CN103911593B - A kind of titanium alloy surface Ag doped Ti O 2the preparation method of film - Google Patents
A kind of titanium alloy surface Ag doped Ti O 2the preparation method of film Download PDFInfo
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- CN103911593B CN103911593B CN201410129298.6A CN201410129298A CN103911593B CN 103911593 B CN103911593 B CN 103911593B CN 201410129298 A CN201410129298 A CN 201410129298A CN 103911593 B CN103911593 B CN 103911593B
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Abstract
The present invention discloses a kind of titanium alloy surface Ag doped Ti O
2the preparation method of film, belongs to technical field of metal material surface modification.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, formed with matrix in conjunction with good Ag doped rutile type TiO at titanium alloy surface
2film.Compared with prior art, the film of preparation not only has good bonding force with matrix, and solidity to corrosion and wear resistance significantly improve; Solve titanium alloy easily causes bacteriological infection in human body problem as implant; Also can stop the release of harmful element in titanium alloy substrate, there is good biocompatibility; The method is simple to operate, reproducible, 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 technical field of metal material surface modification.
Background technology
Titanium alloy has the advantages such as density is low, corrosion-resistant close to people's bone, Young's modulus, 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, easily cause bacteriological infection when Clinical practice in implant into body, thus cause graft failure.Inorganic antiseptic is because have the antibacterial ability that good antibacterial ability and thermostability are widely used for improving biomaterial.In all inorganic antiseptics, Ag, as a kind of broad spectrum antimicrobicide, has efficient antibacterial ability, and suitable Ag content does not have toxicity to cell, thus receives the extensive concern of investigator.
Some process for modifying surface of current employing, as ion implantation, plated film, chemosynthesis etc., can form at titanium alloy surface the antibacterial modified layer containing Ag.But as embedded material, in use also want taking up wear, corrosion and synergistic infringement thereof.Prepared by these methods above-mentioned 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.At TiO prepared by metal material surface
2modified layer, except having good photocatalysis performance, also has excellent anticorrosive and wear resisting property.TiO is prepared 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 being CN1557990A as publication number discloses the one " Ag/TiO that contact angle is adjustable
2laminated film and preparation method thereof ", the method is devoted to the anti-fog thin film that preparation table mask has hydrophobicity performance.Ag doped Ti O is prepared at titanium alloy surface according to this method
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 cause " target poison ing ", 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 with matrix in conjunction with good Ag doped Ti O at titanium alloy surface by the method
2film, makes matrix have excellent antibacterial, anti-corrosion, wear-resisting and biocompatibility, solves titanium alloy easily causes bacteriological infection problem as implant, and avoid the problem of the easy loss failure of traditional antibacterial film when Clinical practice.
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, is formed with matrix in conjunction with good Ag doped rutile type TiO 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 magnetic-controlled sputtering coating equipment, are evacuated to 1 × 10
-4after below Pa, close high threshold, pass into high-purity argon gas, air pressure controls at 3 ~ 8Pa; Open workpiece voltage, workpiece voltage controls at-800V, carries out 20min ion bombardment sputter process to workpiece; After cleaning terminates, close voltage and gas, be evacuated to final vacuum;
2. again pour argon gas, open workpiece power supply and source electrode power supply, slow boosted voltage, adjust voltage and gas pressure intensity gradually, make workpiece voltage control at-100V, source voltage controls at 350 ~ 450V, and operating air pressure remains on 6 ~ 10Pa; Plated film 20 ~ 120min, close source class 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; TiAg film has been prepared 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 DEG C, there is thermooxidizing in atmosphere 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 smelts according to following atomic ratio to form: the atomic percentage conc of Ag is the atomic percentage conc of 1%-20%, Ti is 80%-99%.
Further, 40 ~ 80min is preferably in the titanium alloy surface plated film time.
Further, in retort furnace, Heating temperature is preferably 600 ~ 800 DEG C, and thermal oxidation 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, effectively controls the Ag content in film; Then the titanium alloy sample that deposited TiAg film being placed in retort furnace and heating, by controlling Heating temperature, Ti, Ag and the matrix generation mutual diffusion of deposition can be made on the one hand, the bonding force of enhanced film and matrix; Directly utilize the oxygen in air and TiAg film to react on the other hand, 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 thermal oxidative treatment heated perimeter in the stable and retort furnace of thin-film technique controlled, and can complete the feature of oxidation and mutual diffusion simultaneously, has good process repeatability, the advantage that film quality is controlled;
(2) Ag doped Ti O is formed at titanium alloy surface
2film, solves titanium alloy easily causes bacteriological infection in human body problem 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 prepared 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 balance scheme.
