CN102691088A - Method for fluorinion sedimentation and anode oxidization for improving bonding strength of titanium oxide nanotube on titanium-based surface - Google Patents
Method for fluorinion sedimentation and anode oxidization for improving bonding strength of titanium oxide nanotube on titanium-based surface Download PDFInfo
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- CN102691088A CN102691088A CN2012101523182A CN201210152318A CN102691088A CN 102691088 A CN102691088 A CN 102691088A CN 2012101523182 A CN2012101523182 A CN 2012101523182A CN 201210152318 A CN201210152318 A CN 201210152318A CN 102691088 A CN102691088 A CN 102691088A
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Abstract
The invention discloses a method for fluorinion sedimentation and anode oxidization for improving bonding strength of a titanium oxide nanotube layer on a titanium-based surface. The method comprises the steps of preparing fluoride salt electrolyte for anode oxidization of a titanium or a titanium alloy substrate to obtain a TiO2 nanotube, adding magnesium salt solution into the electrolyte, and gradually settling the fluorinions in the electrolyte, wherein the electrolyte used for fluorinion sedimentation is magnesium salt ethylene glycol solution. According to the invention, a self-assembly titanium oxide nanotube layer with firm combination and a certain thickness can be formed on the surface of the titanium or the titanium alloy. A film layer is 5-30 microns thick, a compact TiO2 nano-crystal grain transition layer with the thickness of about 0.15-0.3 micron is formed between the nanotube and the titanium base, no titanium fluoride is provided, and a bonding strength Lc between the TiO2 nanotube layer and the titanium base is increased to 12-18 N from about 3 N in sedimentation process in the absence of a fluorinion.
Description
Technical field
The invention belongs to the titanium-based surface processing technology field, especially a kind of fluorion sedimentation anode oxidation method, this method can be improved the bonding strength of titanium or titanium alloy surface titania nanotube.
Background technology
Titanium and alloy thereof have good corrosion-resistant, mechanical property, biocompatibility etc. and are widely used in hard tissue repair and replacement field.Yet titanium and alloy lifeless matter thereof are active, can not with the bone forming Chemical bond, must carry out surface-treated to obtain biological activity.With respect to the fine and close form of same material, nanotube-shaped can the promotion osteoblasticly sticked and breeds; In the implantation animal body, can and promote the formation of new bone with the bone forming Chemical bond.Simultaneously, nanotube has big specific surface area, and as carrier, nano tube supported resisting/biocidal efficacies component such as antimicrobial factorses such as Ag, qingfengmeisu qiong prevent the osseous tissue gangrene; Biologically active factorss such as load bone morphogenetic protein, RGD peptide are for the sticking of cell, breed, break up good interface is provided.The high-specific surface area of nanotube and unique nanostructure make it be considered to planting body, fill the ideal material of biologic applications aspects such as formula drug delivery system, organizational project.
Up to now, though anonizing prepares the research of oxide nano in the metallic surface a large amount of reports is arranged, mostly that touches is properties relation such as electrochemical parameter, structure, optics, biology; Though have few studies to disclose the mechanics parameter such as hardness, Young's modulus of nanotube, the bonding strength between nanotube and the matrix is extremely low, peels off often, this has become its actual key in application problem that limits.Know that adding fluorion in the electrolytic solution is that anonizing prepares the good TiO of arrayed
2The prerequisite of nanotube.Discover: in anode oxidation process, the fluorion in the electrolytic solution is prone to pass TiO
2The nanotube bottom is at TiO
2/ Ti enrichment and form one deck titanium fluoride soluble in water at the interface, this existence of fluoridizing titanium layer is TiO
2The root of nanotube films film-substrate binding strength difference.Though propose at present to form the micron order groove scheme the mechanical riveted of enhancing nanotube layer and matrix at matrix surface through laser processing, or through the thermal treatment after the anodic oxidation to scheme combining between enhancing nanotube layer and the metallic matrix, produce little effect.This shows that though the nanotube of existing anode oxidation process preparation has excellent biology performance, under the carrying situation, be on active service, small shearing force can both make between nanotube and the metallic matrix and peel off, and causes the inefficacy of rete.In view of above consideration, the TiO that anodic oxidation is prepared
2The exploitation of bonding strength improvement method between nanotube and the titanium or titanium alloy has become decision TiO
2Nanotube can practical application key.
