CN104313661B - A kind of TiO of Ca and Si codope2film - Google Patents
A kind of TiO of Ca and Si codope2film Download PDFInfo
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Abstract
The invention discloses the TiO of a kind of Ca and Si codope2Film, the TiO of described Ca and Si codope2In film, the atomic percentage conc of Ca is 0.4%～0.8%, and the atomic percentage conc of Si is 2.0%～3.0%, the TiO of described Ca and Si codope2Film is less than 28 ° with the contact angle of water, the TiO of described Ca and Si codope2The preparation method of film comprises the following steps: one, by matrix carborundum paper polishing light, uses ethanol and acetone to clean and dry the most successively；Two, the matrix after drying is as anode, and platinized platinum is negative electrode, then matrix and platinized platinum is concurrently placed in electrolyte and carries out anodized, obtains the TiO of Ca and Si codope2Film.The TiO of Ca and the Si codope of the present invention2Membrane preparation method is simple, and hydrophilicity is excellent, hardness is high, and corrosion resistance is good, and antiwear property is strong.
Description
Technical field
The invention belongs to nano material technology and technical field of biological materials, be specifically related to the TiO of a kind of Ca and Si codope2Film.
Background technology
Titanium or titanium alloy has high specific strength, biocompatibility and corrosion resistance, and its application is the most wide.At present, titanium or titanium alloy is owing to having good biocompatibility, and density close with people's bone strength is light, can be as implants such as titanium or titanium alloy bone clamping plate, for the reparation of human body hard tissue damage.
Titanium base or titanium alloy substrate at the one layer of densification of its Surface Creation or the titanium oxide film layer of porous, owing to this film layer can improve the biocompatibility of titanium or titanium alloy, have become as current study hotspot by anodic oxidation.Additionally, the TiO that Titanium base or titanium alloy-based surface obtain2Film layer, is effectively improved the intensity of titanium or titanium alloy, adds the wear-resisting of titanium or titanium alloy and corrosion resistance.
The surface of Titanium base or titanium alloy substrate uses anodic oxidation typically can only obtain TiO2Film layer, is especially adapted for use in biologic implant application, and for modified TiO2The research of film layer is the most fewer, only has minority literature research micro-arc oxidation to prepare Ca doping TiO at present2Film, to improve the biocompatibility of film.Therefore, research and develop and a kind of i.e. there is good biocompatibility there is again the functional TiO of high intensity2Film is of great significance for the application tool of titanium and titanium alloy.
Summary of the invention
The technical problem to be solved is for above-mentioned the deficiencies in the prior art, it is provided that the TiO of a kind of Ca and Si codope2Film.The TiO of this Ca and Si codope2The hardness of film reaches more than 700HV, has good wearability and high corrosion resistance, the simultaneously TiO of this Ca and Si codope2Film surface hydrophilicity is good, has excellent biologically active, can be applicable to the reparation of human body hard tissue damage.
For solving above-mentioned technical problem, the technical solution used in the present invention is: the TiO of a kind of Ca and Si codope2Film, it is characterised in that the TiO of described Ca and Si codope2In film, the atomic percentage conc of Ca is 0.4%～0.8%, and the atomic percentage conc of Si is 2.0%～3.0%, the TiO of described Ca and Si codope2Film is less than 28 ° with the contact angle of water；The TiO of described Ca and Si codope2The preparation method of film comprises the following steps:
Step one, matrix is polished light with 280 mesh, 600 mesh and 1200 mesh carborundum papers successively, use ethanol and acetone to clean and dry the most successively；Described matrix is Titanium base or titanium alloy substrate；
Step 2, will in step one dry after matrix as anode, matrix and platinized platinum, as negative electrode, are then concurrently placed in electrolyte by platinized platinum, are 20V～80V at voltage, electrolyte temperature is anodized 0.5h～8h under conditions of 10 DEG C～30 DEG C, obtains the TiO of Ca and Si codope2Film；Containing 5g～20g sodium oxalate in every liter of described electrolyte, 3g～8g sodium dihydrogen phosphate, 1g～3g sodium metasilicate and 3g～8g calcium hydroxide, surplus is water；Or containing 5g～20g sodium oxalate in every liter of described electrolyte, 0.5g～2g ammonium fluoride, 1g～3g sodium metasilicate and 3g～8g calcium hydroxide, surplus is water.
The TiO of above-mentioned a kind of Ca and Si codope2Film, it is characterised in that voltage described in step 2 is 50V～60V, electrolyte temperature is 15 DEG C～25 DEG C, and the time of anodized is 3.5h～5.5h.
