CN103911593A - Preparation method of titanium alloy surface Ag-doped TiO2 thin film - Google Patents
Preparation method of titanium alloy surface Ag-doped TiO2 thin film Download PDFInfo
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- CN103911593A CN103911593A CN201410129298.6A CN201410129298A CN103911593A CN 103911593 A CN103911593 A CN 103911593A CN 201410129298 A CN201410129298 A CN 201410129298A CN 103911593 A CN103911593 A CN 103911593A
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Abstract
The invention discloses a preparation method of a titanium alloy surface Ag-doped TiO2 thin film, belonging to the technical field of metal material surface modification. The preparation method comprises the steps of firstly preparing a TiAg thin film on a titanium alloy surface by using a magnetron sputtering technique, then performing thermal oxidation treatment in a muffle furnace, and forming an Ag-doped rutile TiO2 thin film which can be well bound with a matrix on the titanium alloy surface through oxidation and diffusion. Compared with the prior art, the prepared thin film not only has a good binding force with the matrix, but also has significantly-improved corrosion resistance and wear resistance; the problem that a titanium alloy is easy to cause bacterial infection in a human body when used as an implant is solved; the release of harmful elements in the titanium alloy matrix also can be prevented, so that the thin film has good biocompatibility. The preparation method is simple in operation and good in repeatability, and is suitable for mass production.
Description
Technical field
The present invention relates to a kind of titanium alloy surface Ag doped Ti O
2the preparation method of film, belongs to metal surface properties modification technical field.
Background technology
Titanium alloy has density and approaches the advantages such as people's bone, Young's modulus are low, corrosion-resistant, good biocompatibility, and is widely used in bio-medical field, as joint prosthesis, tooth implant, cardiovascular implant frame and other implant and medicine equipment etc.But titanium alloy does not possess antibacterial ability, in the time of clinical use, in implant into body, easily cause that bacterium infects, thereby cause graft failure.Inorganic antiseptic is because have good antibacterial ability and thermostability and be widely used for improving the antibacterial ability of biomaterial.In all inorganic antiseptics, Ag, as a kind of broad spectrum antimicrobicide, has efficient antibacterial ability, and suitable Ag content do not have toxicity to cell, thereby has been subject to investigator's extensive concern.
Some process for modifying surface that adopt at present, as ion implantation, plated film, chemosynthesis etc., can form the antibacterial modified layer containing Ag at titanium alloy surface.But as embedded material, in use also want taking up wear, corrosion and synergistic infringement thereof.Prepared by above-mentioned these methods is difficult to allow titanium alloy possess in antibacterial situation containing Ag modified layer, has better anti-corrosion and wear resisting property simultaneously.Modified layer prepared by ion implantation and chemosynthesis is thinner, very easily loss in corrosion and wear process; Antibacterial film in use easily ftractures.
TiO
2stable chemical nature, safety non-toxic, is a kind of important inorganic functional material.The TiO preparing at metal material surface
2modified layer, except having good photocatalysis performance, also has good anticorrosive and wear resisting property.Prepare TiO at titanium alloy implant surfaces
2modified layer, can also stop the release of harmful element in body material (as Al, V).In addition, research shows, TiO
2in artificial body fluid, also there is good biocompatibility.
Prior art directly adopts magnetron sputtering, and the Chinese patent that is CN 1557990A as publication number discloses a kind of " Ag/TiO that contact angle is adjustable
2laminated film and preparation method thereof ", the method is devoted to preparation table mask the anti-fog thin film of hydrophobicity performance.If adopt in this way and prepare Ag doped Ti O at titanium alloy surface
2film, the film of formation, due to large with body material nature difference, easily produce cracking, peeling phenomenon, and directly in reactive sputtering process, passes into oxygen, easily causes " target is poisoning ", can affect technology stability and film deposition rate.
Summary of the invention
The present invention aims to provide a kind of titanium alloy surface Ag doped Ti O
2the preparation method of film, has been prepared and has been combined good Ag doped Ti O with matrix at titanium alloy surface by the method
2film, makes matrix have good antibacterial, anti-corrosion, wear-resisting and biocompatibility, has solved titanium alloy and has easily caused as implant the problem that bacterium infects, and avoided the problem of the easy loss failure of traditional antibacterial film in the time of clinical use.
The present invention is achieved by the following technical solutions:
A kind of titanium alloy surface Ag doped Ti O
2the preparation method of film, first utilizes magnetron sputtering technique to prepare TiAg film at titanium alloy surface, then in retort furnace, carries out thermal oxidative treatment, by being oxidized and spreading, forms and is combined good Ag doped rutile type TiO with matrix at titanium alloy surface
2film.