Summary of the invention
The objective of the invention is to overcome the shortcoming of above-mentioned prior art, a kind of fluorion sedimentation anode oxidation method is provided, this method can combine firmly, have certain thickness self-assembly titanium oxide nanotubes layer at titanium or titanium alloy surface generation.The thicknesses of layers of gained is 5～30 microns, is thick about 0.15 ~ 0.3 micron fine and close TiO between nanotube and the titanium base
2The nanocrystal transition layer does not exist and fluoridizes titanium layer, TiO
2The about 3N of bonding strength Lc value between nanotube layer and the titanium base (scratch method survey) during by floride-free ionic operation is increased to 12 ~ 18N.
The objective of the invention is to solve through following technical scheme:
This fluorion sedimentation anode oxidation method is: preparation fluoride salt used for electrolyte obtains TiO in titanium or titanium alloy substrate anodic oxidation
2Behind the nanotube, in electrolytic solution, add magnesium salt solution, the fluorion in the electrolytic solution is carried out progressively sedimentation; Wherein being used for the settled ionogen of fluorion is: the magnesium salts ethylene glycol solution.
Further; Above method concrete operations are: in fluoride salt solution, be anode with titanium or titanium alloy, graphite rod is a negative electrode, and used power supply is a direct supply; In constant voltage is 60 volts; Distance between the anode and cathode is 5 ~ 8 centimetres, and titanium or titanium alloy are carried out anodize, and the treatment time is 5 ~ 60 minutes; Then; Speed with 0.005 ~ 2 volt of per second boosts to 80 ~ 140 volts to the anode and cathode two ends; And in electrolytic solution, add magnesium salts with the speed of 5 ~ 50 milliliters of per seconds; The amount of adding magnesium salts in every liter of electrolytic solution is 0.02 ~ 0.16 mole, and in electrolytic solution, adding magnesium salts is to carry out with the form of magnesium salt solution; Treatment time is 30 ~ 120 minutes.
Magnesium salts in the above-mentioned magnesium salt solution is a kind of of magnesium acetate, magnesium chloride, sal epsom, magnesium nitrate or it is composite; Said magnesium salt solution is to be that solvent, magnesium salts are that the concentration that solute is prepared is the solution of 0.1 ~ 0.8M with terepthaloyl moietie.
The TiO of above gained
2Thicknesses of layers is 5 ~ 30 microns, and the top layer is the TiO that self-assembly forms
2Nanotube, TiO
2Be fine and close TiO between nanotube and the titanium base
2The nanocrystal transition layer.
The present invention has following beneficial effect:
1. anode oxidation method of the present invention is easy to control, and the anodic oxidation electrolyte composition is simple, process stabilizing.
2. the thicknesses of layers that adopts the present invention to make is 5～30 microns, through the prolongation treatment time film thickness is further increased as required, and surface and section SEM pattern photo show that the rete upper strata is TiO
2Nanotube is thick about 0.15 ~ 0.3 micron fine and close TiO between nanotube and the titanium base
2The nanocrystal transition layer does not exist and fluoridizes titanium layer, and the about 3N when scratch method is surveyed the rete critical load Lc by floride-free ionic operation is increased to 12 ~ 18N.
3. the rete that adopts the present invention to make is by main amorphous TiO
2Constitute.
4. raw material of the present invention is easy to get, cheap, constant voltage oxidation, simple to operate.
Description of drawings
Fig. 1 uses the surface topography SEM photo of the present invention through fluorion sedimentation anodize gained rete (embodiment 1 rete).
Fig. 2 uses scratch test acoustic emission signal and the cut pattern of the present invention through fluorion sedimentation anodize gained rete (embodiment 1 rete).
Fig. 3 uses the surface topography SEM photo of the present invention through fluorion sedimentation anodize gained rete (embodiment 2 retes).
Fig. 4 uses scratch test acoustic emission signal and the cut pattern of the present invention through fluorion sedimentation anodize gained rete (embodiment 2 retes).
Fig. 5 uses the surface topography SEM photo of the present invention through fluorion sedimentation anodize gained rete (embodiment 3 retes).
Fig. 6 uses the xsect pattern SEM photo of the present invention through fluorion sedimentation anodize gained rete (embodiment 3 retes).
Fig. 7 uses scratch test acoustic emission signal and the cut pattern of the present invention through fluorion sedimentation anodize gained rete (embodiment 3 retes).