The TiO of above-mentioned a kind of Ca and Si codope2Film, it is characterised in that when in electrolyte described in step 2 containing sodium dihydrogen phosphate, the TiO of prepared Ca and Si codope2Film is dense film.
The TiO of above-mentioned a kind of Ca and Si codope2Film, it is characterised in that the thickness of described dense film is 3 μm～5 μm.
The TiO of above-mentioned a kind of Ca and Si codope2Film, it is characterised in that when in electrolyte described in step 2 containing ammonium fluoride, the TiO of prepared Ca and Si codope2Film is perforated membrane.
The TiO of above-mentioned a kind of Ca and Si codope2Film, it is characterised in that the aperture of described perforated membrane is 30nm～50nm, thickness is 3 μm～5 μm.
The present invention compared with prior art has the advantage that
1, the TiO of Ca and the Si codope of the present invention2Film has high hardness, and its hardness reaches more than 700HV, simultaneously this TiO2Film corrosion resistance is good, and antiwear property is strong.
2, the TiO of Ca and the Si codope of the present invention2Film is less than 28 ° with the contact angle of water, shows this TiO2The hydrophilicity of film is excellent, has good biocompatibility.
3, the TiO of Ca and the Si codope of the preparation present invention2The raw materials used wide material sources of film, being easy to get, preparation process is simple, and in preparation process, the shape to Titanium base or titanium alloy substrate is not limited, and all can obtain the TiO of Ca and Si codope in its surface2Film.
4, Ca and Si is successfully doped to TiO by the present invention2On film, high rigidity and the TiO of biocompatibility preferable Ca and Si codope can be prepared according to different electrolyte prescriptions2Dense film and the TiO of Ca and Si codope2Perforated membrane.The TiO of Ca and Si codope2The thickness of dense film is 3 μm～5 μm, the TiO of Ca and Si codope2The aperture of perforated membrane is 30nm～50nm, and thickness is 3 μm～5 μm, and both films are both less than 28 ° with the contact angle of water, meets the needs being applied to repair human body hard tissue of titanium and titanium alloy.
Below by drawings and Examples, technical scheme is described in further detail.
Accompanying drawing explanation
Fig. 1 is the TiO of Ca and the Si codope of the embodiment of the present invention 1 preparation2The XPS spectrum figure of dense film.
Fig. 2 is the TiO of Ca and the Si codope of the embodiment of the present invention 1 preparation2The scanning electron microscope (SEM) photograph of dense membrane surface.
Fig. 3 is the TiO of Ca and the Si codope that the embodiment of the present invention 1 is prepared in TA1 titanium sheet2The scanning electron microscope (SEM) photograph in dense film cross section.
Fig. 4 is the TiO of Ca and the Si codope of the embodiment of the present invention 1 preparation2The contact angle test photo of dense film.
Fig. 5 is the TiO of Ca and the Si codope of the embodiment of the present invention 2 preparation2The scanning electron microscope (SEM) photograph of porous film surface.
Fig. 6 is the TiO of Ca and the Si codope that the embodiment of the present invention 2 is prepared in TA1 titanium sheet2The scanning electron microscope (SEM) photograph in perforated membrane cross section.
Detailed description of the invention
Embodiment 1
The TiO of Ca and the Si codope of the present embodiment2In film, the atomic percentage conc of Ca is 0.53%, and the atomic percentage conc of Si is 2.86%, the TiO of described Ca and Si codope2Film is 21.3 ° with the contact angle of water；The TiO of described Ca and Si codope2The preparation method of film comprises the following steps:
Step one, TA1 titanium sheet that specification is 10mm × 10mm is polished light with 280 mesh, 600 mesh and 1200 mesh carborundum papers successively, use ethanol and acetone to clean and dry the most successively；
Step 2, will in step one dry after TA1 titanium sheet as anode, TA1 titanium sheet and platinized platinum, as negative electrode, are then concurrently placed in electrolyte by platinized platinum, are 55V at voltage, electrolyte temperature is anodized 4.5h under conditions of 20 DEG C, obtains the TiO of Ca and Si codope2Dense film；Containing 15g sodium oxalate in every liter of described electrolyte, 6g sodium dihydrogen phosphate, 2g sodium metasilicate and 5.5g calcium hydroxide, surplus is water.
Fig. 1 is the TiO of Ca and Si codope prepared by the present embodiment2The XPS spectrum figure of dense film, from figure 1 it appears that TA1 titanium plate surface prepares one layer of Ca and Si codope TiO2Film, draws the TiO of Ca and the Si codope of the present embodiment by XPS spectrum map analysis2In dense film, the atomic percentage conc of Ca is 0.53%, and the atomic percentage conc of Si is 2.86%.