Specifically, described preparation method comprises the following steps:
(1) magnetron sputtering plating
1. the titanium alloy base material after polishing and TiAg alloy target material are placed in to magnetic-controlled sputtering coating equipment, are evacuated to 1 × 10
-4after Pa is following, close high threshold, pass into high-purity argon gas, air pressure is controlled at 3～8Pa; Open workpiece voltage, be controlled at-800V of workpiece voltage, carries out 20min ion bombardment sputter process to workpiece; After cleaning finishes, close voltage and gas, be evacuated to final vacuum;
2. again pour argon gas, open workpiece power supply and source electrode power supply, slowly boosted voltage, adjusts voltage and gas pressure intensity gradually, makes be controlled at-100V of workpiece voltage, and source voltage is controlled at 350～450V, and operating air pressure remains on 6～10 Pa; Plated film 20 ~ 120min, closes source class power supply, and workpiece power supply and argon gas continue to vacuumize, and treats that workpiece temperature is down to room temperature, closes water coolant, opens body of heater and takes out sample; Prepare TiAg film at titanium alloy surface;
(2) thermal oxidative treatment:
Titanium alloy workpiece after surface coating is placed in retort furnace, control Heating temperature be 400 ~ 1000 ℃, in air, there is thermooxidizing in TiAg film, and with matrix mutual diffusion, insulation 1 ~ 6h, powered-down, is cooled to room temperature, take out sample.
Further, described TiAg alloy target material is to smelt and form according to following atomic ratio: the atomic percentage conc of Ag is 1%-20%, and the atomic percentage conc of Ti is 80%-99%.
Further, be preferably 40 ~ 80min in the titanium alloy surface plated film time.
Further, in retort furnace, Heating temperature is preferably 600 ~ 800 ℃, and the thermooxidizing time is preferably 2 ~ 4h.
Titanium alloy surface Ag doped Ti O provided by the invention
2the preparation method of film, its reaction mechanism is: first the present invention adopts magnetron sputtering to prepare TiAg film at titanium alloy surface, by using the TiAg target of heterogeneity, has effectively controlled the Ag content in film; Then the titanium alloy sample that has deposited TiAg film is placed in retort furnace and is heated, by controlling Heating temperature, can make on the one hand Ti, Ag and the matrix generation mutual diffusion of deposition, the bonding force of enhanced film and matrix; Directly utilize on the other hand airborne oxygen to react with TiAg film, form the TiO of Ag doping at titanium alloy surface
2film.
Beneficial effect of the present invention:
(1) the method combines magnetron sputtering to prepare in the stable and retort furnace of thin-film technique thermal oxidative treatment heated perimeter controlled, and can complete the feature of oxidation and mutual diffusion simultaneously, has good process repeatability, the advantage that film quality is controlled;
(2) form Ag doped Ti O at titanium alloy surface
2film, has solved titanium alloy and in human body, has easily caused the problem that bacterium infects as implant;
(3) compared with the prior art, the film of preparation not only has good bonding force with matrix, and solidity to corrosion and wear resistance significantly improve;
(4) film of preparing also can stop the release of harmful element in titanium alloy substrate, has good biocompatibility;
(5) the method is simple to operate, reproducible, is suitable for mass production.
Accompanying drawing explanation
Fig. 1 is Ag doped Ti O
2film surface SEM photo.
Fig. 2 is Ag doped Ti O
2film antibacterial effect figure.
Fig. 3 is bacterium colony photo after untreated titanium alloy contacts with bacterium.
Fig. 4 is Ag doped Ti O
2film and untreated titanium alloy hardness comparison diagram.
Fig. 5 is Ag doped Ti O
2film and untreated titanium alloy solidity to corrosion comparison diagram.
Fig. 6 is Ag doped Ti O
2film surface Growth of Cells design sketch.
Embodiment
Further illustrate the present invention below by embodiment, but be not limited to following examples.
Implement a kind of titanium alloy surface Ag of the present invention doped Ti O
2the preparation method of film, in magnetron sputtering equipment, using TiAg alloy target material is source electrode, the low-temperature plasma that utilizes glow discharge to produce, by bombardment source electrode surface, make preplating metallic element from source electrode surface sputtering out, be deposited on titanium alloy surface through transportation and form TiAg settled layer.Again the titanium alloy substrate workpiece after surface coating is placed in common retort furnace and carries out thermal oxidative treatment, obtain Ag doped Ti O at titanium alloy surface
2film.
