layer thickness is limited, only has at most 200nm, and the dosage of doped element is very limited, the effective antibacterial dosage of separating out in vivo far from can meet kills whole bacteriums, do not there is the requirement of long-acting bactericidal effect, and ion implantation equipment price costliness, process costs is very high; Antibacterials load method is generally by pickling process, freeze-drying and photoreduction method etc., and it is that the medicine that has an antibacterial effect at material surface Gentamicin Sulfate-loaded etc. reaches antibacterial object.This processing method can obtain the antibacterial effect stronger than ion implantation, but the antibacterials of load are all that physical adsorption is at material surface, after in implantable bioartificial body, can meet in a short time antibacterial requirement completely, but along with the prolongation of Implantation Time, the dosage that it is separated out declines rapidly, make long acting antibiotic poor effect, and can make bacterium produce resistance.
Heavy metal is a kind of important inorganic antiseptic, and it can make protein precipitation, produces antimetabolism, makes metabolite become invalid compound, thereby suppresses microbial growth or cause its death.Because some metallic elements with antibacterial ability have toxicity simultaneously, as Hg, the elements such as Cd, therefore in fact have the elements such as Ag, Cu and Zn as the metallic element of sterilant, wherein the bactericidal properties of Ag is the strongest, and Ag appropriate in human body not only can kill harmful bacterium, can also help repair and reconstruction to the vital tissue of life.
Summary of the invention
Based on the deficiency of above-mentioned various surface modifying methods, the present invention seeks to, a kind of method of preparing Ag-Ti-O nanotube antibacterial film at titanium alloy surface is provided, be expected to fundamentally solve the shortcoming existing in prior art.
The present invention seeks to realize like this, it is characterized in that implementation step is as follows:
(1) titanium alloy test specimen pre-treatment: titanium alloy test specimen is carried out to mechanical mill, polishing, and then order immerses and carries out ultrasonic cleaning in acetone, alcohol and distilled water;
(2) titanium alloy test specimen 10 good pre-treatment is put in the rotatable sample table 8 of vacuum chamber 1 of pulse direct current magnetic-controlled sputtering coating equipment as shown in Figure 1, permanent magnet 2 is placed on the outside surface of vacuum chamber 1, the plane TiAg alloys target 3 in Ti in film and Ag source is arranged in the vacuum chamber 1 at the back side of permanent magnet 2, and the distance of adjusting between TiAg alloys target 3 and test specimen 10 is 75-95cm;
(3) first with vacuum extractor 5, the air pressure of vacuum chamber 1 is evacuated to 5.0 × 10 by the pore 4 of giving vent to anger
-3pa, then passing into flow by air inlet pipe hole 9 is that the argon gas of 60sccm is in vacuum chamber 1, when vacuum chamber 1 stable gas pressure is during at 4.8-5.2Pa, to open grid bias power supply 7 and bias voltage is slowly added to-800～-900V vacuum chamber 1 and test specimen 10 surfaces are carried out to sputter clean, scavenging period is 15-30min.
(4) after having cleaned, open vacuum extractor 5 and extract residual gas out by the pore 4 of giving vent to anger, then regulate argon flow amount to 80sccm by air inlet pipe hole 9, make vacuum chamber 1 air pressure remain on 8.0 × 10
-1pa to 8.5 × 10
-1pa, opens TiAg alloys target shielding power supply 6 and voltage is slowly added to 350-380V, regulates electric current to 0.8-1.2A, then opens grid bias power supply 7 and adjust to be biased into 80-120V, and at test specimen 10 plated surface Ti-Ag composite films, the plated film time is 4h;
(5) will be containing 2.5-3.5wt%NH
4f, 1-1.5vol%H
2the ethylene glycol electrolytic solution 15 of O is put in the electrolyzer 12 of anodic oxidation equipment as shown in Figure 2, the lower end that the test specimen 10 of supporting electrode 11 and process coating film treatment is fixed on to support 13 is immersed in electrolytic solution, then open direct supply 14 test specimen 10 through coating film treatment is carried out to anodic oxidation treatment, prepare Ag-Ti-O nanotube antibacterial film, oxidation voltage is 25-35V, and oxidization time is 3-5h.
Advantage of the present invention and positively effect are:
(1) the Ag-Ti-O nanotube antibacterial film that adopts the present invention to prepare, in first week, the sterilizing rate of antibacterial film remains on 100%, though slightly decline and all remain on more than 90% subsequently, proves that antibacterial film has powerful long acting antibiotic ability.