Embodiment
Fluorion sedimentation anode oxidation method of the present invention is: preparation fluoride salt used for electrolyte obtains TiO in titanium or titanium alloy substrate anodic oxidation
2Behind the nanotube, in electrolytic solution, add magnesium salt solution, the fluorion in the electrolytic solution is carried out progressively sedimentation; Wherein being used for the settled ionogen of fluorion is: the magnesium salts ethylene glycol solution.
Below in conjunction with accompanying drawing and embodiment the present invention is done and to describe in further detail:
Embodiment 1:
Preparing electrolyte contains 0.08M NH for (1) 250 milliliter
4F+2wt.%H
2The ethylene glycol solution of O is used for the titanium alloy substrate anodic oxidation and obtains TiO
2Nanotube, preparing electrolyte contains 0.06M (CH for (2) 50 milliliters
3COO)
2Mg is used for the fluorion sedimentation and improves film substrate bond strength.
With the titanium is that anode, graphite rod are negative electrode, adopts direct supply, in electrolytic solution (1), is that 60 volts, cathode-anode plate spacing are to carry out anodize 60 minutes under 8 centimetres the condition in constant voltage; Adopt the drop rate of 5 milliliters of per seconds in electrolytic solution, to drip electrolytic solution (2); Adopt the rate of pressure rise of 0.005 volt of per second simultaneously; The anode and cathode two ends are boosted to 80 volts, pressurize 60 minutes, the film substrate bond strength Lc value of the anode oxidation membrane that forms at matrix surface is 12.4N.Its surface microscopic topographic SEM photo is consulted Fig. 1, and the acoustic emission signal of scratch test and cut pattern SEM photo are consulted Fig. 2.
Embodiment 2:
Preparing electrolyte contains 0.08M NH for (1) 250 milliliter
4F+2wt.%H
2The ethylene glycol solution of O is used for the titanium alloy substrate anodic oxidation and obtains TiO
2Nanotube, preparing electrolyte contains 0.06M (CH for (2) 50 milliliters
3COO)
2Mg is used for the fluorion sedimentation and improves film substrate bond strength.
With the titanium is that anode, graphite rod are negative electrode, adopts direct supply, in electrolytic solution (1), is that 60 volts, cathode-anode plate spacing are to carry out anodize 60 minutes under 8 centimetres the condition in constant voltage; Adopt the drop rate of 5 milliliters of per seconds in electrolytic solution, to drip electrolytic solution (2); Adopt the rate of pressure rise of 0.005 volt of per second simultaneously; The anode and cathode two ends are boosted to 80 volts, pressurize 90 minutes, the film substrate bond strength Lc value of the anode oxidation membrane that forms at matrix surface is 11N.Its surface microscopic topographic SEM photo is consulted Fig. 3, and the acoustic emission signal of scratch test and cut pattern SEM photo are consulted Fig. 4.
Embodiment 3:
Preparing electrolyte contains 0.08M NH for (1) 250 milliliter
4F+2wt.%H
2The ethylene glycol solution of O is used for the titanium alloy substrate anodic oxidation and obtains TiO
2Nanotube, preparing electrolyte contains 0.06M (CH for (2) 50 milliliters
3COO)
2Mg is used for the fluorion sedimentation and improves film substrate bond strength.
With the titanium is that anode, graphite rod are negative electrode, adopts direct supply, in electrolytic solution (1), is that 60 volts, cathode-anode plate spacing are to carry out anodize 60 minutes under 8 centimetres the condition in constant voltage; Adopt the drop rate of 5 milliliters of per seconds in electrolytic solution, to drip electrolytic solution (2); Adopt the rate of pressure rise of 0.005 volt of per second simultaneously; The anode and cathode two ends are boosted to 80 volts, pressurize 70 minutes, the film substrate bond strength Lc value of the anode oxidation membrane that forms at matrix surface is 17.6N.Its surface microscopic topographic SEM photo is consulted Fig. 5, and section microscopic appearance SEM photo is consulted Fig. 6, and the acoustic emission signal of scratch test and cut pattern SEM photo are consulted Fig. 7.