Fig. 2 is the TiO of Ca and Si codope prepared by the present embodiment2The scanning electron microscope (SEM) photograph of dense membrane surface, multiplication factor is 5000 times, from figure 2 it can be seen that the TiO of Ca and Si codope2The even structure of dense film is fine and close.
Fig. 3 is the TiO of Ca and the Si codope that the present embodiment is prepared in TA1 titanium sheet2The scanning electron microscope (SEM) photograph in dense film cross section, multiplication factor is 1600 times, from figure 3, it can be seen that the TiO of Ca and Si codope2The thickness of dense film is 4.6 μm.
Fig. 4 is the TiO of Ca and Si codope prepared by the present embodiment2The contact angle test photo of dense film, figure 4, it is seen that the TiO of Ca and Si codope2Dense film is 21.3 ° with the contact angle of water.The TiO of Ca and the Si codope of the present embodiment2The hardness of dense film is 750HV.
Comparative example 1
The TiO of the Ca doping of this comparative example2In film, the atomic percentage conc of Ca is 0.96%, the TiO of described Ca doping2Film is 20.1 ° with the contact angle of water.The TiO of the Ca doping of this comparative example2The preparation method of film is same as in Example 1, obtains the TiO of Ca doping2Film is dense film, and its difference is: containing 15g sodium oxalate in every liter of described electrolyte, 6g sodium dihydrogen phosphate and 5.5g calcium hydroxide, surplus is water.
After testing, the TiO of the Ca doping of preparation in this comparative example2In dense film, the atomic percentage conc of Ca is 0.96%, the TiO of Ca doping2Dense film is 20.1 ° with the contact angle of water, the TiO of Ca doping2The thickness of dense film is 4.6 μm, the TiO of the Ca doping of this comparative example2The hardness of dense film is 650HV.
Embodiment 2
The TiO of Ca and the Si codope of the present embodiment2In film, the atomic percentage conc of Ca is 0.51%, and the atomic percentage conc of Si is 2.89%, the TiO of described Ca and Si codope2Film is 19.8 ° with the contact angle of water.The TiO of Ca and the Si codope of the present embodiment2The preparation method of film is same as in Example 1, obtains the TiO of Ca and Si codope2Film is perforated membrane, and its difference is: containing 15g sodium oxalate in every liter of electrolyte, 1.2g ammonium fluoride, 2g sodium metasilicate and 5.5g calcium hydroxide, surplus is water.
Fig. 5 is the TiO of Ca and Si codope prepared by the present embodiment2The scanning electron microscope (SEM) photograph of porous film surface, multiplication factor is 20000 times, from figure 5 it can be seen that the TiO of Ca and Si codope2The aperture ratio of perforated membrane is more uniform, and aperture is 45nm.Fig. 6 is the TiO of Ca and the Si codope that the present embodiment is prepared in TA1 titanium sheet2The scanning electron microscope (SEM) photograph in perforated membrane cross section, multiplication factor is 2000 times, from fig. 6 it can be seen that the TiO of Ca and Si codope2The thickness of perforated membrane is 4.7 μm.
After testing, the TiO of Ca and the Si codope of preparation in the present embodiment2In perforated membrane, the atomic percentage conc of Ca is 0.51%, and the atomic percentage conc of Si is 2.89%, the TiO of described Ca and Si codope2Perforated membrane is 19.8 ° with the contact angle of water, the TiO of Ca and Si codope prepared by the present embodiment2The hardness of perforated membrane is 730HV.
Comparative example 2
The TiO of the Ca doping of this comparative example2In film, the atomic percentage conc of Ca is 0.92%, the TiO of described Ca doping2Film is 19.4 ° with the contact angle of water.The TiO of the Ca doping of this comparative example2The preparation method of film is same as in Example 2, obtains the TiO of Ca doping2Film is perforated membrane, and its difference is: containing 15g sodium oxalate in every liter of electrolyte, 1.2g ammonium fluoride and 5.5g calcium hydroxide, surplus is water.
After testing, the TiO of the Ca doping that prepared by this comparative example2In perforated membrane, the atomic percentage conc of Ca is 0.92%, the TiO of Ca doping2Perforated membrane is 19.4 ° with the contact angle of water, the TiO of Ca doping2The aperture of perforated membrane is 45nm, and thickness is 4.7 μm, the TiO of the Ca doping of this comparative example2The hardness of perforated membrane is 630HV.
In conjunction with the embodiments 1 and comparative example 1, embodiment 2 and the test result analysis of comparative example 2, it can be seen that the introducing of Si can make the TiO of Ca and Si codope2The hardness of film significantly increases.
