CN102100926A - Medical titanium or titanium alloy surface activation modifying method - Google Patents
Medical titanium or titanium alloy surface activation modifying method Download PDFInfo
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- CN102100926A CN102100926A CN2010102048577A CN201010204857A CN102100926A CN 102100926 A CN102100926 A CN 102100926A CN 2010102048577 A CN2010102048577 A CN 2010102048577A CN 201010204857 A CN201010204857 A CN 201010204857A CN 102100926 A CN102100926 A CN 102100926A
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- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 120
- 239000010936 titanium Substances 0.000 title claims abstract description 119
- 229910052719 titanium Inorganic materials 0.000 title claims abstract description 118
- 229910001069 Ti alloy Inorganic materials 0.000 title claims abstract description 72
- 238000000034 method Methods 0.000 title claims abstract description 38
- 230000004913 activation Effects 0.000 title claims abstract description 7
- 239000004793 Polystyrene Substances 0.000 claims abstract description 212
- 229920002223 polystyrene Polymers 0.000 claims abstract description 207
- 239000011159 matrix material Substances 0.000 claims abstract description 63
- 239000004094 surface-active agent Substances 0.000 claims abstract description 59
- 239000008367 deionised water Substances 0.000 claims abstract description 48
- 150000003608 titanium Chemical class 0.000 claims abstract description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000002243 precursor Substances 0.000 claims abstract description 10
- 238000002791 soaking Methods 0.000 claims abstract description 9
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 7
- 239000003960 organic solvent Substances 0.000 claims abstract description 7
- 239000000243 solution Substances 0.000 claims description 151
- 230000004048 modification Effects 0.000 claims description 70
- 238000012986 modification Methods 0.000 claims description 70
- 239000004005 microsphere Substances 0.000 claims description 67
- 239000007788 liquid Substances 0.000 claims description 65
- 239000006185 dispersion Substances 0.000 claims description 54
- 238000002156 mixing Methods 0.000 claims description 48
- 239000012530 fluid Substances 0.000 claims description 47
- 239000003643 water by type Substances 0.000 claims description 44
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims description 43
- 229910052753 mercury Inorganic materials 0.000 claims description 43
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 41
- 239000007864 aqueous solution Substances 0.000 claims description 29
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 25
- MNCGMVDMOKPCSQ-UHFFFAOYSA-M sodium;2-phenylethenesulfonate Chemical group [Na+].[O-]S(=O)(=O)C=CC1=CC=CC=C1 MNCGMVDMOKPCSQ-UHFFFAOYSA-M 0.000 claims description 23
- 238000000151 deposition Methods 0.000 claims description 15
- 239000010409 thin film Substances 0.000 claims description 15
- 150000002500 ions Chemical class 0.000 claims description 9
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 8
- 239000000758 substrate Substances 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 6
- 238000002425 crystallisation Methods 0.000 claims description 5
- 230000008025 crystallization Effects 0.000 claims description 5
- 238000005137 deposition process Methods 0.000 claims description 5
- 238000002715 modification method Methods 0.000 claims description 5
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 3
- 229910000349 titanium oxysulfate Inorganic materials 0.000 claims description 3
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 3
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- 239000004141 Sodium laurylsulphate Substances 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 235000019333 sodium laurylsulphate Nutrition 0.000 claims description 2
- JHJUUEHSAZXEEO-UHFFFAOYSA-M sodium;4-dodecylbenzenesulfonate Chemical compound [Na+].CCCCCCCCCCCCC1=CC=C(S([O-])(=O)=O)C=C1 JHJUUEHSAZXEEO-UHFFFAOYSA-M 0.000 claims description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 2
- XROWMBWRMNHXMF-UHFFFAOYSA-J titanium tetrafluoride Chemical compound [F-].[F-].[F-].[F-].[Ti+4] XROWMBWRMNHXMF-UHFFFAOYSA-J 0.000 claims description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 abstract description 127
- 239000004408 titanium dioxide Substances 0.000 abstract description 17
- 230000008021 deposition Effects 0.000 abstract description 11
- 239000003094 microcapsule Substances 0.000 abstract description 6
- 238000012545 processing Methods 0.000 abstract description 6
- 239000002994 raw material Substances 0.000 abstract description 3
- 239000002159 nanocrystal Substances 0.000 abstract 1
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 abstract 1
- 239000010408 film Substances 0.000 description 65
- 239000011259 mixed solution Substances 0.000 description 47
- 239000000523 sample Substances 0.000 description 41
- 238000000427 thin-film deposition Methods 0.000 description 40
- 229910000883 Ti6Al4V Inorganic materials 0.000 description 21
- 239000012890 simulated body fluid Substances 0.000 description 19
- 239000000463 material Substances 0.000 description 15
- 229910010413 TiO 2 Inorganic materials 0.000 description 14
- 229910052588 hydroxylapatite Inorganic materials 0.000 description 13
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 description 13
- 230000004071 biological effect Effects 0.000 description 12
- 229910052586 apatite Inorganic materials 0.000 description 9
- VSIIXMUUUJUKCM-UHFFFAOYSA-D pentacalcium;fluoride;triphosphate Chemical compound [F-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O VSIIXMUUUJUKCM-UHFFFAOYSA-D 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 238000001338 self-assembly Methods 0.000 description 7
- 210000004027 cell Anatomy 0.000 description 6
- 241000292525 Titanio Species 0.000 description 5
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- 229910045601 alloy Inorganic materials 0.000 description 5
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- 239000012620 biological material Substances 0.000 description 5
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- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 230000000975 bioactive effect Effects 0.000 description 3
- 239000010839 body fluid Substances 0.000 description 3
- 210000001124 body fluid Anatomy 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 238000000338 in vitro Methods 0.000 description 3
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- 238000004549 pulsed laser deposition Methods 0.000 description 3
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- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
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- 102000007350 Bone Morphogenetic Proteins Human genes 0.000 description 1
- 108010007726 Bone Morphogenetic Proteins Proteins 0.000 description 1
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- 102000010834 Extracellular Matrix Proteins Human genes 0.000 description 1
- 108010037362 Extracellular Matrix Proteins Proteins 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 201000010814 Synostosis Diseases 0.000 description 1
- 229910004537 TaCl5 Inorganic materials 0.000 description 1
- 229910003074 TiCl4 Inorganic materials 0.000 description 1
- LCKIEQZJEYYRIY-UHFFFAOYSA-N Titanium ion Chemical compound [Ti+4] LCKIEQZJEYYRIY-UHFFFAOYSA-N 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
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- 239000011575 calcium Substances 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 239000001506 calcium phosphate Substances 0.000 description 1
- 229910000389 calcium phosphate Inorganic materials 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
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- GROMGGTZECPEKN-UHFFFAOYSA-N sodium metatitanate Chemical compound [Na+].[Na+].[O-][Ti](=O)O[Ti](=O)O[Ti]([O-])=O GROMGGTZECPEKN-UHFFFAOYSA-N 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
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- OEIMLTQPLAGXMX-UHFFFAOYSA-I tantalum(v) chloride Chemical compound Cl[Ta](Cl)(Cl)(Cl)Cl OEIMLTQPLAGXMX-UHFFFAOYSA-I 0.000 description 1
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Abstract
The invention relates to a medical titanium or titanium alloy surface activation modifying method which comprises the steps of: 1, with a surfactant modified monodisperse polystyrene (PS) sphere as a template and an inorganic titanium salt water solution as a precursor solution, preparing a processing solution; 2, with pure titanium or titanium alloy as a matrix, immersing the pure titanium or titanium alloy in the processing solution, and keeping the temperature of the processing solution to be 60-100 DEG C for 24-50h, wherein UV-irradiation is carried out within at least 0.25-2h, and the matrix is soaked in the processing solution with the temperature of 60-100 DEG C; and taking the soaked matrix out, immersing into an organic solvent capable of dissolving the PS for soaking to remove the PS, soaking and crystallizing in deionized water, and completing the deposition of a film. The self-assembling nano crystal titanium dioxide microcapsule biological film is prepared by using the monodisperse polystyrene sphere as the template and the low-price inorganic titanium salt as the raw material at low temperature through a hydrolysis-sol method, and has better bioactivity.
Description
(1) technical field
The present invention relates to a kind of medical titanium or titanium alloy surface activation modification method,, improve surface bioactive by the titanium or the titanium alloy of modification.
(2) background technology
Titanium and alloy essence thereof belong to bio-inert material, and be that a kind of machinery is chimeric between the bone, but not strong chemical synostosis, therefore the formation of good titanium implant-osseous tissue interface is to guarantee to transplant to repair successful key factor, also is the critical problem that this class transplant operation faces.Studies show that in recent years, the structure, chemical analysis etc. that change the titanium surface film oxide by physics, chemistry and electrochemical surface modification ground method can be given the titanium biological activity, thereby realize the biological activity combination between material and sclerous tissues in vivo.
Cotell etc. 1992 have founded the hydroxyapatite films method of utilizing pulsed laser deposition PLD (Pulsed laser deposition) preparation.Control than technological parameters such as kind that can be by regulating substrate temperature, atmosphere and pressure by its degree of crystallinity of hydroxyapatite of this method preparation and Ca/P.The shortcoming of this deposition technique is that substrate and hydroxyapatite bond strength are not high.
Plasma spraying (Plasma spraying) is to go up the bioactive method that obtains with hydroxyapatite sprayed to Ti and Ti-6Al-4V.The thickness of spraying hydroxyapatite coating is 30-150mm, and the control of film quality is also relevant with composition with the particle diameter of hydroxyapatite powder except arc discharge.In the crystalline phase of hydroxyapatite, do not deposit generations such as thing phase, R-calcium phosphate, calcium oxide in addition, also have noncrystalline existence mutually.Infrared spectrum analysis shows that the oxygen in the lattice is lost or the dehydration of structure top.