Embodiment 4
In the present embodiment, in fluoride salt solution, be anode with titanium or titanium alloy, graphite rod is a negative electrode; Used power supply is a direct supply; In constant voltage is that distance between 60 volts, anode and cathode is under 5 centimetres the condition, and titanium or titanium alloy are carried out anodize, and the treatment time is 5 minutes; Then; Speed with 0.005 volt of per second boosts to 80 volts to the anode and cathode two ends, and in electrolytic solution, adds magnesium salts with the speed of 5 milliliters of per seconds, and wherein magnesium salts is selected magnesium acetate; The amount of adding magnesium salts in every liter of electrolytic solution is 0.02 mole, and the treatment time is 30 minutes.In electrolytic solution, adding magnesium salts is to carry out with the form of magnesium salt solution, and this magnesium salt solution is to be that solvent, magnesium salts are that the concentration that solute is prepared is the solution of 0.1M with terepthaloyl moietie.
In the present embodiment, in fluoride salt solution, be anode with titanium or titanium alloy, graphite rod is a negative electrode; Used power supply is a direct supply; In constant voltage is that distance between 60 volts, anode and cathode is under 8 centimetres the condition, and titanium or titanium alloy are carried out anodize, and the treatment time is 60 minutes; Then; Speed with 2 volts of per seconds boosts to 140 volts to the anode and cathode two ends, and in electrolytic solution, adds magnesium salts with the speed of 50 milliliters of per seconds, wherein magnesium salts selective chlorination magnesium; The amount of adding magnesium salts in every liter of electrolytic solution is 0.16 mole, and the treatment time is 120 minutes.In electrolytic solution, adding magnesium salts is to carry out with the form of magnesium salt solution, and this magnesium salt solution is to be that solvent, magnesium salts are that the concentration that solute is prepared is the solution of 0.8M with terepthaloyl moietie.
Embodiment 6
In the present embodiment, in fluoride salt solution, be anode with titanium or titanium alloy, graphite rod is a negative electrode; Used power supply is a direct supply; In constant voltage is that distance between 60 volts, anode and cathode is under 6 centimetres the condition, and titanium or titanium alloy are carried out anodize, and the treatment time is 10 minutes; Then; Speed with 0.01 volt of per second boosts to 90 volts to the anode and cathode two ends, and in electrolytic solution, adds magnesium salts with the speed of 10 milliliters of per seconds, and wherein magnesium salts is selected sal epsom; The amount of adding magnesium salts in every liter of electrolytic solution is 0.08 mole, and the treatment time is 60 minutes.In electrolytic solution, adding magnesium salts is to carry out with the form of magnesium salt solution, and this magnesium salt solution is to be that solvent, magnesium salts are that the concentration that solute is prepared is the solution of 0.3M with terepthaloyl moietie.
Embodiment 7
In the present embodiment, in fluoride salt solution, be anode with titanium or titanium alloy, graphite rod is a negative electrode; Used power supply is a direct supply; In constant voltage is that distance between 60 volts, anode and cathode is under 7 centimetres the condition, and titanium or titanium alloy are carried out anodize, and the treatment time is 30 minutes; Then; Speed with 1 volt of per second boosts to 120 volts to the anode and cathode two ends, and in electrolytic solution, adds magnesium salts with the speed of 30 milliliters of per seconds, and wherein magnesium salts is selected magnesium nitrate; The amount of adding magnesium salts in every liter of electrolytic solution is 0.1 mole, and the treatment time is 100 minutes.In electrolytic solution, adding magnesium salts is to carry out with the form of magnesium salt solution, and this magnesium salt solution is to be that solvent, magnesium salts are that the concentration that solute is prepared is the solution of 0.6M with terepthaloyl moietie.
Embodiment 8
In the present embodiment, in fluoride salt solution, be anode with titanium or titanium alloy, graphite rod is a negative electrode; Used power supply is a direct supply; In constant voltage is that distance between 60 volts, anode and cathode is under 7 centimetres the condition, and titanium or titanium alloy are carried out anodize, and the treatment time is 30 minutes; Then; Speed with 1 volt of per second boosts to 120 volts to the anode and cathode two ends; And in electrolytic solution, add magnesium salts with the speed of 30 milliliters of per seconds; Wherein magnesium salts is selected wherein one or more composite of magnesium acetate, magnesium chloride, sal epsom, magnesium nitrate, and the amount of adding magnesium salts in every liter of electrolytic solution is 0.1 mole, and the treatment time is 100 minutes.In electrolytic solution, adding magnesium salts is to carry out with the form of magnesium salt solution, and this magnesium salt solution is to be that solvent, magnesium salts are that the concentration that solute is prepared is the solution of 0.6M with terepthaloyl moietie.