(2) biological experiment shows that Ag-Ti-O nano-tube film prepared by the method has extremely low cytotoxicity, compared with traditional titanium alloy, can promote the activity of osteoblastic propagation and alkaline phosphatase, accelerates the generation of new bone.Therefore, Ag-Ti-O nanotube antibacterial film prepared by this kind of method can significantly improve antibacterial ability and the biology performance of titanium alloy, has a good application prospect.
Brief description of the drawings
Fig. 1 is the pulse direct current magnetron sputtering equipment structural representation that the present invention uses;
Fig. 2 is the anodic oxidation equipment schematic diagram that the present invention uses;
Fig. 3 is the design sketch (in figure, 1 white point represents the bacterium colony being grown up to by 1 bacterium) after titanium alloy of the present invention and bacteriological action.
Fig. 4 is the design sketch (in figure, 1 white point represents the bacterium colony being grown up to by 1 bacterium) after Ag-Ti-O nano-tube film of the present invention and bacteriological action.
In figure: the 1-vacuum chamber 2-permanent magnet 3-TiAg alloys target 4-pore 5-vacuum extractor 6-TiAg alloys target shielding power supply 7-grid bias power supply 8-sample table 9-air inlet pipe hole 10-test specimen 11-supporting electrode 12-electrolyzer 13-support 14-direct supply 15-electrolytic solution of giving vent to anger.
Embodiment
Below in conjunction with accompanying drawing, the present invention is described in further detail:
As shown in Figure 1, 2, existing is that the TC4 titanium alloy test specimen that 14mm, thickness are 2mm is tested to diameter, and its operation steps is as follows:
(1) titanium alloy test specimen pre-treatment: titanium alloy test specimen is carried out to mechanical mill, polishing, and then order immerses and carries out ultrasonic cleaning in acetone, alcohol and distilled water;
(2) titanium alloy test specimen 10 good pre-treatment is put in the rotatable sample table 8 of vacuum chamber 1 of pulse direct current magnetic-controlled sputtering coating equipment as shown in Figure 1, permanent magnet 2 is placed on the outside surface of vacuum chamber 1, the plane TiAg alloys target 3 in Ti in film and Ag source is arranged in the vacuum chamber 1 at the back side of permanent magnet 2, and the distance of adjusting between TiAg alloys target 3 and test specimen 10 is 80cm;
(3) first with vacuum extractor 5, the air pressure of vacuum chamber 1 is evacuated to 5.0 × 10 by the pore 4 of giving vent to anger
-3pa, then passing into flow by air inlet pipe hole 9 is that the argon gas of 60sccm is in vacuum chamber 1, when vacuum chamber 1 stable gas pressure is during at 5.0Pa, open grid bias power supply 7 and slowly add to-800V carries out sputter clean to vacuum chamber 1 and test specimen 10 surfaces by bias voltage, scavenging period is 25min.
(4) after having cleaned, open vacuum extractor 5 and extract residual gas out by the pore 4 of giving vent to anger, then regulate argon flow amount to 80sccm by air inlet pipe hole 9, make vacuum chamber 1 air pressure remain on 8.2 × 10
-1pa, opens TiAg alloys target shielding power supply 6 and voltage is slowly added to 350V, regulates electric current to 1.0A, then opens grid bias power supply 7 and adjust to be biased into 100V, and at test specimen 10 plated surface Ti-Ag composite films, the plated film time is 4h;
(5) will be containing 3.0wt%NH4F, 1.2vol%H
2the ethylene glycol electrolytic solution 15 of O is put in the electrolyzer 12 of anodic oxidation equipment as shown in Figure 2, the lower end that the test specimen 10 of supporting electrode 11 and process coating film treatment is fixed on to support 13 is immersed in electrolytic solution, then open direct supply 14 test specimen 10 through coating film treatment is carried out to anodic oxidation treatment, on the outside surface of test specimen 10, prepare Ag-Ti-O nanotube antibacterial film, anodic oxidation voltage is 30V, and anodizing time is 4h.
Through above-mentioned processing, there is the Ag-Ti-O nanotube antibacterial film of long acting antibiotic ability in the preparation of titanium alloy test specimen surface.The average caliber 70nm of nano-tube film after measured, thickness is 9 μ m.