Professors Kokubo etc. have delivered a series of research papers, titanium or titanium alloy are immersed in 60 ℃ the NaOH solution 24 hours, heat treated 1 hour under 600 ℃ temperature then, and make this metal biologically active.When initial processing, generated on the surface and to have contained-water and the titanium oxide film layer of OH, during subsequently 600 ℃ heat treatment, this rete is as amorphous sodium titanate and stable existence.The Na when titanium of the above-mentioned processing of process and titanium alloy immerse in the simulated body fluid
+Form the Ti-OH group by H3O+ exchange from the metallic surface stripping with simulated body fluid, the Ti-OH group can induce the interface between formed hydroxyapatite layer of hydroxyapatite nucleation and the substrate to have gradient-structure, thereby hydroxyapatite and substrate are combined closely.
X.X.Wang etc. handle pure titanizing at 80 ℃ with H2O2/TaCl5 solution, have generated titania gel on the surface of titanium, and this gel is an amorphous state.This gel still is amorphous state after heat-treating below 200 ℃.Heat-treat between 300 and 600 ℃, this gel conversion is an anatase titanium dioxide.The titanium that will change anatase titanium dioxide into is immersed in the simulated body fluid just found have hydroxyapatite to be deposited on metallic surface in one day.But the amorphous titanium dioxide gel after heat-treating below 200 ℃ is immersed in does not have hydroxyapatite deposition deposition a week yet in the simulated body fluid.X.X.Wang etc. think that the surface chemical property of structure, gel of crystalline titania gel, porous surface is to its biological activity decisive role.Also pure titanizing is handled with H2O2/HCl solution at 80 ℃, generated the amorphous titanium dioxide gel on the surface of titanium, this gel is heat-treated at 400 ℃, and then titanium being immersed in the simulated body fluid 2 days same discoveries has hydroxyapatite to be deposited on metallic surface.
In order to solve the integrity problem at bone-implantation body interface, Kokubo has proposed the bionic method, earlier pretreatment is carried out on the titanium surface, heating then, make its surface obtain titanium dioxide, its surperficial titanium hydroxyl (Ti-OH) can bring out surface hydroxyl apatite nucleus growth under bionical condition, but this crystalline state titanium dioxide layer is by the oxidation gained of titanio body own, be subjected to the restriction of high temperature heating condition simultaneously, make the range of choice of matrix material very narrow, the shape of titanio body material is also had very strict requirement.How under cryogenic conditions, to obtain the research of crystalline state titanium dioxide layer, will expand the selective category of biomaterial matrix, shape, the film separation problem that the thermal stress height causes when solving because of high temperature cooling.
In recent years, development along with fields such as cytobiology, genetic engineerings, brand-new medical skill has appearred, as organizational project, and gene therapy etc., it is good thus the requirement of biomaterial not only to be confined to non-toxic and safe, biocompatibility, blood compatibility, and require biomaterial to have the effect of extracellular matrix, promptly in physiological environment, should produce interaction with the somatic cell of living, there is special cell corresponding, becomes the organ alive of the cambium with vitality thereby bring out.Therefore, the research of current material should be started with from the interaction of material and cell, understands between cell and the material, and the information transmission between cell and the cell by MOLECULE DESIGN and structural simulation, has been prepared bioactive bio-medical material.The biological activity of this material should be able to satisfy the requirement of cell on chemistry and mechanical property, and the physiological requirement of tissue.Require the titanium dioxide layer on surface to have property for this reason.
(3) summary of the invention
The object of the present invention is to provide a kind of method that titanium and alloy surface thereof are carried out modification, prepared nano-crystalline titanium dioxide microcapsule compound bio thin film at titanium and alloy surface thereof, to improve its biological activity.
For achieving the above object, the present invention adopts following technical scheme:
A kind of medical titanium or titanium alloy surface activation modification method, it is characterized in that described method is (1) preparation treatment fluid: being template through surfactant-modified monodisperse polystyrene (PS) ball, promptly under the ultrasonic dispersing condition, polystyrene microsphere joined disperse modification in the surfactant, make the monodisperse polystyrene microsphere dispersion liquid of modification, adding the inorganic titanium saline solution is precursor liquid, fully mix homogeneously is made Treatment Solution, the monodisperse polystyrene microsphere dispersion liquid of modification is to add polystyrene microsphere 0.01～0.10g in every 1ml surfactant, the volume ratio of the monodisperse polystyrene microsphere dispersion liquid of titanium salt aqueous solution and modification was 10～1: 1 when described treatment fluid was prepared, the molar concentration of described titanium salt aqueous solution is 0.01～0.08mol/L, and the ion attribute after described surfactant is water-soluble is opposite with the ion attribute of described titanium salt aqueous solution; (2) deposition processes of pure titanium or titanium alloy thin films: with pure titanium or titanium alloy as matrix, pure titanium or titanium alloy are immersed in the Treatment Solution, keep the Treatment Solution temperature at 60～100 ℃, in 60～100 ℃ Treatment Solution, soaked 24～50 hours, and wherein soaked in 60～100 ℃ Treatment Solution with irradiation under ultraviolet ray and described matrix simultaneously at least 0.25～2 hours; Matrix after soaking is taken out, immerse and to soak 0.5～1 hour in the organic solvent of dissolved polystyrene, after polystyrene is removed in dissolving, through washed with de-ionized water, in 60～100 ℃ of deionized waters, soak 24～48 hours crystallization again, finish depositing of thin film, take out and promptly get the titanium or the titanium alloy of surface active modification.Opposite being meant of ion attribute of the ion attribute after surfactant described here is water-soluble and described titanium salt aqueous solution, as titanium salt aqueous solution band cation, the surfactant that adds should select anion surfactant for use, opposite to titanium salt aqueous solution band anion, the surfactant that adds should select cationic surfactant for use.
The present invention is to medical titanium or titanium alloy surface activation modification method, is recommended in to add in the described pretreatment liquid again and make H
2O
2And to make final concentration be 0.01～0.08mol/L, described H
2O
2Identical with the titanium molal quantity in the titanium salt aqueous solution, described H
2O
2Open type with aqueous solution adds.In the present invention, the H of adding
2O
2, can form complex with the titanium ion in the solution, to control the hydrolysis rate of inorganic titanium salt in water, finally obtain the biofilm of different densityes.Concrete, added H
2O
2The Treatment Solution preparation process of aqueous solution is as follows: in the ratio that adds polystyrene microsphere 0.01～0.10g in every 1ml surfactant, polystyrene microsphere joined disperse modification in the surfactant, the monodisperse polystyrene microsphere dispersion liquid of making modification is standby, refabrication inorganic titanium saline solution adds H
2O
2, be made into H
2O
2Content is the mixed solution of 0.01～0.08mol/L, H in the described mixed solution
2O
2Identical with the titanium molal quantity in the titanium salt, again mixed solution is joined in the monodisperse polystyrene microsphere dispersion liquid of modification fully mix homogeneously and make Treatment Solution, the volume ratio of the monodisperse polystyrene microsphere dispersion liquid of titanium salt aqueous solution and modification was 10～1: 1 when described treatment fluid was prepared, the molar concentration of described titanium salt aqueous solution is 0.01～0.08mol/L, and the ion attribute after described surfactant is water-soluble is opposite with the ion attribute of described titanium salt aqueous solution.
Surfactant-modified monodisperse polystyrene of the present invention (PS) ball makes as follows: under the ultrasonic dispersing condition, polystyrene microsphere joined disperse modification in the surfactant, make the monodisperse polystyrene microsphere dispersion liquid of modification, in the monodisperse polystyrene microsphere dispersion liquid of modification, the addition of polystyrene microsphere is that the surfactant of every ml adds 0.01～0.10g, described ultrasonic dispersing is often referred under the room temperature, is uniformly dispersed by supersonic oscillations.
Further, inorganic titanium salt is one of following or the mixing of any several arbitrary proportions in the described inorganic titanium saline solution: titanyl sulfate, titanium tetrachloride, titanium tetrafluoride, tantalic chloride, hydrogen peroxide, most preferably titanyl sulfate.
The organic solvent of described energy dissolved polystyrene is oxolane, toluene, dimethylbenzene, chloroform, acetone, butanone or dimethyl formamide etc.
Method of the present invention, step (2) is preferably carried out as follows, the deposition processes of pure titanium or titanium alloy thin films is: with pure titanium or titanium alloy as matrix, pure titanium or titanium alloy are immersed in the Treatment Solution, keep the Treatment Solution temperature at 60～100 ℃, simultaneously, remove ultraviolet source, more described matrix is continued to soak in 60～100 ℃ Treatment Solution 24～48 hours with irradiation under ultraviolet ray 0.25～2 hour; Matrix after soaking is taken out, immerse and to soak 0.5～1 hour in the organic solvent of dissolved polystyrene, after polystyrene is removed in dissolving, in 60～100 ℃ of deionized waters, soak 24～48 hours crystallization again, finish depositing of thin film, take out the titanium or the titanium alloy of the surface active modification that promptly gets surface modification.
The preferred 0.03mol/L of the molar concentration of described titanium salt aqueous solution.
The concentration of polystyrene microsphere is 0.01～0.10g/ml in the monodisperse polystyrene microsphere dispersion liquid of described modification, the preferred 0.06g/ml of the concentration of polystyrene microsphere.