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, TiAg alloy target material is used to be source electrode, utilize the low-temperature plasma that glow discharge produces, by bombardment source electrode surface, make preplating metallic element from source electrode surface sputtering out, be deposited on titanium alloy surface through transport 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 of concrete enforcement doped Ti O
2the technical scheme of the preparation method of film is: first, by using the alloy target material of different Ag content, forms 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 prepares: titanium alloy sample being processed into diameter is 20mm, and thickness is the disk of 4mm, and polishing, is taken up in order of priority sample after polishing and puts into acetone, ethanol and deionized water, ultrasonic cleaning 5min successively, drying for standby.
(2) sample surfaces bombardment activation treatment: the titanium alloy base material after polishing and TiAg alloy target material are placed in magnetic-controlled sputtering coating equipment, are evacuated to 1 × 10
-4after below Pa, close high threshold, pass into high-purity argon gas, air pressure controls at 5Pa.Open workpiece voltage, workpiece voltage controls at-800V, carries out 20min ion bombardment sputter process to workpiece, activated sample surface.After end of bombardment, close voltage and gas, be evacuated to final vacuum;
(3) plated film: again pour argon gas, opens workpiece power supply and source electrode power supply, slow boosted voltage, in the process, adjust voltage and gas pressure intensity gradually, make workpiece voltage control at-100V, source voltage controls at 380V, and operating air pressure remains on 8Pa.After insulation 1h, close target power supply (i.e. 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: be placed in retort furnace by the titanium alloy workpiece after surface coating, after temperature to be heated rises to preset temperature 600 DEG C, insulation 2h, powered-down, cool to room temperature, takes out sample.
By the titanium alloy surface Ag doped Ti O prepared by above-mentioned steps
2film, Fig. 1 shows this film surface microscopic appearance, and Fig. 2 is this film antibacterial effect figure, 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 balance of film and untreated titanium alloy schemes.Untreated titanium alloy surface hardness is 220HV, Ag doped Ti O prepared by the present invention
2film hardness reaches 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, with TiAg alloy target material for 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, the TiAg film of different Ag content can be formed.Again the titanium alloy sample that deposited TiAg film being placed in retort furnace and heating, by controlling acid extraction, the Ag doped Ti O of different Ag content and weave construction can be prepared
2film.Prepared film and matrix have good combination power, and have excellent antibacterial, wear-resisting, anti-corrosion and biocompatibility.
Claims (4)
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, formed with matrix in conjunction with good Ag doped rutile type TiO at titanium alloy surface
2film; Comprise the following steps:
(1) magnetron sputtering plating
1. the titanium alloy base material after polishing and TiAg alloy target material are placed in magnetic-controlled sputtering coating equipment, are evacuated to 1 × 10
-4after below Pa, close high threshold, pass into high-purity argon gas, air pressure controls at 3 ~ 8Pa; Open workpiece voltage, workpiece voltage controls at-800V, carries out 20min ion bombardment sputter process to workpiece; After cleaning terminates, close voltage and gas, be evacuated to final vacuum;
2. again pour argon gas, open workpiece power supply and source electrode power supply, slow boosted voltage, adjust voltage and gas pressure intensity gradually, make workpiece voltage control at-100V, source voltage controls at 350 ~ 450V, and operating air pressure remains on 6 ~ 10Pa; Plated film 20 ~ 120min, close source class 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; TiAg film has been prepared 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 DEG C, there is thermooxidizing in atmosphere in TiAg film, and with matrix mutual diffusion, insulation 1 ~ 6h, powered-down, is cooled to room temperature, take out sample.
2. titanium alloy surface Ag doped Ti O according to claim 1
2the preparation method of film, is characterized in that: described TiAg alloy target material smelts according to following atomic ratio to form: the atomic percentage conc of Ag is the atomic percentage conc of 1% ~ 20%, Ti is 80% ~ 99%.
3. titanium alloy surface Ag doped Ti O according to claim 1
2the preparation method of film, is characterized in that: be 40 ~ 80min in the titanium alloy surface plated film time.
4. titanium alloy surface Ag doped Ti O according to claim 1
2the preparation method of film, is characterized in that: in retort furnace, Heating temperature is 600 ~ 800 DEG C, and thermal oxidation time is 2 ~ 4h.
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| 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 |
| DE112017004063B4 (en) | 2016-08-12 | 2022-06-02 | Istanbul Teknik Universitesi | Process for producing a thick coating with a layered structure |
| 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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|---|---|---|---|---|
| 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 |
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| US20030026848A1 (en) * | 2001-07-06 | 2003-02-06 | Joshi Ashok V. | Beneficial materials for topical or internal use by a human or other animal |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
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