Embodiment 3
The TiO of Ca and the Si codope of the present embodiment2In film, the atomic percentage conc of Ca is 0.67%, and the atomic percentage conc of Si is 2.75%, the TiO of described Ca and Si codope2Film is 26.5 ° with the contact angle of water；The TiO of described Ca and Si codope2The preparation method of film comprises the following steps:
Step one, it is that the TC4 alloy bar material of Φ 5mm × 10mm is polished light with 280 mesh, 600 mesh and 1200 mesh carborundum papers successively by specification, uses ethanol and acetone to clean and dry the most successively；
Step 2, will in step one dry after TC4 alloy bar material as anode, TC4 alloy bar material and platinized platinum, as negative electrode, are then concurrently placed in electrolyte by platinized platinum, are 50V at voltage, electrolyte temperature is anodized 5.5h under conditions of 25 DEG C, obtains the TiO of Ca and Si codope2Dense film；Containing 20g sodium oxalate in every liter of described electrolyte, 3g sodium dihydrogen phosphate, 1.5g sodium metasilicate and 6.5g calcium hydroxide, surplus is water.
After testing, the TiO of Ca and the Si codope of the preparation of the present embodiment2In dense film, the atomic percentage conc of Ca is 0.67%, and the atomic percentage conc of Si is 2.75%, the TiO of described Ca and Si codope2Dense film is 26.5 ° with the contact angle of water；The TiO of described Ca and Si codope2The thickness of dense film is 4.6 μm, the TiO of Ca and Si codope prepared by the present embodiment2The hardness of dense film is 720HV.
Comparative example 3
The TiO of the Si doping of this comparative example2In film, the atomic percentage conc of Si is 3.1%, the TiO of described Si doping2Film is 33.5 ° with the contact angle of water.The TiO of the Si doping of this comparative example2The preparation method of film is same as in Example 3, obtains the TiO of Si doping2Film is dense film, and its difference is: containing 20g sodium oxalate in every liter of described electrolyte, 3g sodium dihydrogen phosphate and 1.5g sodium metasilicate, surplus is water.
After testing, the TiO of the Si doping that prepared by this comparative example2In dense film, the atomic percentage conc of Si is 3.1%, the TiO of Si doping2Dense film is 33.5 ° with the contact angle of water, the TiO of Si doping2The thickness of dense film is 4.6 μm, the TiO of the Si doping of this comparative example2The hardness of dense film is 710HV.
Embodiment 4
The TiO of Ca and the Si codope of the present embodiment2In film, the atomic percentage conc of Ca is 0.69%, and the atomic percentage conc of Si is 2.51%, the TiO of described Ca and Si codope2Film is 28 ° with the contact angle of water.The TiO of Ca and the Si codope of the present embodiment2The preparation method of film is same as in Example 3, obtains the TiO of Ca and Si codope2Film is perforated membrane, and its difference is: containing 20g sodium oxalate in every liter of electrolyte, 0.5g ammonium fluoride, 1.5g sodium metasilicate and 6.5g calcium hydroxide, surplus is water.
After testing, the TiO of Ca and the Si codope that prepared by the present embodiment2In perforated membrane, the atomic percentage conc of Ca is 0.69%, and the atomic percentage conc of Si is 2.51%, the TiO of described Ca and Si codope2Perforated membrane is 28 ° with the contact angle of water, the TiO of Ca and Si codope2The aperture of perforated membrane is 46nm, and thickness is 4.5 μm, the TiO of Ca and the Si codope of the present embodiment2The hardness of perforated membrane is 700HV.
Comparative example 4
The TiO of the Si doping of this comparative example2In film, the atomic percentage conc of Si is 3.2%, the TiO of described Si doping2Film is 34.2 ° with the contact angle of water.The TiO of the Si doping of this comparative example2The preparation method of film is the same as in Example 4, obtains the TiO of Si doping2Film is perforated membrane, and its difference is: containing 20g sodium oxalate in every liter of electrolyte, 0.5g ammonium fluoride and 1.5g sodium metasilicate, surplus is water.
After testing, the TiO of the Si doping that prepared by this comparative example2In perforated membrane, the atomic percentage conc of Si is 3.2%, the TiO of Si doping2Perforated membrane is 34.2 ° with the contact angle of water, the TiO of Si doping2The aperture of perforated membrane is 46nm, and thickness is 4.5 μm, the TiO of the Si doping of this comparative example2The hardness of perforated membrane is 700HV.
In conjunction with the embodiments 3 and comparative example 3, embodiment 4 and the test result analysis of comparative example 4, it can be seen that Ca introduces the TiO improving Ca and Si codope2The hydrophilicity of film has and interferes significantly on, and promotes Ca and Si codope TiO2Film has more preferable biocompatibility.