Detect Ag by inductivity coupled plasma mass spectrometry
+separate out behavior, find Ag
+can continue to separate out, in phosphate buffered saline buffer, soak after 4 weeks and still there is the higher amount of separating out.As shown in Figure 3, untreated titanium alloy surface has a large amount of bacterial colonys to exist, and treated titanium alloy surface does not have bacterial colony in surface as shown in Figure 4, illustrates that the sterilizing rate of nano-tube film is 100% after treatment.Biological experiment shows that Ag-Ti-O nano-tube film prepared by the method has extremely low cytotoxicity, compared with undressed titanium alloy, can promote the activity of osteoblastic propagation and alkaline phosphatase, accelerates the generation of new bone.
Claims (1)
1. prepare a method for Ag-Ti-O nanotube antibacterial film at titanium alloy surface, it is characterized in that operation steps is:
(1) titanium alloy test specimen pre-treatment: titanium alloy test specimen is carried out to mechanical mill, polishing, and then order immerses and carries out ultrasonic cleaning in acetone, alcohol and distilled water;
(2) titanium alloy test specimen (10) good pre-treatment is put in the rotatable sample table of vacuum chamber (1) (8) of pulse direct current magnetic-controlled sputtering coating equipment, permanent magnet (2) is placed on the outside surface of vacuum chamber (1), the plane TiAg alloys target (3) in Ti in film and Ag source is arranged in the vacuum chamber (1) at the back side of permanent magnet (2), and the distance of adjusting between TiAg alloys target (3) and test specimen 10 is 75-95cm;
(3) first use vacuum extractor (5) that the air pressure of vacuum chamber (1) is evacuated to 5.0 × 10 by the pore of giving vent to anger (4)
-3pa, then passing into flow by air inlet pipe hole (9) is that the argon gas of 60sccm is in vacuum chamber (1), when vacuum chamber (1) stable gas pressure is during at 4.8-5.2Pa, open grid bias power supply (7) and bias voltage is slowly added to-800～-900V vacuum chamber (1) and test specimen (10) surface are carried out to sputter clean, scavenging period is 15-30min;
(4) after having cleaned, open vacuum extractor (5) and extract residual gas out by the pore of giving vent to anger (4), then regulate argon flow amount to 80sccm by air inlet pipe hole (9), make vacuum chamber (1) air pressure remain on 8.0 × 10
-1pa to 8.5 × 10
-1pa, open TiAg alloys target shielding power supply (6) and voltage is slowly added to 350-380V, regulate electric current to 0.8-1.2A, then open grid bias power supply (7) and adjust and be biased into 80-120V, at test specimen (10) plated surface Ti-Ag composite film, the plated film time is 4h;
(5) will be containing 2.5-3.5wt%NH
4f, 1-1.5vol%H
2the ethylene glycol electrolytic solution (15) of O is put in the electrolyzer (12) of anodic oxidation equipment, the lower end that the test specimen (10) of supporting electrode (11) and process coating film treatment is fixed on to support (13) is immersed in electrolytic solution, then open direct supply (14) test specimen (10) through coating film treatment is carried out to anodic oxidation treatment, prepare Ag-Ti-O nanotube antibacterial film, oxidation voltage is 25-35V, and oxidization time is 3-5h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210559876.0A CN103046056B (en) | 2012-12-21 | 2012-12-21 | Method for preparing Ag-Ti-O antibacterial nanotube film on surface of titanium alloy |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210559876.0A CN103046056B (en) | 2012-12-21 | 2012-12-21 | Method for preparing Ag-Ti-O antibacterial nanotube film on surface of titanium alloy |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103046056A CN103046056A (en) | 2013-04-17 |
| CN103046056B true CN103046056B (en) | 2014-11-26 |
Family
ID=48058913
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210559876.0A Expired - Fee Related CN103046056B (en) | 2012-12-21 | 2012-12-21 | Method for preparing Ag-Ti-O antibacterial nanotube film on surface of titanium alloy |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103046056B (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103695707B (en) * | 2013-10-18 | 2015-08-19 | 中国医科大学 | A kind of titanium silver alloy nanotube for surgical fixator tool and preparation method thereof |
| CN103911593B (en) * | 2014-04-02 | 2016-02-10 | 太原理工大学 | A kind of titanium alloy surface Ag doped Ti O 2the preparation method of film |