Further again, the volume ratio of the monodisperse polystyrene microsphere dispersion liquid of titanium salt aqueous solution and modification in the described treatment fluid is 2: 1.
Further, described surfactant is Sodium styrene sulfonate, dodecylbenzene sodium sulfonate, dodecyl sodium sulfate, sodium lauryl sulphate, diphenylamines-4-sodium sulfonate, cetyl trimethyl ammonium bromide etc.
Described irradiation under ultraviolet ray can adopt the equipment of low pressure, middle pressure, high voltage mercury lamp or other emission ultraviolet light wave bands, and the present invention recommends to adopt the high voltage mercury lamp irradiation device, and power 1000W is 65 ± 5w/m in 254nm place light intensity
2, preferred 30 minutes of exposure time.
The present invention is immersed in pure titanium or titanium alloy in the Treatment Solution, recommends to keep the Treatment Solution temperature at 100 ℃.And recommend pure titanium or titanium alloy substrate be immersed in that total time is 36 hours in the Treatment Solution, the time that includes irradiation under ultraviolet ray and do not have irradiation under ultraviolet ray in Treatment Solution, to soak.
Method of the present invention, recommend the dissolving of described matrix to remove polystyrene after, in temperature is 80 ℃ deionized water, soak again, soak time is 48 hours.
The present invention adopts low temperature hydrolysis-colloidal sol technology to carry out modification at titanium and alloy surface thereof, prepared self-assembly nano-crystalline titanium dioxide microcapsule compound bio thin film, the present invention fully utilizes transmission electron microscope (TEM), scanning electron microscope (SEM), electron probe (EPMA), X-ray diffraction (XRD), fourier transform infrared spectroscopy method of testings such as (FTIR) characterizes the heterogeneous microstructure of deposit film, studies the biological activity of this thin film by in-vitro simulated body fluid soak time.
Test result shows: self-assembly nano-crystalline titanium dioxide with spherical uniform deposition on titanium and alloy substrate surface thereof, the compound bio thin film that formative tissue is orderly, its form is subjected to the influence of deposition process conditions to a great extent.The titanium dioxide layer of this method preparation has the ability of inducing apatite to be shaped.Matrix is immersed SBF solution after 12 hours, the deposition of obvious apatite is just arranged, demonstrate the good in vitro biological activity.
The size of self assembly titanium dioxide microcapsule and shell thickness can be regulated and control by changing template size, titanium source concentration and assembling number of times among the present invention, can make nanometer to micron-sized hollow ball.If introduce bone morphogenetic protein(BMP) in shell or in the spherical shell, various cell growth factor, material of different nature such as antibiotic or antitumor drug, can also further enrich the various physical and chemical performances of hollow compound bio thin film, make them at biocompatibility, reaction engineering, numerous areas such as medicament slow release have wide practical use.
It is template with monodisperse polystyrene (PS) ball that beneficial effect of the present invention is embodied in the present invention, cheap inorganic titanium salt is a raw material, prepared self-assembly nano-crystalline titanium dioxide microcapsule biofilm by hydrolysis-sol method at low temperatures, overcome in the additive method because of the restriction of hot conditions to material.This thin film has big specific surface energy, more helps the deposition of apatite on the surface.And improved the biological activity of matrix greatly, TiO
2Film is subjected to become super hydrophilic surface after the UV rayed, and its minimum contact angle is 1 °.Water dissociates at the oxygen defect place to adsorb and generates hydroxyl, forms Ti-OH functional group, thereby makes TiO
2The film possess hydrophilic property, thus regain good biological activity.
(4) description of drawings
Fig. 1 embodiment 1 is at 100 ℃ of TiOSO
4Deposit in the precursor liquid, after subsequent technique is handled, obtain TiO
2The XRD figure spectrum of laminated film
Fig. 2 embodiment 1 is at 100 ℃ of TiOSO
4Deposit in the precursor liquid, after subsequent technique is handled, obtain TiO
2The surface topography of laminated film (SEM)
Fig. 3 is at 100 ℃ of TiOSO
4Deposit in the precursor liquid, after subsequent technique is handled, obtain TiO
2The surperficial EDS of laminated film can spectrogram
Fig. 4 embodiment 1 is at 100 ℃ of TiOSO
4Deposit in the precursor liquid, after subsequent technique is handled, obtain TiO
2Laminated film soaks the film surface XRD figure spectrum that obtains after 12 hours in simulated body fluid (SBF).
Fig. 5 embodiment 1 is at 100 ℃ of TiOSO
4Deposit in the precursor liquid, after subsequent technique is handled, obtain TiO
2Laminated film soaks the surface topography (SEM) that obtains after 12 hours in simulated body fluid (SBF)
Fig. 6 embodiment 1 is at 100 ℃ of TiOSO
4Deposit in the precursor liquid, after subsequent technique is handled, obtain TiO
2Laminated film, soaking the film surface EDS that obtains after 12 hours in simulated body fluid (SBF) can spectrogram
Fig. 7 embodiment 1 is at 100 ℃ of TiOSO
4Deposit in the precursor liquid, after subsequent technique is handled, obtain TiO
2Laminated film soaks the surface topography (SEM) that obtains after 24 hours in simulated body fluid (SBF)
(5) specific embodiment
The invention will be further described below in conjunction with specific embodiment, but protection scope of the present invention is not limited thereto.
With 350ml surfactant Sodium styrene sulfonate (PSS),, make the polystyrene microsphere dispersion liquid after the modification of 0.06g/ml with abundant ultrasonic mixing of 21g polystyrene microsphere (PS).
H with 1.02g
2O
2(30%wt) add fully mixing in the 300ml deionized water, obtain the H of 0.03mol/L
2O
2Aqueous solution.Get the TiOSO of 1.44g
4Powder adds the H of 0.03mol/L
2O
2Aqueous solution makes 0.03mol/L TiOSO
4, 0.03mol/L H
2O
2Mixed solution.
Sample is the pure titanium of 10 * 10 * 1mm, and it is standby to clean the back.Get above-mentioned 0.03mol/L TiOSO
4, 0.03mol/L H
2O
2Mixed solution 30ml adds above-mentioned polystyrene microsphere with the modification of surfactant Sodium styrene sulfonate (PS) dispersion liquid 20ml, and abundant ultrasonic mixing obtains Treatment Solution.Treatment fluid is heated to 100 ℃, and remains on this temperature, the titanium sheet is immersed in the Treatment Solution soaked 0.5 hour, use high voltage mercury lamp simultaneously, power 1000W, 254nm place light intensity is 65 ± 5w/m
20.5 hour ultraviolet light of irradiation, remove ultraviolet source again, allow the titanium sheet in 100 ℃ Treatment Solution, soak 35.5 hours more again, take out the back and in the oxolane of 50ml, soaked 0.5 hour, remove polystyrene, take out the matrix of removing polystyrene, after washed with de-ionized water, immersed in 80 ℃ of deionized waters 48 hours, and finished thin film deposition, obtain titania coextruded film.
Embodiment 2
Sample is the pure titanium of 10 * 10 * 1mm, and it is standby to clean the back.Get the 0.03mol/LTiOSO that makes among the embodiment 1
4, 0.03mol/L H
2O
2Mixed solution 30ml adds the polystyrene microsphere with the modification of surfactant Sodium styrene sulfonate (PS) the dispersion liquid 20ml that makes among the embodiment 1, and abundant ultrasonic mixing obtains Treatment Solution.Treatment fluid is heated to 80 ℃, and remains on this temperature, the titanium sheet is immersed in the Treatment Solution soaked 0.5 hour, use high voltage mercury lamp simultaneously, power 1000W, 254nm place light intensity is 65 ± 5w/m
20.5 hour ultraviolet light of irradiation, remove ultraviolet source again, allow the titanium sheet in 80 ℃ Treatment Solution, soak 35.5 hours more again, take out the back and in the oxolane of 50ml, soaked 0.5 hour, remove polystyrene, take out the matrix of removing polystyrene, after washed with de-ionized water, immersed in 80 ℃ of deionized waters 48 hours, and finished thin film deposition, obtain titania coextruded film.
Sample is the pure titanium of 10 * 10 * 1mm, and it is standby to clean the back.Get the 0.03mol/LTiOSO that makes among the embodiment 1
4, 0.03mol/L H
2O
2Mixed solution 30ml adds the polystyrene microsphere with the modification of surfactant Sodium styrene sulfonate (PS) the dispersion liquid 20ml that makes among the embodiment 1, and abundant ultrasonic mixing obtains Treatment Solution.Treatment fluid is heated to 60 ℃, and remains on this temperature, the titanium sheet is immersed in the Treatment Solution soaked 0.5 hour, use high voltage mercury lamp simultaneously, power 1000W, 254nm place light intensity is 65 ± 5w/m
20.5 hour ultraviolet light of irradiation, remove ultraviolet source again, allow the titanium sheet in 60 ℃ Treatment Solution, soak 35.5 hours more again, take out the back and in the oxolane of 50ml, soaked 0.5 hour, remove polystyrene, take out the matrix of removing polystyrene, after washed with de-ionized water, immersed in 80 ℃ of deionized waters 48 hours, and finished thin film deposition, obtain titania coextruded film.