Embodiment 5
The TiO of Ca and the Si codope of the present embodiment2In film, the atomic percentage conc of Ca is 0.4%, and the atomic percentage conc of Si is 2.15%, the TiO of described Ca and Si codope2Film is 18.6 ° with the contact angle of water；The TiO of described Ca and Si codope2The preparation method of film comprises the following steps:
Step one, it is that the Ti6Al7Nb alloy bar material of Φ 5mm × 10mm is polished light with 280 mesh, 600 mesh and 1200 mesh carborundum papers successively by specification, uses ethanol and acetone to clean and dry the most successively；
Step 2, will in step one dry after Ti6Al7Nb alloy bar material as anode, platinized platinum is as negative electrode, then Ti6Al7Nb alloy bar material and platinized platinum are concurrently placed in electrolyte, it is 20V at voltage, electrolyte temperature is anodized 8h under conditions of 30 DEG C, obtains the TiO of Ca and Si codope2Dense film；Containing 5g sodium oxalate in every liter of described electrolyte, 8g sodium dihydrogen phosphate, 1g sodium metasilicate and 3g calcium hydroxide, surplus is water.
After testing, the TiO of Ca and the Si codope of the present embodiment2In dense film, the atomic percentage conc of Ca is 0.4%, and the atomic percentage conc of Si is 2.15%, the TiO of Ca and Si codope2Dense film is 18.6 ° with the contact angle of water, the TiO of Ca and Si codope2The thickness of dense film is 3.2 μm, the TiO of Ca and the Si codope of the present embodiment2The hardness of dense film is 710HV.
Embodiment 6
The TiO of Ca and the Si codope of the present embodiment2In film, the atomic percentage conc of Ca is 0.40%, and the atomic percentage conc of Si is 2%, the TiO of described Ca and Si codope2Film is 19 ° with the contact angle of water.The TiO of Ca and the Si codope of the present embodiment2The preparation method of film is same as in Example 5, obtains the TiO of Ca and Si codope2Film is perforated membrane, and its difference is: containing 5g sodium oxalate in every liter of electrolyte, 2g ammonium fluoride, 1g sodium metasilicate and 3g calcium hydroxide, surplus is water.
After testing, the TiO of Ca and the Si codope of preparation in the present embodiment2In perforated membrane, the atomic percentage conc of Ca is 0.40%, and the atomic percentage conc of Si is 2%, the TiO of Ca and Si codope2Perforated membrane is 19 ° with the contact angle of water, the TiO of Ca and Si codope2The aperture of perforated membrane is 30nm, and thickness is 3.0 μm, the TiO of Ca and the Si codope of the present embodiment2The hardness of perforated membrane is 708HV.
Embodiment 7
The TiO of Ca and the Si codope of the present embodiment2In film, the atomic percentage conc of Ca is 0.79%, and the atomic percentage conc of Si is 2.76%, the TiO of described Ca and Si codope2Film is 21.6 ° with the contact angle of water；The TiO of described Ca and Si codope2The preparation method of film comprises the following steps:
Step one, it is that the alloy bar material of the TiNi of Φ 5mm × 10mm is polished light with 280 mesh, 600 mesh and 1200 mesh carborundum papers successively by specification, uses ethanol and acetone to clean and dry the most successively；
Step 2, will in step one dry after TiNi alloy bar as anode, TiNi alloy bar and platinized platinum, as negative electrode, are then concurrently placed in electrolyte by platinized platinum, are 60V at voltage, electrolyte temperature is anodized 3.5h under conditions of 15 DEG C, obtains the TiO of Ca and Si codope2Dense film；Containing 12g sodium oxalate in every liter of described electrolyte, 5.5g sodium dihydrogen phosphate, 3g sodium metasilicate and 8g calcium hydroxide, surplus is water.
After testing, the TiO of Ca and the Si codope of the present embodiment2In dense film, the atomic percentage conc of Ca is 0.79%, and the atomic percentage conc of Si is 2.76%, the TiO of described Ca and Si codope2Dense film is 21.6 ° with the contact angle of water, the TiO of Ca and Si codope2The thickness of dense film is 4.9 μm, the TiO of Ca and the Si codope of the present embodiment2The hardness of dense film is 715HV.
Embodiment 8
The TiO of Ca and the Si codope of the present embodiment2In film, the atomic percentage conc of Ca is 0.76%, and the atomic percentage conc of Si is 2.81%, the TiO of described Ca and Si codope2Film is 22.3 ° with the contact angle of water.The TiO of Ca and the Si codope of the present embodiment2The preparation method of film is same as in Example 7, obtains the TiO of Ca and Si codope2Film is perforated membrane, and its difference is: containing 12g sodium oxalate in every liter of electrolyte, 1.5g ammonium fluoride, 3g sodium metasilicate and 8g calcium hydroxide, surplus is water.