A kind of titanium alloy surface Ag doped Ti O of concrete enforcement
2the preparation method's of film technical scheme is: first, by using the alloy target material of different Ag content, form heterogeneity TiAg settled layer in advance at titanium alloy surface.Then, the titanium alloy workpiece of effects on surface plating TiAg carries out thermal oxidative treatment, by regulating oxidate temperature, forms the Ag doped Ti O of different tissues structure at titanium alloy surface
2film.Through performance is evaluated, and determines the experimental technique of suitable application.Concrete step of preparation process is as follows:
(1) sample is prepared: it is 20mm that titanium alloy sample is processed into diameter, the disk that thickness is 4mm, and polishing, is taken up in order of priority sample to put into acetone, ethanol and deionized water, ultrasonic cleaning 5min successively, drying for standby after polishing.
(2) sample surfaces bombardment activation treatment: the titanium alloy base material after polishing and TiAg alloy target material are placed in to magnetic-controlled sputtering coating equipment, are evacuated to 1 × 10
-4after Pa is following, close high threshold, pass into high-purity argon gas, air pressure is controlled at 5Pa.Open workpiece voltage, be controlled at-800V of workpiece voltage, carries out 20min ion bombardment sputter process, activated sample surface to workpiece.After end of bombardment, close voltage and gas, be evacuated to final vacuum;
(3) plated film: again pour argon gas, open workpiece power supply and source electrode power supply, slowly boosted voltage, in this process, adjust gradually voltage and gas pressure intensity, make be controlled at-100V of workpiece voltage, source voltage is controlled at 380V, and operating air pressure remains on 8Pa.After insulation 1h, close target power supply (being source electrode power supply), workpiece power supply and argon gas, continue to vacuumize, and treats that workpiece temperature is down to room temperature, closes water coolant, opens body of heater and take out sample.
(4) thermooxidizing and diffusion: the titanium alloy workpiece after surface coating is placed in retort furnace, and temperature to be heated rises to after 600 ℃ of preset temperatures, insulation 2h, powered-down, cool to room temperature, takes out sample.
By the prepared titanium alloy surface Ag doped Ti O of above-mentioned steps
2film, Fig. 1 shows this film surface microscopic appearance, and Fig. 2 is this film antibacterial effect figure, and Fig. 3 is that untreated titanium alloy contacts rear surface bacterium colony photo with bacterium.Comparison diagram 2, Fig. 3 can obtain, Ag doped Ti O prepared by the present invention
2film has good sterilization effect.
Fig. 4 is Ag doped Ti O
2the hardness comparison diagram of film and untreated titanium alloy.Untreated titanium alloy surface hardness is 220HV, Ag doped Ti O prepared by the present invention
2film hardness has reached 620HV, and the raising of hardness can improve the wear resisting property of titanium alloy.
Fig. 5 is Ag doped Ti O
2the solidity to corrosion comparison diagram of film and untreated titanium alloy.Untreated titanium alloy erosion rate is about 0.0025, Ag doped Ti O prepared by the present invention
2thin film corrosive speed is 0.0006, and solidity to corrosion is significantly improved.
Fig. 6 is Ag doped Ti O
2film surface Growth of Cells design sketch.
In embodiment of the present invention, take TiAg alloy target material as source electrode, adopt magnetron sputtering to prepare TiAg film at titanium alloy surface, can accurately control Ag content in film.By using the alloys target of heterogeneity, can form the TiAg film of different Ag content.Again the titanium alloy sample that has deposited TiAg film is placed in retort furnace and is heated, by controlling acid extraction, can prepare the Ag doped Ti O of different Ag content and weave construction
2film.Prepared film and matrix have good combination power, and have good antibacterial, wear-resisting, anti-corrosion and biocompatibility.
Claims (5)
1. a titanium alloy surface Ag doped Ti O
2the preparation method of film, it is characterized in that: first utilize magnetron sputtering technique to prepare TiAg film at titanium alloy surface, then in retort furnace, carry out thermal oxidative treatment, by being oxidized and spreading, form and be combined good Ag doped rutile type TiO with matrix at titanium alloy surface
2film.
2. titanium alloy surface Ag doped Ti O according to claim 1
2the preparation method of film, is characterized in that: comprise the following steps:
(1) magnetron sputtering plating
1. the titanium alloy base material after polishing and TiAg alloy target material are placed in to magnetic-controlled sputtering coating equipment, are evacuated to 1 × 10
-4after Pa is following, close high threshold, pass into high-purity argon gas, air pressure is controlled at 3～8Pa; Open workpiece voltage, be controlled at-800V of workpiece voltage, carries out 20min ion bombardment sputter process to workpiece; After cleaning finishes, close voltage and gas, be evacuated to final vacuum;
2. again pour argon gas, open workpiece power supply and source electrode power supply, slowly boosted voltage, adjusts voltage and gas pressure intensity gradually, makes be controlled at-100V of workpiece voltage, and source voltage is controlled at 350～450V, and operating air pressure remains on 6～10Pa; Plated film 20 ~ 120min, closes source class power supply, and workpiece power supply and argon gas continue to vacuumize, and treats that workpiece temperature is down to room temperature, closes water coolant, opens body of heater and takes out sample; Prepare TiAg film at titanium alloy surface;
(2) thermal oxidative treatment:
Titanium alloy workpiece after surface coating is placed in retort furnace, control Heating temperature be 400 ~ 1000 ℃, in air, there is thermooxidizing in TiAg film, and with matrix mutual diffusion, insulation 1 ~ 6h, powered-down, is cooled to room temperature, take out sample.