Embodiment 4
Sample is the pure titanium of 10 * 10 * 1mm, and it is standby to clean the back.Get the 0.03mol/LTiOSO that makes among the embodiment 1
4, 0.03mol/L H
2O
2Mixed solution 30ml adds the polystyrene microsphere with the modification of surfactant Sodium styrene sulfonate (PS) the dispersion liquid 20ml that makes among the embodiment 1, and abundant ultrasonic mixing obtains Treatment Solution.Treatment fluid is heated to 100 ℃, and remains on this temperature, the titanium sheet is immersed in the Treatment Solution soaked 1 hour, use high voltage mercury lamp simultaneously, power 1000W, 254nm place light intensity is 65 ± 5w/m
21 hour ultraviolet light of irradiation, remove ultraviolet source again, allow the titanium sheet in 100 ℃ Treatment Solution, soak 23 hours more again, take out the back and in the oxolane of 50ml, soaked 0.5 hour, remove polystyrene, take out the matrix of removing polystyrene, after washed with de-ionized water, immersed in 80 ℃ of deionized waters 48 hours, and finished thin film deposition, obtain titania coextruded film.
Embodiment 5
Sample is the pure titanium of 10 * 10 * 1mm, and it is standby to clean the back.Get the 0.03mol/LTiOSO that makes among the embodiment 1
4, 0.03mol/L H
2O
2Mixed solution 30ml adds the polystyrene microsphere with the modification of surfactant Sodium styrene sulfonate (PS) the dispersion liquid 20ml that makes among the embodiment 1, and abundant ultrasonic mixing obtains Treatment Solution.Treatment fluid is heated to 100 ℃, and remains on this temperature, the titanium sheet is immersed in the Treatment Solution soaked 2 hours, use high voltage mercury lamp simultaneously, power 1000W, 254nm place light intensity is 65 ± 5w/m
22 hours ultraviolet lights of irradiation, remove ultraviolet source again, allow the titanium sheet in 100 ℃ Treatment Solution, soak 46 hours more again, take out the back and in the oxolane of 50ml, soaked 0.5 hour, remove polystyrene, take out the matrix of removing polystyrene, after washed with de-ionized water, immersed in 80 ℃ of deionized waters 48 hours, and finished thin film deposition, obtain titania coextruded film.
Embodiment 6
Sample is the Ti-6Al-4V of 10 * 10 * 1mm, and it is standby to clean the back.Get the 0.03mol/L TiOSO that makes among the embodiment 1
4, 0.03mol/L H
2O
2Mixed solution 30ml adds the polystyrene microsphere with the modification of surfactant Sodium styrene sulfonate (PS) the dispersion liquid 20ml that makes among the embodiment 1, and abundant ultrasonic mixing obtains Treatment Solution.Treatment fluid is heated to 100 ℃, and remains on this temperature, the titanium alloy sheet is immersed in the Treatment Solution soaked 0.5 hour, use high voltage mercury lamp simultaneously, power 1000W, 254nm place light intensity is 65 ± 5w/m
20.5 hour ultraviolet light of irradiation, remove ultraviolet source again, allow the titanium alloy sheet in 100 ℃ Treatment Solution, soak 35.5 hours more again, take out the back and in the oxolane of 50ml, soaked 0.5 hour, remove polystyrene, take out the matrix of removing polystyrene, after washed with de-ionized water, immersed in 80 ℃ of deionized waters 48 hours, and finished thin film deposition, obtain titania coextruded film.
Embodiment 7
Sample is the Ti-6Al-4V of 10 * 10 * 1mm, and it is standby to clean the back.Get the 0.03mol/L TiOSO that makes among the embodiment 1
4, 0.03mol/L H
2O
2Mixed solution 30ml adds the polystyrene microsphere with the modification of surfactant Sodium styrene sulfonate (PS) the dispersion liquid 20ml that makes among the embodiment 1, and abundant ultrasonic mixing obtains Treatment Solution.Treatment fluid is heated to 80 ℃, and remains on this temperature, the titanium alloy sheet is immersed in the Treatment Solution soaked 0.5 hour, use high voltage mercury lamp simultaneously, power 1000W, 254nm place light intensity is 65 ± 5w/m
20.5 hour ultraviolet light of irradiation, remove ultraviolet source again, allow the titanium alloy sheet in 80 ℃ Treatment Solution, soak 35.5 hours more again, take out the back and in the oxolane of 50ml, soaked 0.5 hour, remove polystyrene, take out the matrix of removing polystyrene, after washed with de-ionized water, immersed in 80 ℃ of deionized waters 48 hours, and finished thin film deposition, obtain titania coextruded film.
Embodiment 8
Sample is the Ti-6Al-4V of 10 * 10 * 1mm, and it is standby to clean the back.Get the 0.03mol/L TiOSO that makes among the embodiment 1
4, 0.03mol/L H
2O
2Mixed solution 30ml adds the polystyrene microsphere with the modification of surfactant Sodium styrene sulfonate (PS) the dispersion liquid 20ml that makes among the embodiment 1, and abundant ultrasonic mixing obtains Treatment Solution.Treatment fluid is heated to 60 ℃, and remains on this temperature, the titanium alloy sheet is immersed in the Treatment Solution soaked 0.5 hour, use high voltage mercury lamp simultaneously, power 1000W, 254nm place light intensity is 65 ± 5w/m
20.5 hour ultraviolet light of irradiation, remove ultraviolet source again, allow the titanium alloy sheet in 60 ℃ Treatment Solution, soak 35.5 hours more again, take out the back and in the oxolane of 50ml, soaked 0.5 hour, remove polystyrene, take out the matrix of removing polystyrene, after washed with de-ionized water, immersed in 80 ℃ of deionized waters 48 hours, and finished thin film deposition, obtain titania coextruded film.
Embodiment 9
Sample is the Ti-6Al-4V of 10 * 10 * 1mm, and it is standby to clean the back.Get the 0.03mol/L TiOSO that makes among the embodiment 1
4, 0.03mol/L H
2O
2Mixed solution 30ml adds the polystyrene microsphere with the modification of surfactant Sodium styrene sulfonate (PS) the dispersion liquid 20ml that makes among the embodiment 1, and abundant ultrasonic mixing obtains Treatment Solution.Treatment fluid is heated to 100 ℃, and remains on this temperature, the titanium alloy sheet is immersed in the Treatment Solution soaked 1 hour, use high voltage mercury lamp simultaneously, power 1000W, 254nm place light intensity is 65 ± 5w/m
21 hour ultraviolet light of irradiation, remove ultraviolet source again, allow the titanium alloy sheet in 100 ℃ Treatment Solution, soak 23 hours more again, take out the back and in the oxolane of 50ml, soaked 0.5 hour, remove polystyrene, take out the matrix of removing polystyrene, after washed with de-ionized water, immersed in 80 ℃ of deionized waters 48 hours, and finished thin film deposition, obtain titania coextruded film.
Embodiment 10
Sample is the Ti-6Al-4V of 10 * 10 * 1mm, and it is standby to clean the back.Get the 0.03mol/L TiOSO that makes among the embodiment 1
4, 0.03mol/L H
2O
2Mixed solution 30ml adds the polystyrene microsphere with the modification of surfactant Sodium styrene sulfonate (PS) the dispersion liquid 20ml that makes among the embodiment 1, and abundant ultrasonic mixing obtains Treatment Solution.Treatment fluid is heated to 100 ℃, and remains on this temperature, the titanium alloy sheet is immersed in the Treatment Solution soaked 2 hours, use high voltage mercury lamp simultaneously, power 1000W, 254nm place light intensity is 65 ± 5w/m
22 hours ultraviolet lights of irradiation, remove ultraviolet source again, allow the titanium alloy sheet in 100 ℃ Treatment Solution, soak 46 hours more again, take out the back and in the oxolane of 50ml, soaked 0.5 hour, remove polystyrene, take out the matrix of removing polystyrene, after washed with de-ionized water, immersed in 80 ℃ of deionized waters 48 hours, and finished thin film deposition, obtain titania coextruded film.
H with 0.34g
2O
2(30%wt) add fully mixing in the 300ml deionized water, obtain the H of 0.01mol/L
2O
2Aqueous solution.Get the TiOSO of 0.48g
4Powder adds the H2O2 aqueous solution of 0.01mol/L, makes 0.01mol/L TiOSO
4, 0.01mol/L H
2O
2Mixed solution.
Sample is the pure titanium of 10 * 10 * 1mm, and it is standby to clean the back.Get above-mentioned 0.01mol/L TiOSO
4, 0.01mol/L H
2O
2Mixed solution 30ml adds the polystyrene microsphere with the modification of surfactant Sodium styrene sulfonate (PS) the dispersion liquid 15ml that makes among the embodiment 1, and abundant ultrasonic mixing obtains Treatment Solution.Treatment fluid is heated to 100 ℃, and remains on this temperature, the titanium sheet is immersed in the Treatment Solution soaked 0.5 hour, use high voltage mercury lamp simultaneously, power 1000W, 254nm place light intensity is 65 ± 5w/m
20.5 hour ultraviolet light of irradiation, remove ultraviolet source again, allow the titanium sheet in 100 ℃ Treatment Solution, soak 35.5 hours more again, take out the back and in the oxolane of 50ml, soaked 0.5 hour, remove polystyrene, take out the matrix of removing polystyrene, after washed with de-ionized water, immersed in 80 ℃ of deionized waters 48 hours, and finished thin film deposition, obtain titania coextruded film.