After testing, the TiO of Ca and the Si codope that prepared by the present embodiment2In perforated membrane, the atomic percentage conc of Ca is 0.76%, and the atomic percentage conc of Si is 2.81%, the TiO of described Ca and Si codope2Perforated membrane is 22.3 ° with the contact angle of water, the TiO of Ca and Si codope2The aperture of perforated membrane is 48nm, and thickness is 4.8 μm, the TiO of Ca and the Si codope of the present embodiment2The hardness of perforated membrane is 720HV.
Embodiment 9
The TiO of Ca and the Si codope of the present embodiment2In film, the atomic percentage conc of Ca is 0.56%, and the atomic percentage conc of Si is 3%, the TiO of described Ca and Si codope2Film is 27 ° with the contact angle of water；The TiO of described Ca and Si codope2The preparation method of film comprises the following steps:
Step one, TA1 titanium sheet that specification is 10mm × 10mm is polished light with 280 mesh, 600 mesh and 1200 mesh carborundum papers successively, use ethanol and acetone to clean and dry the most successively；
Step 2, will in step one dry after TA1 titanium sheet as anode, TA1 titanium sheet and platinized platinum, as negative electrode, are then concurrently placed in electrolyte by platinized platinum, are 50V at voltage, electrolyte temperature is anodized 4h under conditions of 20 DEG C, obtains the TiO of Ca and Si codope2Dense film；Containing 20g sodium oxalate in every liter of described electrolyte, 4g sodium dihydrogen phosphate, 3g sodium metasilicate and 5.5g calcium hydroxide, surplus is water.
After testing, the TiO of Ca and the Si codope that prepared by the present embodiment2In dense film, the atomic percentage conc of Ca is 0.56%, and the atomic percentage conc of Si is 3%, the TiO of Ca and Si codope2Dense film is 27 ° with the contact angle of water, the TiO of Ca and Si codope2The thickness of dense film is 4.3 μm, the TiO of Ca and the Si codope of the present embodiment2The hardness of dense film is 712HV.
Embodiment 10
The TiO of Ca and the Si codope of the present embodiment2In film, the atomic percentage conc of Ca is 0.57%, and the atomic percentage conc of Si is 3%, the TiO of described Ca and Si codope2Film is 27.5 ° with the contact angle of water.The TiO of Ca and the Si codope of the present embodiment2The preparation method of film is the same as in Example 9, obtains the TiO of Ca and Si codope2Film is perforated membrane, and its difference is: containing 20g sodium oxalate in every liter of electrolyte, 1g ammonium fluoride, 3g sodium metasilicate and 5.5g calcium hydroxide, surplus is water.
After testing, the TiO of Ca and the Si codope that prepared by the present embodiment2In perforated membrane, the atomic percentage conc of Ca is 0.57%, and the atomic percentage conc of Si is 3%, the TiO of described Ca and Si codope2Perforated membrane is 27.5 ° with the contact angle of water；The TiO of Ca and Si codope2The aperture of perforated membrane is 42nm, and thickness is 4.1 μm, the TiO of Ca and the Si codope of the present embodiment2The hardness of perforated membrane is 720HV.
Embodiment 11
The TiO of Ca and the Si codope of the present embodiment2In film, the atomic percentage conc of Ca is 0.75%, and the atomic percentage conc of Si is 2.56%, the TiO of described Ca and Si codope2Film is 18.3 ° with the contact angle of water；The TiO of described Ca and Si codope2The preparation method of film comprises the following steps:
Step one, Ti3Zr2Sn3Mo15Nb alloy sheet material that specification is 10mm × 10mm is polished light with 280 mesh, 600 mesh and 1200 mesh carborundum papers successively, use ethanol and acetone to clean and dry the most successively；
Step 2, will in step one dry after Ti3Zr2Sn3Mo15Nb alloy sheet material as anode, platinized platinum is as negative electrode, then Ti3Zr2Sn3Mo15Nb alloy sheet material and platinized platinum are concurrently placed in electrolyte, it is 30V at voltage, electrolyte temperature is anodized 8h under conditions of 25 DEG C, obtains the TiO of Ca and Si codope2Dense film；Containing 15g sodium oxalate in every liter of described electrolyte, 5g sodium dihydrogen phosphate, 2g sodium metasilicate and 6.5g calcium hydroxide, surplus is water.
After testing, the TiO of Ca and the Si codope that prepared by the present embodiment2In dense film, the atomic percentage conc of Ca is 0.75%, and the atomic percentage conc of Si is 2.56%, the TiO of Ca and Si codope2Dense film is 18.3 ° with the contact angle of water, the TiO of Ca and Si codope2The thickness of dense film is 3 μm, the TiO of Ca and the Si codope of the present embodiment2The hardness of dense film is 735HV.