Embodiment can give an example many, as space is limited, does not list one by one here.In a word, in scope provided by the invention, can prepare at titanium-based surface and combine firmly, certain thickness titania nanotube layer is arranged, greatly improve titanium and alloy thereof and implant or the practical application of aspect such as pharmaceutical carrier in sclerous tissues.
In sum, the TiO of gained of the present invention
2Thicknesses of layers is 5 ~ 30 microns, and the top layer is the TiO that self-assembly forms
2Nanotube, TiO
2It between nanotube and the titanium base compact nanometer crystal grain transition layer.
Claims (4)
1. a fluorion sedimentation anode oxidation method that improves titanium-based surface titanium oxide nanotubes layer bonding strength is characterized in that, preparation fluoride salt used for electrolyte obtains TiO in titanium or titanium alloy substrate anodic oxidation
2Behind the nanotube, in electrolytic solution, add magnesium salt solution, the fluorion in the electrolytic solution is carried out progressively sedimentation; Wherein being used for the settled ionogen of fluorion is: the magnesium salts ethylene glycol solution.
2. fluorion sedimentation anode oxidation method according to claim 1 is characterized in that, is specially: in fluoride salt solution, be anode with titanium or titanium alloy; Graphite rod is a negative electrode; Used power supply is a direct supply, and constant voltage is 60 volts, and the distance between the anode and cathode is 5 ~ 8 centimetres; Titanium or titanium alloy are carried out anodize, and the treatment time is 5 ~ 60 minutes; Then; Speed with 0.005 ~ 2 volt of per second boosts to 80 ~ 140 volts to the anode and cathode two ends; And in electrolytic solution, add magnesium salts with the speed of 5 ~ 50 milliliters of per seconds; The amount of adding magnesium salts in every liter of electrolytic solution is 0.02 ~ 0.16 mole, and in electrolytic solution, adding magnesium salts is to carry out with the form of magnesium salt solution; Treatment time is 30 ~ 120 minutes.
3. fluorion sedimentation anode oxidation method according to claim 2 is characterized in that, the magnesium salts in the said magnesium salt solution is a kind of of magnesium acetate, magnesium chloride, sal epsom, magnesium nitrate or it is composite; Said magnesium salt solution is to be that solvent, magnesium salts are that the concentration that solute is prepared is the solution of 0.1 ~ 0.8M with terepthaloyl moietie.
4. according to any described fluorion sedimentation anode oxidation method of claim 1-3, it is characterized in that the TiO of gained
2Thicknesses of layers is 5 ~ 30 microns, and the top layer is the TiO that self-assembly forms
2Nanotube, TiO
2Between nanotube layer and the titanium base thick 0.15 ~ 0.3 micron fine and close TiO
2The nanocrystal transition layer does not exist and fluoridizes titanium layer, TiO
2The about 3N of bonding strength Lc value between nanotube layer and the titanium base during by floride-free ionic operation is increased to 12 ~ 18N.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2021093791A1 (en) * | 2019-11-12 | 2021-05-20 | 中国科学院深圳先进技术研究院 | Anodized titanium dioxide nanotube array and preparation method therefor |
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| US5185075A (en) * | 1990-10-25 | 1993-02-09 | The Alta Group | Surface treated titanium/titanium alloy articles and process for producing |
| CN101660189A (en) * | 2008-08-28 | 2010-03-03 | 中国科学院合肥物质科学研究院 | Branch controllable titanium dioxide nanotube array film and preparation method thereof |
| CN102220616A (en) * | 2011-05-26 | 2011-10-19 | 东南大学 | Method for preparing titanium dioxide nanotube array |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5185075A (en) * | 1990-10-25 | 1993-02-09 | The Alta Group | Surface treated titanium/titanium alloy articles and process for producing |
| CN101660189A (en) * | 2008-08-28 | 2010-03-03 | 中国科学院合肥物质科学研究院 | Branch controllable titanium dioxide nanotube array film and preparation method thereof |
| CN102220616A (en) * | 2011-05-26 | 2011-10-19 | 东南大学 | Method for preparing titanium dioxide nanotube array |
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|---|
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2021093791A1 (en) * | 2019-11-12 | 2021-05-20 | 中国科学院深圳先进技术研究院 | Anodized titanium dioxide nanotube array and preparation method therefor |
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