Embodiment 12
Sample is the titanium sheet of 10 * 10 * 1mm, and it is standby to clean the back.Get the 0.01mol/LTiOSO that makes among the embodiment 11
4, 0.01mol/L H
2O
2Mixed solution 30ml adds the polystyrene microsphere with the modification of surfactant Sodium styrene sulfonate (PS) the dispersion liquid 15ml that makes among the embodiment 1, and abundant ultrasonic mixing obtains Treatment Solution.Treatment fluid is heated to 80 ℃, and remains on this temperature, the titanium sheet is immersed in the Treatment Solution soaked 0.5 hour, use high voltage mercury lamp simultaneously, power 1000W, 254nm place light intensity is 65 ± 5w/m
20.5 hour ultraviolet light of irradiation, remove ultraviolet source again, allow the titanium sheet in 80 ℃ Treatment Solution, soak 35.5 hours more again, take out the back and in the oxolane of 50ml, soaked 0.5 hour, remove polystyrene, take out the matrix of removing polystyrene, after washed with de-ionized water, immersed in 80 ℃ of deionized waters 48 hours, and finished thin film deposition, obtain titania coextruded film.
Embodiment 13
Sample is the pure titanium of 10 * 10 * 1mm, and it is standby to clean the back.Get the 0.01mol/LTiOSO that makes among the embodiment 11
4, 0.01mol/L H
2O
2Mixed solution 30ml adds the polystyrene microsphere with the modification of surfactant Sodium styrene sulfonate (PS) the dispersion liquid 15ml that makes among the embodiment 1, and abundant ultrasonic mixing obtains Treatment Solution.Treatment fluid is heated to 60 ℃, and remains on this temperature, the titanium sheet is immersed in the Treatment Solution soaked 0.5 hour, use high voltage mercury lamp simultaneously, power 1000W, 254nm place light intensity is 65 ± 5w/m
20.5 hour ultraviolet light of irradiation, remove ultraviolet source again, allow the titanium sheet in 60 ℃ Treatment Solution, soak 35.5 hours more again, take out the back and in the oxolane of 50ml, soaked 0.5 hour, remove polystyrene, take out the matrix of removing polystyrene, after washed with de-ionized water, immersed in 80 ℃ of deionized waters 48 hours, and finished thin film deposition, obtain titania coextruded film.
Embodiment 14
Sample is the pure titanium of 10 * 10 * 1mm, and it is standby to clean the back.Get the 0.01mol/LTiOSO that makes among the embodiment 11
4, 0.01mol/L H
2O
2Mixed solution 30ml adds the polystyrene microsphere with the modification of surfactant Sodium styrene sulfonate (PS) the dispersion liquid 15ml that makes among the embodiment 1, and abundant ultrasonic mixing obtains Treatment Solution.Treatment fluid is heated to 100 ℃, and remains on this temperature, the titanium sheet is immersed in the Treatment Solution soaked 1 hour, use high voltage mercury lamp simultaneously, power 1000W, 254nm place light intensity is 65 ± 5w/m
21 hour ultraviolet light of irradiation, remove ultraviolet source again, allow the titanium sheet in 100 ℃ Treatment Solution, soak 23 hours more again, take out the back and in the oxolane of 50ml, soaked 0.5 hour, remove polystyrene, take out the matrix of removing polystyrene, after washed with de-ionized water, immersed in 80 ℃ of deionized waters 48 hours, and finished thin film deposition, obtain titania coextruded film.
Sample is the pure titanium of 10 * 10 * 1mm, and it is standby to clean the back.Get the 0.01mol/LTiOSO that makes among the embodiment 11
4, 0.01mol/L H
2O
2Mixed solution 30ml adds the polystyrene microsphere with the modification of surfactant Sodium styrene sulfonate (PS) the dispersion liquid 15ml that makes among the embodiment 1, and abundant ultrasonic mixing obtains Treatment Solution.Treatment fluid is heated to 100 ℃, and remains on this temperature, the titanium sheet is immersed in the Treatment Solution soaked 2 hours, use high voltage mercury lamp simultaneously, power 1000W, 254nm place light intensity is 65 ± 5w/m
22 hours ultraviolet lights of irradiation, remove ultraviolet source again, allow the titanium sheet in 100 ℃ Treatment Solution, soak 46 hours more again, take out the back and in the oxolane of 50ml, soaked 0.5 hour, remove polystyrene, take out the matrix of removing polystyrene, after washed with de-ionized water, immersed in 80 ℃ of deionized waters 48 hours, and finished thin film deposition, obtain titania coextruded film.
Embodiment 16
Sample is the Ti-6Al-4V of 10 * 10 * 1mm, and it is standby to clean the back.Get the 0.01mol/L TiOSO that makes among the embodiment 11
4, 0.01mol/L H
2O
2Mixed solution 30ml adds the polystyrene microsphere with the modification of surfactant Sodium styrene sulfonate (PS) the dispersion liquid 15ml that makes among the embodiment 1, and abundant ultrasonic mixing obtains Treatment Solution.Treatment fluid is heated to 100 ℃, and remains on this temperature, the titanium alloy sheet is immersed in the Treatment Solution soaked 0.5 hour, use high voltage mercury lamp simultaneously, power 1000W, 254nm place light intensity is 65 ± 5w/m
20.5 hour ultraviolet light of irradiation, remove ultraviolet source again, allow the titanium alloy sheet in 100 ℃ Treatment Solution, soak 35.5 hours more again, take out the back and in the oxolane of 50ml, soaked 0.5 hour, remove polystyrene, take out the matrix of removing polystyrene, after washed with de-ionized water, immersed in 80 ℃ of deionized waters 48 hours, and finished thin film deposition, obtain titania coextruded film.
Embodiment 17
Sample is the Ti-6Al-4V of 10 * 10 * 1mm, and it is standby to clean the back.Get the 0.01mol/L TiOSO that makes among the embodiment 11
4, 0.01mol/L H
2O
2Mixed solution 30ml adds the polystyrene microsphere with the modification of surfactant Sodium styrene sulfonate (PS) the dispersion liquid 15ml that makes among the embodiment 1, and abundant ultrasonic mixing obtains Treatment Solution.Treatment fluid is heated to 80 ℃, and remains on this temperature, the titanium alloy sheet is immersed in the Treatment Solution soaked 0.5 hour, use high voltage mercury lamp simultaneously, power 1000W, 254nm place light intensity is 65 ± 5w/m
20.5 hour ultraviolet light of irradiation, remove ultraviolet source again, allow the titanium alloy sheet in 80 ℃ Treatment Solution, soak 35.5 hours more again, take out the back and in the oxolane of 50ml, soaked 0.5 hour, remove polystyrene, take out the matrix of removing polystyrene, after washed with de-ionized water, immersed in 80 ℃ of deionized waters 48 hours, and finished thin film deposition, obtain titania coextruded film.
Embodiment 18
Sample is the Ti-6Al-4V of 10 * 10 * 1mm, and it is standby to clean the back.Get the 0.01mol/L TiOSO that makes among the embodiment 11
4, 0.01mol/L H
2O
2Mixed solution 30ml adds the polystyrene microsphere with the modification of surfactant Sodium styrene sulfonate (PS) the dispersion liquid 15ml that makes among the embodiment 1, and abundant ultrasonic mixing obtains Treatment Solution.Treatment fluid is heated to 60 ℃, and remains on this temperature, the titanium alloy sheet is immersed in the Treatment Solution soaked 0.5 hour, use high voltage mercury lamp simultaneously, power 1000W, 254nm place light intensity is 65 ± 5w/m
20.5 hour ultraviolet light of irradiation, remove ultraviolet source again, allow the titanium alloy sheet in 60 ℃ Treatment Solution, soak 35.5 hours more again, take out the back and in the oxolane of 50ml, soaked 0.5 hour, remove polystyrene, take out the matrix of removing polystyrene, after washed with de-ionized water, immersed in 80 ℃ of deionized waters 48 hours, and finished thin film deposition, obtain titania coextruded film.
Embodiment 19
Sample is the Ti-6Al-4V of 10 * 10 * 1mm, and it is standby to clean the back.Get the 0.01mol/L TiOSO that makes among the embodiment 11
4, 0.01mol/L H
2O
2Mixed solution 30ml adds the polystyrene microsphere with the modification of surfactant Sodium styrene sulfonate (PS) the dispersion liquid 15ml that makes among the embodiment 1, and abundant ultrasonic mixing obtains Treatment Solution.Treatment fluid is heated to 100 ℃, and remains on this temperature, the titanium alloy sheet is immersed in the Treatment Solution soaked 1 hour, use high voltage mercury lamp simultaneously, power 1000W, 254nm place light intensity is 65 ± 5w/m
21 hour ultraviolet light of irradiation, remove ultraviolet source again, allow the titanium alloy sheet in 100 ℃ Treatment Solution, soak 23 hours more again, take out the back and in the oxolane of 50ml, soaked 0.5 hour, remove polystyrene, take out the matrix of removing polystyrene, after washed with de-ionized water, immersed in 80 ℃ of deionized waters 48 hours, and finished thin film deposition, obtain titania coextruded film.
Sample is the Ti-6Al-4V of 10 * 10 * 1mm, and it is standby to clean the back.Get the 0.01mol/L TiOSO that makes among the embodiment 11
4, 0.01mol/L H
2O
2Mixed solution 30ml adds the polystyrene microsphere with the modification of surfactant Sodium styrene sulfonate (PS) the dispersion liquid 15ml that makes among the embodiment 1, and abundant ultrasonic mixing obtains Treatment Solution.Treatment fluid is heated to 100 ℃, and remains on this temperature, the titanium alloy sheet is immersed in the Treatment Solution soaked 2 hours, use high voltage mercury lamp simultaneously, power 1000W, 254nm place light intensity is 65 ± 5w/m
22 hours ultraviolet lights of irradiation, remove ultraviolet source again, allow the titanium alloy sheet in 100 ℃ Treatment Solution, soak 46 hours more again, take out the back and in the oxolane of 50ml, soaked 0.5 hour, remove polystyrene, take out the matrix of removing polystyrene, after washed with de-ionized water, immersed in 80 ℃ of deionized waters 48 hours, and finished thin film deposition, obtain titania coextruded film.