Embodiment 12
The TiO of Ca and the Si codope of the present embodiment2In film, the atomic percentage conc of Ca is 0.79%, and the atomic percentage conc of Si is 2.43%, the TiO of described Ca and Si codope2Film is 17.6 ° with the contact angle of water.The TiO of Ca and the Si codope of the present embodiment2The preparation method of film is identical with embodiment 11, obtains the TiO of Ca and Si codope2Film is perforated membrane, and its difference is: containing 15g sodium oxalate in every liter of electrolyte, 0.5g ammonium fluoride, 2g sodium metasilicate and 6.5g calcium hydroxide, surplus is water.
After testing, the TiO of Ca and the Si codope that prepared by the present embodiment2In perforated membrane, the atomic percentage conc of Ca is 0.79%, and the atomic percentage conc of Si is 2.43%, the TiO of Ca and Si codope2Perforated membrane is 17.6 ° with the contact angle of water, the TiO of Ca and Si codope2The aperture of perforated membrane is 32nm, and thickness is 3.1 μm, the TiO of Ca and the Si codope of the present embodiment2The hardness of perforated membrane is 740HV.
Embodiment 13
The TiO of Ca and the Si codope of the present embodiment2In film, the atomic percentage conc of Ca is 0.42%, and the atomic percentage conc of Si is 2%, the TiO of described Ca and Si codope2Film is 22.6 ° with the contact angle of water；The TiO of described Ca and Si codope2The preparation method of film comprises the following steps:
Step one, it is that the TC4 alloy bar material of Φ 5mm × 10mm is polished light with 280 mesh, 600 mesh and 1200 mesh carborundum papers successively by specification, uses ethanol and acetone to clean and dry the most successively；
Step 2, will in step one dry after TC4 alloy bar material as anode, TC4 alloy bar material and platinized platinum, as negative electrode, are then concurrently placed in electrolyte by platinized platinum, are 80V at voltage, electrolyte temperature is anodized 0.5h under conditions of 10 DEG C, obtains the TiO of Ca and Si codope2Dense film；Containing 5g sodium oxalate in every liter of described electrolyte, 8g sodium dihydrogen phosphate, 1g sodium metasilicate and 3g calcium hydroxide, surplus is water.
After testing, the TiO of Ca and the Si codope that prepared by the present embodiment2In dense film, the atomic percentage conc of Ca is 0.42%, and the atomic percentage conc of Si is 2%, the TiO of Ca and Si codope2Dense film is 22.6 ° with the contact angle of water, the TiO of Ca and Si codope2The thickness of dense film is 5 μm, the TiO of Ca and the Si codope of the present embodiment2The hardness of dense film is 730HV.
Embodiment 14
The TiO of Ca and the Si codope of the present embodiment2In film, the atomic percentage conc of Ca is 0.46%, and the atomic percentage conc of Si is 2.23%, the TiO of described Ca and Si codope2Film is 19.6 ° with the contact angle of water.The TiO of Ca and the Si codope of the present embodiment2The preparation method of film is identical with embodiment 13, obtains the TiO of Ca and Si codope2Film is perforated membrane, and its difference is: containing 5g sodium oxalate in every liter of electrolyte, 2g ammonium fluoride, 1g sodium metasilicate and 3g calcium hydroxide, surplus is water.
After testing, the TiO of Ca and the Si codope that prepared by the present embodiment2In perforated membrane, the atomic percentage conc of Ca is 0.46%, and the atomic percentage conc of Si is 2.23%, the TiO of Ca and Si codope2Perforated membrane is 19.6 ° with the contact angle of water, the TiO of Ca and Si codope2The aperture of perforated membrane is 50nm, and thickness is 4.8 μm, the TiO of Ca and the Si codope of the present embodiment2The hardness of perforated membrane is 710HV.
Embodiment 15
The TiO of Ca and the Si codope of the present embodiment2In film, the atomic percentage conc of Ca is 0.8%, and the atomic percentage conc of Si is 2.66%, the TiO of described Ca and Si codope2Film is 26.2 ° with the contact angle of water；The TiO of described Ca and Si codope2The preparation method of film comprises the following steps:
Step one, it is that the Ti6Al7Nb alloy bar material of Φ 5mm × 10mm is polished light with 280 mesh, 600 mesh and 1200 mesh carborundum papers successively by specification, uses ethanol and acetone to clean and dry the most successively；
Step 2, will in step one dry after Ti6Al7Nb alloy bar material as anode, platinized platinum is as negative electrode, then Ti6Al7Nb alloy bar material and platinized platinum are concurrently placed in electrolyte, it is 70V at voltage, electrolyte temperature is anodized 2h under conditions of 12 DEG C, obtains the TiO of Ca and Si codope2Dense film；Containing 10g sodium oxalate in every liter of described electrolyte, 6g sodium dihydrogen phosphate, 2g sodium metasilicate and 8g calcium hydroxide, surplus is water.