| CN104878351B (en) * | 2015-06-03 | 2017-08-25 | 太原理工大学 | A kind of method that titanium metalized ag layer is prepared on Nitinol surface |
| CN104988557A (en) * | 2015-06-03 | 2015-10-21 | 太原理工大学 | Method for preparing zinc oxide-doped titanium dioxide nanotube on pure titanium surface |
| CN105420680B (en) * | 2015-11-18 | 2018-06-22 | 太原理工大学 | A kind of preparation method of pure titanium surface A g/Sr codope TiO2 porous membranes |
| CN107779814B (en) * | 2017-08-31 | 2020-02-21 | 昆明贵金属研究所 | Preparation method of Ag-nanoparticle-containing gradient wear-resistant coating |
| CN112813392A (en) * | 2020-12-31 | 2021-05-18 | 中国科学院宁波材料技术与工程研究所 | Solid-liquid compound wear-resistant antibacterial material based on capillary action, preparation method and application |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101358349A (en) * | 2008-09-16 | 2009-02-04 | 徐钲鉴 | Surface treating method of electronic apparatus shell |
| CN101717920A (en) * | 2009-12-29 | 2010-06-02 | 浙江大学 | Method for preparing composite Ag-Ti oxide antibacterial film by magnetron sputtering |
-
2012
- 2012-12-21 CN CN201210559876.0A patent/CN103046056B/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN103046056A (en) | 2013-04-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103046056B (en) | Method for preparing Ag-Ti-O antibacterial nanotube film on surface of titanium alloy | |
| Zhang et al. | Synergistic antibacterial activity of physical-chemical multi-mechanism by TiO2 nanorod arrays for safe biofilm eradication on implant | |
| CN107304472B (en) | Have both the medical titanium-based composite coat and preparation method thereof of Bone Defect Repari function and anti-microbial property | |
| Xu et al. | Zinc-ion implanted and deposited titanium surfaces reduce adhesion of Streptococccus mutans | |
| CN104357814A (en) | Titanium alloy containing antibacterial coating as well as preparation method and application thereof | |
| CN103110981B (en) | Method for preparing antibacterial active titanium oxide nanotube array composite coating material | |
| Du et al. | Evaluation of antibacterial effects by atmospheric pressure nonequilibrium plasmas against Enterococcus faecalis biofilms in vitro | |
| CN110896607B (en) | Surface super-capacitance modified material and preparation method and application thereof | |
| CN105688278A (en) | Method for preparing antibacterial coating on surface of titanium implant | |
| CN102191454B (en) | Surface modification method for medical titanium metal material | |
| Jeong et al. | Bacterial attachment on titanium surfaces is dependent on topography and chemical changes induced by nonthermal atmospheric pressure plasma | |
| Jang et al. | Direct-deposited graphene oxide on dental implants for antimicrobial activities and osteogenesis | |
| CN102330051A (en) | Surface modifying method for improving antibacterial property and biological activity of medicinal titanium | |
| CN111719172B (en) | Preparation method and application of iodine-loaded antibacterial coating on titanium alloy surface | |
| Si et al. | A heterogeneous TiO2/SrTiO3 coating on titanium alloy with excellent photocatalytic antibacterial, osteogenesis and tribocorrosion properties | |
| CN107937880A (en) | A kind of method of metal surface properties modification and products thereof and purposes | |
| CN103695707A (en) | Titanium silver alloy nanotube for surgery fixing apparatus and preparation method thereof | |
| CN114053481A (en) | Preparation method of titanium-based bone dental implant material loaded with antibacterial polypeptide and antibacterial ions | |
| Lu et al. | Nanostructured Cu-doped TiO2 with photothermal effect for prevention of implant-associated infection | |
| CN106637121A (en) | Medical titanium based metal material and manufacturing method thereof | |
| CN104988557A (en) | Method for preparing zinc oxide-doped titanium dioxide nanotube on pure titanium surface | |
| Yang et al. | Time-dependent reactive oxygen species inhibit Streptococcus mutans growth on zirconia after a helium cold atmospheric plasma treatment | |
| CN109652766B (en) | Magnesium-silver-copper coating for medical implant material and preparation method thereof | |
| CN104878351A (en) | Method for preparing titanium-silver alloy layer on surface of nickel-titanium alloy | |
| CN112239848B (en) | Antibacterial dental implant and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20141126 Termination date: 20171221 |