Embodiment 21
With 350ml surfactant dodecyl sodium sulfate (SDS),, make the polystyrene microsphere dispersion liquid after the modification of 0.06g/ml with abundant ultrasonic mixing of 21g polystyrene microsphere (PS).
H with 1.02g
2O
2(30%wt) add fully mixing in the 300ml deionized water, obtain the H of 0.03mol/L
2O
2Aqueous solution.Get the TiCl of 2.16g
4Powder adds the H2O2 aqueous solution of 0.03mol/L, makes 0.04mol/L TiCl
4, 0.03mol/L H
2O
2Mixed solution.
Sample is the pure titanium of 10 * 10 * 1mm, and it is standby to clean the back.Get above-mentioned 0.04mol/L TiCl
4, 0.03mol/LH
2O
2Mixed solution 30ml adds above-mentioned polystyrene microsphere with the modification of surfactant dodecyl sodium sulfate (PS) dispersion liquid 20ml, and abundant ultrasonic mixing obtains Treatment Solution.Treatment fluid is heated to 90 ℃, and remains on this temperature, the titanium sheet is immersed in the Treatment Solution soaked 0.5 hour, use high voltage mercury lamp simultaneously, power 1000W, 254nm place light intensity is 65 ± 5w/m
20.5 hour ultraviolet light of irradiation, remove ultraviolet source again, allow the titanium sheet in 90 ℃ Treatment Solution, soak 35.5 hours more again, take out the back and in the oxolane of 50ml, soaked 0.5 hour, remove polystyrene, take out the matrix of removing polystyrene, after washed with de-ionized water, immersed in 80 ℃ of deionized waters 48 hours, and finished thin film deposition, obtain titania coextruded film.
Embodiment 22
Sample is the pure titanium of 10 * 10 * 1mm, and it is standby to clean the back.Get the 0.04mol/LTiCl that makes among the embodiment 21
4, 0.03mol/L H
2O
2Mixed solution 30ml adds the polystyrene microsphere with the modification of surfactant dodecyl sodium sulfate (PS) the dispersion liquid 20ml that makes among the embodiment 21, and abundant ultrasonic mixing obtains Treatment Solution.Treatment fluid is heated to 70 ℃, and remains on this temperature, the titanium sheet is immersed in the Treatment Solution soaked 0.5 hour, use high voltage mercury lamp simultaneously, power 1000W, 254nm place light intensity is 65 ± 5w/m
20.5 hour ultraviolet light of irradiation, remove ultraviolet source again, allow the titanium sheet in 70 ℃ Treatment Solution, soak 35.5 hours more again, take out the back and in the oxolane of 50ml, soaked 0.5 hour, remove polystyrene, take out the matrix of removing polystyrene, after washed with de-ionized water, immersed in 80 ℃ of deionized waters 48 hours, and finished thin film deposition, obtain titania coextruded film.
Embodiment 23
Sample is the pure titanium of 10 * 10 * 1mm, and it is standby to clean the back.Get the 0.04mol/LTiCl that makes among the embodiment 21
4, 0.03mol/L H
2O
2Mixed solution 30ml adds the polystyrene microsphere with the modification of surfactant dodecyl sodium sulfate (PS) the dispersion liquid 20ml that makes among the embodiment 21, and abundant ultrasonic mixing obtains Treatment Solution.Treatment fluid is heated to 60 ℃, and remains on this temperature, the titanium sheet is immersed in the Treatment Solution soaked 0.5 hour, use high voltage mercury lamp simultaneously, power 1000W, 254nm place light intensity is 65 ± 5w/m
20.5 hour ultraviolet light of irradiation, remove ultraviolet source again, allow the titanium sheet in 60 ℃ Treatment Solution, soak 35.5 hours more again, take out the back and in the oxolane of 50ml, soaked 0.5 hour, remove polystyrene, take out the matrix of removing polystyrene, after washed with de-ionized water, immersed in 80 ℃ of deionized waters 48 hours, and finished thin film deposition, obtain titania coextruded film.
Embodiment 24
Sample is the pure titanium of 10 * 10 * 1mm, and it is standby to clean the back.Get the 0.04mol/LTiCl that makes among the embodiment 21
4, 0.03mol/L H
2O
2Mixed solution 30ml adds the polystyrene microsphere with the modification of surfactant dodecyl sodium sulfate (PS) the dispersion liquid 20ml that makes among the embodiment 21, and abundant ultrasonic mixing obtains Treatment Solution.Treatment fluid is heated to 90 ℃, and remains on this temperature, the titanium sheet is immersed in the Treatment Solution soaked 1 hour, use high voltage mercury lamp simultaneously, power 1000W, 254nm place light intensity is 65 ± 5w/m
21 hour ultraviolet light of irradiation, remove ultraviolet source again, allow the titanium sheet in 90 ℃ Treatment Solution, soak 23 hours more again, take out the back and in the oxolane of 50ml, soaked 0.5 hour, remove polystyrene, take out the matrix of removing polystyrene, after washed with de-ionized water, immersed in 80 ℃ of deionized waters 48 hours, and finished thin film deposition, obtain titania coextruded film.
Sample is the pure titanium of 10 * 10 * 1mm, and it is standby to clean the back.Get the 0.04mol/LTiCl that makes among the embodiment 21
4, 0.03mol/L H
2O
2Mixed solution 30ml adds the polystyrene microsphere with the modification of surfactant dodecyl sodium sulfate (PS) the dispersion liquid 20ml that makes among the embodiment 21, and abundant ultrasonic mixing obtains Treatment Solution.Treatment fluid is heated to 100 ℃, and remains on this temperature, the titanium sheet is immersed in the Treatment Solution soaked 2 hours, use high voltage mercury lamp simultaneously, power 1000W, 254nm place light intensity is 65 ± 5w/m
22 hours ultraviolet lights of irradiation, remove ultraviolet source again, allow the titanium sheet in 100 ℃ Treatment Solution, soak 46 hours more again, take out the back and in the oxolane of 50ml, soaked 0.5 hour, remove polystyrene, take out the matrix of removing polystyrene, after washed with de-ionized water, immersed in 80 ℃ of deionized waters 48 hours, and finished thin film deposition, obtain titania coextruded film.
Embodiment 26
Sample is the Ti-6Al-4V of 10 * 10 * 1mm, and it is standby to clean the back.Get the 0.04mol/L TiCl that makes among the embodiment 21
4, 0.03mol/L H
2O
2Mixed solution 30ml adds the polystyrene microsphere with the modification of surfactant dodecyl sodium sulfate (PS) the dispersion liquid 20ml that makes among the embodiment 21, and abundant ultrasonic mixing obtains Treatment Solution.Treatment fluid is heated to 90 ℃, and remains on this temperature, the titanium alloy sheet is immersed in the Treatment Solution soaked 0.5 hour, use high voltage mercury lamp simultaneously, power 1000W, 254nm place light intensity is 65 ± 5w/m
20.5 hour ultraviolet light of irradiation, remove ultraviolet source again, allow the titanium alloy sheet in 90 ℃ Treatment Solution, soak 35.5 hours more again, take out the back and in the oxolane of 50ml, soaked 0.5 hour, remove polystyrene, take out the matrix of removing polystyrene, after washed with de-ionized water, immersed in 80 ℃ of deionized waters 48 hours, and finished thin film deposition, obtain titania coextruded film.
Embodiment 27
Sample is the Ti-6Al-4V of 10 * 10 * 1mm, and it is standby to clean the back.Get the 0.04mol/L TiCl that makes among the embodiment 21
4, 0.03mol/L H
2O
2Mixed solution 30ml adds the polystyrene microsphere with the modification of surfactant dodecyl sodium sulfate (PS) the dispersion liquid 20ml that makes among the embodiment 21, and abundant ultrasonic mixing obtains Treatment Solution.Treatment fluid is heated to 70 ℃, and remains on this temperature, the titanium alloy sheet is immersed in the Treatment Solution soaked 0.5 hour, use high voltage mercury lamp simultaneously, power 1000W, 254nm place light intensity is 65 ± 5w/m
20.5 hour ultraviolet light of irradiation, remove ultraviolet source again, allow the titanium alloy sheet in 70 ℃ Treatment Solution, soak 35.5 hours more again, take out the back and in the oxolane of 50ml, soaked 0.5 hour, remove polystyrene, take out the matrix of removing polystyrene, after washed with de-ionized water, immersed in 80 ℃ of deionized waters 48 hours, and finished thin film deposition, obtain titania coextruded film.
Embodiment 28
Sample is the Ti-6Al-4V of 10 * 10 * 1mm, and it is standby to clean the back.Get the 0.04mol/L TiCl that makes among the embodiment 21
4, 0.03mol/L H
2O
2Mixed solution 30ml adds the polystyrene microsphere with the modification of surfactant dodecyl sodium sulfate (PS) the dispersion liquid 20ml that makes among the embodiment 21, and abundant ultrasonic mixing obtains Treatment Solution.Treatment fluid is heated to 60 ℃, and remains on this temperature, the titanium alloy sheet is immersed in the Treatment Solution soaked 0.5 hour, use high voltage mercury lamp simultaneously, power 1000W, 254nm place light intensity is 65 ± 5w/m
20.5 hour ultraviolet light of irradiation, remove ultraviolet source again, allow the titanium alloy sheet in 60 ℃ Treatment Solution, soak 35.5 hours more again, take out the back and in the oxolane of 50ml, soaked 0.5 hour, remove polystyrene, take out the matrix of removing polystyrene, after washed with de-ionized water, immersed in 80 ℃ of deionized waters 48 hours, and finished thin film deposition, obtain titania coextruded film.