After testing, the TiO of Ca and the Si codope of the present embodiment2In dense film, the atomic percentage conc of Ca is 0.8%, and the atomic percentage conc of Si is 2.66%, the TiO of Ca and Si codope2Dense film is 26.2 ° with the contact angle of water, the TiO of Ca and Si codope2The thickness of dense film is 4.9 μm, the TiO of Ca and the Si codope of the present embodiment2The hardness of dense film is 740HV.
Embodiment 16
The TiO of Ca and the Si codope of the present embodiment2In film, the atomic percentage conc of Ca is 0.8%, and the atomic percentage conc of Si is 2.15%, the TiO of described Ca and Si codope2Film is 26.1 ° with the contact angle of water.The TiO of Ca and the Si codope of the present embodiment2The preparation method of film is identical with embodiment 15, obtains the TiO of Ca and Si codope2Film is perforated membrane, and its difference is: containing 10g sodium oxalate in every liter of electrolyte, 1.2g ammonium fluoride, 2g sodium metasilicate and 8g calcium hydroxide, surplus is water.
After testing, the TiO of Ca and the Si codope that prepared by the present embodiment2In perforated membrane, the atomic percentage conc of Ca is 0.8%, and the atomic percentage conc of Si is 2.15%, the TiO of Ca and Si codope2Perforated membrane is 26.1 ° with the contact angle of water, the TiO of Ca and Si codope2The aperture of perforated membrane is 48nm, and thickness is 4.9 μm, the TiO of Ca and the Si codope of the present embodiment2The hardness of perforated membrane is 720HV.
The above, be only presently preferred embodiments of the present invention, not impose any restrictions the present invention.Every any simple amendment, change and equivalence change made above example according to inventive technique essence, all still falls within the protection domain of technical solution of the present invention.
Claims (6)
1. the TiO of a Ca and Si codope2Film, it is characterised in that described Ca and Si is co-doped with
Miscellaneous TiO2In film, the atomic percentage conc of Ca is 0.4%～0.8%, and the atomic percentage conc of Si is
2.0%～3.0%, the TiO of described Ca and Si codope2Film is less than 28 ° with the contact angle of water；Described
The TiO of Ca and Si codope2The preparation method of film comprises the following steps:
Step one, matrix is polished light with 280 mesh, 600 mesh and 1200 mesh carborundum papers successively,
Ethanol and acetone is used to clean and dry the most successively；Described matrix is Titanium base or titanium alloy substrate；
Step 2, will in step one dry after matrix as anode, platinized platinum as negative electrode, then will
Matrix and platinized platinum are concurrently placed in electrolyte, are 20V～80V at voltage, and electrolyte temperature is
Anodized 0.5h～8h under conditions of 10 DEG C～30 DEG C, obtain the TiO of Ca and Si codope2
Film；Containing 5g～20g sodium oxalate in every liter of described electrolyte, 3g～8g sodium dihydrogen phosphate, 1g～3g silicon
Acid sodium and 3g～8g calcium hydroxide, surplus is water；Or containing 5g～20g in every liter of described electrolyte
Sodium oxalate, 0.5g～2g ammonium fluoride, 1g～3g sodium metasilicate and 3g～8g calcium hydroxide, surplus is water.
The TiO of a kind of Ca and Si codope the most according to claim 12Film, its feature exists
In, voltage described in step 2 is 50V～60V, and electrolyte temperature is 15 DEG C～25 DEG C, anodic oxidation
The time processed is 3.5h～5.5h.
The TiO of a kind of Ca and Si codope the most according to claim 12Film, its feature exists
In, when in electrolyte described in step 2 containing sodium dihydrogen phosphate, prepared Ca and Si is co-doped with
Miscellaneous TiO2Film is dense film.
The TiO of a kind of Ca and Si codope the most according to claim 32Film, its feature exists
In, the thickness of described dense film is 3 μm～5 μm.
The TiO of a kind of Ca and Si codope the most according to claim 12Film, its feature exists
In, when in electrolyte described in step 2 containing ammonium fluoride, prepared Ca and Si codope
TiO2Film is perforated membrane.
The TiO of a kind of Ca and Si codope the most according to claim 52Film, its feature exists
In, the aperture of described perforated membrane is 30nm～50nm, and thickness is 3 μm～5 μm.
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