3. titanium alloy surface Ag doped Ti O according to claim 2
2the preparation method of film, is characterized in that: described TiAg alloy target material is to smelt and form according to following atomic ratio: the atomic percentage conc that the atomic percentage conc of Ag is 1% ~ 20%, Ti is 80% ~ 99%.
4. titanium alloy surface Ag doped Ti O according to claim 2
2the preparation method of film, is characterized in that: be 40 ~ 80min in the titanium alloy surface plated film time.
5. titanium alloy surface Ag doped Ti O according to claim 2
2the preparation method of film, is characterized in that: in retort furnace, Heating temperature is 600 ~ 800 ℃, and the thermooxidizing time is 2 ~ 4h.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105420680A (en) * | 2015-11-18 | 2016-03-23 | 太原理工大学 | Preparation method of pure titanium surface Ag/Sr co-doped TiO2 porous film |
| CN107779814A (en) * | 2017-08-31 | 2018-03-09 | 昆明贵金属研究所 | A kind of preparation method of the gradient of nano-particle containing Ag wear-resistant coating |
| WO2018067086A2 (en) | 2016-08-12 | 2018-04-12 | Istanbul Teknik Universitesi | Production method of a thick coating with layered structure |
| CN109487213A (en) * | 2018-11-20 | 2019-03-19 | 山东科技大学 | A kind of anti-corrosion antifouling film and preparation method thereof based on stainless steel |
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| WO2003003831A1 (en) * | 2001-07-06 | 2003-01-16 | Ceramatec, Inc. | Beneficial materials for topical or internal use by a human or other animal |
| CN1570196A (en) * | 2004-04-30 | 2005-01-26 | 麦桥 | Surface antibiotic, wearable stainless steel products and its production method |
| CN101717920A (en) * | 2009-12-29 | 2010-06-02 | 浙江大学 | Method for preparing composite Ag-Ti oxide antibacterial film by magnetron sputtering |
| CN103046056A (en) * | 2012-12-21 | 2013-04-17 | 太原理工大学 | Method for preparing Ag-Ti-O antibacterial nanotube film on surface of titanium alloy |
-
2014
- 2014-04-02 CN CN201410129298.6A patent/CN103911593B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003003831A1 (en) * | 2001-07-06 | 2003-01-16 | Ceramatec, Inc. | Beneficial materials for topical or internal use by a human or other animal |
| CN1570196A (en) * | 2004-04-30 | 2005-01-26 | 麦桥 | Surface antibiotic, wearable stainless steel products and its production method |
| CN101717920A (en) * | 2009-12-29 | 2010-06-02 | 浙江大学 | Method for preparing composite Ag-Ti oxide antibacterial film by magnetron sputtering |
| CN103046056A (en) * | 2012-12-21 | 2013-04-17 | 太原理工大学 | Method for preparing Ag-Ti-O antibacterial nanotube film on surface of titanium alloy |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105420680A (en) * | 2015-11-18 | 2016-03-23 | 太原理工大学 | Preparation method of pure titanium surface Ag/Sr co-doped TiO2 porous film |
| WO2018067086A2 (en) | 2016-08-12 | 2018-04-12 | Istanbul Teknik Universitesi | Production method of a thick coating with layered structure |
| DE112017004063T5 (en) | 2016-08-12 | 2019-06-06 | Istanbul Teknik Universitesi | Process for producing a thick coating with a layered structure |
| DE112017004063B4 (en) | 2016-08-12 | 2022-06-02 | Istanbul Teknik Universitesi | Process for producing a thick coating with a layered structure |
| CN107779814A (en) * | 2017-08-31 | 2018-03-09 | 昆明贵金属研究所 | A kind of preparation method of the gradient of nano-particle containing Ag wear-resistant coating |
| 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 |
| CN109487213A (en) * | 2018-11-20 | 2019-03-19 | 山东科技大学 | A kind of anti-corrosion antifouling film and preparation method thereof based on stainless steel |
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