Embodiment 29
Sample is the Ti-6Al-4V of 10 * 10 * 1mm, and it is standby to clean the back.Get the 0.04mol/L TiCl that makes among the embodiment 21
4, 0.03mol/L H
2O
2Mixed solution 30ml adds the polystyrene microsphere with the modification of surfactant dodecyl sodium sulfate (PS) the dispersion liquid 20ml that makes among the embodiment 21, and abundant ultrasonic mixing obtains Treatment Solution.Treatment fluid is heated to 90 ℃, and remains on this temperature, the titanium alloy sheet is immersed in the Treatment Solution soaked 1 hour, use high voltage mercury lamp simultaneously, power 1000W, 254nm place light intensity is 65 ± 5w/m
21 hour ultraviolet light of irradiation, remove ultraviolet source again, allow the titanium alloy sheet in 90 ℃ Treatment Solution, soak 23 hours more again, take out the back and in the oxolane of 50ml, soaked 0.5 hour, remove polystyrene, take out the matrix of removing polystyrene, after washed with de-ionized water, immersed in 80 ℃ of deionized waters 48 hours, and finished thin film deposition, obtain titania coextruded film.
Sample is the Ti-6Al-4V of 10 * 10 * 1mm, and it is standby to clean the back.Get the 0.04mol/L TiCl that makes among the embodiment 21
4, 0.03mol/L H
2O
2Mixed solution 30ml adds the polystyrene microsphere with the modification of surfactant dodecyl sodium sulfate (PS) the dispersion liquid 20ml that makes among the embodiment 21, and abundant ultrasonic mixing obtains Treatment Solution.Treatment fluid is heated to 90 ℃, and remains on this temperature, the titanium alloy sheet is immersed in the Treatment Solution soaked 2 hours, use high voltage mercury lamp simultaneously, power 1000W, 254nm place light intensity is 65 ± 5w/m
22 hours ultraviolet lights of irradiation, remove ultraviolet source again, allow the titanium alloy sheet in 90 ℃ Treatment Solution, soak 46 hours more again, take out the back and in the oxolane of 50ml, soaked 0.5 hour, remove polystyrene, take out the matrix of removing polystyrene, after washed with de-ionized water, immersed in 80 ℃ of deionized waters 48 hours, and finished thin film deposition, obtain titania coextruded film.
Embodiment 31
H with 0.34g
2O
2(30%wt) add fully mixing in the 300ml deionized water, obtain the H of 0.01mol/L
2O
2Aqueous solution.Get the TiOSO of 1.08g
4Powder adds the H of 0.01mol/L
2O
2Aqueous solution makes 0.02mol/L TiCl
4, 0.01mol/L H
2O
2Mixed solution.
Sample is the pure titanium of 10 * 10 * 1mm, and it is standby to clean the back.Get above-mentioned 0.02mol/L TiCl
4, 0.01mol/LH
2O
2Mixed solution 30ml adds the polystyrene microsphere with the modification of surfactant dodecyl sodium sulfate (PS) the dispersion liquid 15ml that makes among the embodiment 21, and abundant ultrasonic mixing obtains Treatment Solution.Treatment fluid is heated to 90 ℃, and remains on this temperature, the titanium sheet is immersed in the Treatment Solution soaked 0.5 hour, use high voltage mercury lamp simultaneously, power 1000W, 254nm place light intensity is 65 ± 5w/m
20.5 hour ultraviolet light of irradiation, remove ultraviolet source again, allow the titanium sheet in 90 ℃ Treatment Solution, soak 35.5 hours more again, take out the back and in the oxolane of 50ml, soaked 0.5 hour, remove polystyrene, take out the matrix of removing polystyrene, after washed with de-ionized water, immersed in 80 ℃ of deionized waters 48 hours, and finished thin film deposition, obtain titania coextruded film.
Embodiment 32
Sample is the titanium sheet of 10 * 10 * 1mm, and it is standby to clean the back.Get the 0.02mol/LTiCl that makes among the embodiment 31
4, 0.01mol/L H
2O
2Mixed solution 30ml adds the polystyrene microsphere with the modification of surfactant dodecyl sodium sulfate (PS) the dispersion liquid 15ml that makes among the embodiment 21, and abundant ultrasonic mixing obtains Treatment Solution.Treatment fluid is heated to 70 ℃, and remains on this temperature, the titanium sheet is immersed in the Treatment Solution soaked 0.5 hour, use high voltage mercury lamp simultaneously, power 1000W, 254nm place light intensity is 65 ± 5w/m
20.5 hour ultraviolet light of irradiation, remove ultraviolet source again, allow the titanium sheet in 70 ℃ Treatment Solution, soak 35.5 hours more again, take out the back and in the oxolane of 50ml, soaked 0.5 hour, remove polystyrene, take out the matrix of removing polystyrene, after washed with de-ionized water, immersed in 80 ℃ of deionized waters 48 hours, and finished thin film deposition, obtain titania coextruded film.
Embodiment 33
Sample is the pure titanium of 10 * 10 * 1mm, and it is standby to clean the back.Get the 0.02mol/LTiCl that makes among the embodiment 31
4, 0.01mol/L H
2O
2Mixed solution 30ml adds the polystyrene microsphere with the modification of surfactant dodecyl sodium sulfate (PS) the dispersion liquid 15ml that makes among the embodiment 21, and abundant ultrasonic mixing obtains Treatment Solution.Treatment fluid is heated to 60 ℃, and remains on this temperature, the titanium sheet is immersed in the Treatment Solution soaked 0.5 hour, use high voltage mercury lamp simultaneously, power 1000W, 254nm place light intensity is 65 ± 5w/m
20.5 hour ultraviolet light of irradiation, remove ultraviolet source again, allow the titanium sheet in 60 ℃ Treatment Solution, soak 35.5 hours more again, take out the back and in the oxolane of 50ml, soaked 0.5 hour, remove polystyrene, take out the matrix of removing polystyrene, after washed with de-ionized water, immersed in 80 ℃ of deionized waters 48 hours, and finished thin film deposition, obtain titania coextruded film.
Embodiment 34
Sample is the pure titanium of 10 * 10 * 1mm, and it is standby to clean the back.Get the 0.02mol/LTiCl that makes among the embodiment 31
4, 0.01mol/L H
2O
2Mixed solution 30ml adds the polystyrene microsphere with the modification of surfactant dodecyl sodium sulfate (PS) the dispersion liquid 15ml that makes among the embodiment 21, and abundant ultrasonic mixing obtains Treatment Solution.Treatment fluid is heated to 90 ℃, and remains on this temperature, the titanium sheet is immersed in the Treatment Solution soaked 1 hour, use high voltage mercury lamp simultaneously, power 1000W, 254nm place light intensity is 65 ± 5w/m
21 hour ultraviolet light of irradiation, remove ultraviolet source again, allow the titanium sheet in 90 ℃ Treatment Solution, soak 23 hours more again, take out the back and in the oxolane of 50ml, soaked 0.5 hour, remove polystyrene, take out the matrix of removing polystyrene, after washed with de-ionized water, immersed in 80 ℃ of deionized waters 48 hours, and finished thin film deposition, obtain titania coextruded film.
Embodiment 35
Sample is the pure titanium of 10 * 10 * 1mm, and it is standby to clean the back.Get the 0.02mol/LTiCl that makes among the embodiment 31
4, 0.01mol/L H
2O
2Mixed solution 30ml adds the polystyrene microsphere with the modification of surfactant dodecyl sodium sulfate (PS) the dispersion liquid 15ml that makes among the embodiment 21, and abundant ultrasonic mixing obtains Treatment Solution.Treatment fluid is heated to 90 ℃, and remains on this temperature, the titanium sheet is immersed in the Treatment Solution soaked 2 hours, use high voltage mercury lamp simultaneously, power 1000W, 254nm place light intensity is 65 ± 5w/m
22 hours ultraviolet lights of irradiation, remove ultraviolet source again, allow the titanium sheet in 90 ℃ Treatment Solution, soak 46 hours more again, take out the back and in the oxolane of 50ml, soaked 0.5 hour, remove polystyrene, take out the matrix of removing polystyrene, after washed with de-ionized water, immersed in 80 ℃ of deionized waters 48 hours, and finished thin film deposition, obtain titania coextruded film.
Embodiment 36
Sample is the Ti-6Al-4V of 10 * 10 * 1mm, and it is standby to clean the back.Get the 0.02mol/L TiCl that makes among the embodiment 31
4, 0.01mol/L H
2O
2Mixed solution 30ml adds the polystyrene microsphere with the modification of surfactant dodecyl sodium sulfate (PS) the dispersion liquid 15ml that makes among the embodiment 21, and abundant ultrasonic mixing obtains Treatment Solution.Treatment fluid is heated to 90 ℃, and remains on this temperature, the titanium alloy sheet is immersed in the Treatment Solution soaked 0.5 hour, use high voltage mercury lamp simultaneously, power 1000W, 254nm place light intensity is 65 ± 5w/m
20.5 hour ultraviolet light of irradiation, remove ultraviolet source again, allow the titanium alloy sheet in 90 ℃ Treatment Solution, soak 35.5 hours more again, take out the back and in the oxolane of 50ml, soaked 0.5 hour, remove polystyrene, take out the matrix of removing polystyrene, after washed with de-ionized water, immersed in 80 ℃ of deionized waters 48 hours, and finished thin film deposition, obtain titania coextruded film.
Embodiment 37
Sample is the Ti-6Al-4V of 10 * 10 * 1mm, and it is standby to clean the back.Get the 0.02mol/L TiCl that makes among the embodiment 31
4, 0.01mol/L H
2O
2Mixed solution 30ml adds the polystyrene microsphere with the modification of surfactant dodecyl sodium sulfate (PS) the dispersion liquid 15ml that makes among the embodiment 21, and abundant ultrasonic mixing obtains Treatment Solution.Treatment fluid is heated to 70 ℃, and remains on this temperature, the titanium alloy sheet is immersed in the Treatment Solution soaked 0.5 hour, use high voltage mercury lamp simultaneously, power 1000W, 254nm place light intensity is 65 ± 5w/m
20.5 hour ultraviolet light of irradiation, remove ultraviolet source again, allow the titanium alloy sheet in 70 ℃ Treatment Solution, soak 35.5 hours more again, take out the back and in the oxolane of 50ml, soaked 0.5 hour, remove polystyrene, take out the matrix of removing polystyrene, after washed with de-ionized water, immersed in 80 ℃ of deionized waters 48 hours, and finished thin film deposition, obtain titania coextruded film.
Embodiment 38
Sample is the Ti-6Al-4V of 10 * 10 * 1mm, and it is standby to clean the back.Get the 0.02mol/L TiCl that makes among the embodiment 31
4, 0.01mol/L H
2O
2Mixed solution 30ml adds the polystyrene microsphere with the modification of surfactant dodecyl sodium sulfate (PS) the dispersion liquid 15ml that makes among the embodiment 21, and abundant ultrasonic mixing obtains Treatment Solution.Treatment fluid is heated to 60 ℃, and remains on this temperature, the titanium alloy sheet is immersed in the Treatment Solution soaked 0.5 hour, use high voltage mercury lamp simultaneously, power 1000W, 254nm place light intensity is 65 ± 5w/m
20.5 hour ultraviolet light of irradiation, remove ultraviolet source again, allow the titanium alloy sheet in 60 ℃ Treatment Solution, soak 35.5 hours more again, take out the back and in the oxolane of 50ml, soaked 0.5 hour, remove polystyrene, take out the matrix of removing polystyrene, after washed with de-ionized water, immersed in 80 ℃ of deionized waters 48 hours, and finished thin film deposition, obtain titania coextruded film.
Embodiment 39
Sample is the Ti-6Al-4V of 10 * 10 * 1mm, and it is standby to clean the back.Get the 0.02mol/L TiCl that makes among the embodiment 31
4, 0.01mol/L H
2O
2Mixed solution 30ml adds the polystyrene microsphere with the modification of surfactant dodecyl sodium sulfate (PS) the dispersion liquid 15ml that makes among the embodiment 21, and abundant ultrasonic mixing obtains Treatment Solution.Treatment fluid is heated to 90 ℃, and remains on this temperature, the titanium alloy sheet is immersed in the Treatment Solution soaked 1 hour, use high voltage mercury lamp simultaneously, power 1000W, 254nm place light intensity is 65 ± 5w/m
21 hour ultraviolet light of irradiation, remove ultraviolet source again, allow the titanium alloy sheet in 90 ℃ Treatment Solution, soak 23 hours more again, take out the back and in the oxolane of 50ml, soaked 0.5 hour, remove polystyrene, take out the matrix of removing polystyrene, after washed with de-ionized water, immersed in 80 ℃ of deionized waters 48 hours, and finished thin film deposition, obtain titania coextruded film.
Sample is the Ti-6Al-4V of 10 * 10 * 1mm, and it is standby to clean the back.Get the 0.02mol/L TiCl4 that makes among the embodiment 31,0.01mol/L H
2O
2Mixed solution 30ml adds the polystyrene microsphere with the modification of surfactant dodecyl sodium sulfate (PS) the dispersion liquid 15ml that makes among the embodiment 21, and abundant ultrasonic mixing obtains Treatment Solution.Treatment fluid is heated to 90 ℃, and remains on this temperature, the titanium alloy sheet is immersed in the Treatment Solution soaked 2 hours, use high voltage mercury lamp simultaneously, power 1000W, 254nm place light intensity is 65 ± 5w/m
22 hours ultraviolet lights of irradiation, remove ultraviolet source again, allow the titanium alloy sheet in 90 ℃ Treatment Solution, soak 46 hours more again, take out the back and in the oxolane of 50ml, soaked 0.5 hour, remove polystyrene, take out the matrix of removing polystyrene, after washed with de-ionized water, immersed in 80 ℃ of deionized waters 48 hours, and finished thin film deposition, obtain titania coextruded film.
Embodiment 41
(1) embodiment 1 obtains TiO
2The analysis of the surperficial thing phase of laminated film
As shown in Figure 1, soak time is 36 hours, and the titanio surface can obtain the anatase and the rutile titanium dioxide of crystallization.This titanium dioxide small part comes from H
2O
2To the corrosion of titanio body, most of from TiOSO
4Hydrolysis.Simultaneously because H
2O
2The titanium dioxide film that the corrosion of matrix is produced belongs to original position and generates, and with matrix good binding is arranged.This just helps increasing TiO
2The bond strength of/Ti.When the self assembly temperature reached 100 ℃, hydrolytic process was accelerated, and micelle increases, adsorbance increases, and nucleation rate is accelerated, and nucleus forms the back and grows into sphere from all directions, as Fig. 2, in conjunction with Fig. 3 surface EDS energy spectrogram as can be known, this titanio surface mainly is made up of element ti and O.
(2) embodiment 1 obtains TiO
2The active research of the external biological of laminated film.
The biological activity of material is meant that biomaterial and live body osseous tissue produce the ability of chemical bonding, is an important indicator weighing biomaterial.The ability of this chemical bonding is to be determined by the dissolving and the deposition behavior of this material in body fluid.After material implanted, its surface can exchange with the ion in the body fluid, and the calcium ion in the body fluid, phosphate radical plasma can deposit class bone hydroxyapatite at implant surfaces under proper condition, thereby form good chemical bonding with osseous tissue.Therefore the activity of bio-medical material can be estimated by in-vitro simulated body fluid (SBF) soak test.
The titania coextruded film that obtains among the embodiment 1 immersed again in 36.5 ℃ the simulated body fluid after 12 hours, (XRD) carries out material phase analysis by X-ray diffractometer, and observing 32.5 ° has cenotype-apatite to occur, as shown in Figure 4.Observe its surface topography (Fig. 5) by scanning electron microscope (SEM), finding has spherical electrodeposition substance, the EDS energy spectrum analysis of corresponding diagram 6, and this ball is made of elements such as Ca, P.In conjunction with XRD, SEM and EDS, characterizing this sphere is apatite.Find out that thus the titanium dioxide layer for preparing through self-assembly method has good apatite deposition capability, only just can bring out the deposition of apatite in 12 hours.The titania coextruded film that obtains among the embodiment 1 was immersed 36.5 ℃ simulated body fluid after 24 hours, and as shown in Figure 7, film surface has a large amount of apatite depositions.
Comprehensive above-mentioned picture and description, conclusion is as follows:
(1) the present invention is a template with monodisperse polystyrene (PS) ball, cheap inorganic titanium salt is a raw material, prepared self-assembly nano-crystalline titanium dioxide microcapsule biofilm by hydrolysis-sol method at low temperatures, overcome in the additive method because of the restriction of hot conditions to material.This thin film has big specific surface energy, more helps the deposition of apatite on the surface.
(2) under thermal and hydric environment, owing to there is not follow-up heat treatment, make the titanium hydroxyl (Ti-OH) of material surface obtain keeping to greatest extent, improved the biological activity of matrix greatly.
(3) TiO
2Film is subjected to become super hydrophilic surface after the UV rayed, and its minimum contact angle is 1 °.Water dissociates at the oxygen defect place to adsorb and generates hydroxyl, forms Ti-OH functional group, thereby makes TiO
2The film possess hydrophilic property, the Ti-OH functional group disappearance that causes when removing the PS template to remedy, thus regain good biological activity.
Claims (10)
1. medical titanium or titanium alloy surface activation modification method, it is characterized in that described method is (1) preparation treatment fluid: being template through surfactant-modified monodisperse polystyrene (PS) ball, the inorganic titanium saline solution is a precursor liquid, make Treatment Solution, the making of described Treatment Solution comprises the steps: in the ratio that adds polystyrene microsphere 0.01～0.10g in every 1ml surfactant, polystyrene microsphere joined disperse modification in the surfactant, make the monodisperse polystyrene microsphere dispersion liquid of modification, add the inorganic titanium saline solution again, fully mix homogeneously is made Treatment Solution, the volume ratio of the monodisperse polystyrene microsphere dispersion liquid of titanium salt aqueous solution and modification was 10～1: 1 when described treatment fluid was prepared, the molar concentration of described titanium salt aqueous solution is 0.01～0.08mol/L, and the ion attribute after described surfactant is water-soluble is opposite with the ion attribute of described titanium salt aqueous solution; (2) deposition processes of pure titanium or titanium alloy thin films: with pure titanium or titanium alloy as matrix, pure titanium or titanium alloy are immersed in the Treatment Solution, keep the Treatment Solution temperature at 60～100 ℃, 24～50 hours, wherein soaked in 60～100 ℃ Treatment Solution with irradiation under ultraviolet ray and described matrix simultaneously at least 0.25～2 hours; Matrix after soaking is taken out, immerse and to soak 0.5～1 hour in the organic solvent of dissolved polystyrene, after polystyrene is removed in dissolving, in 60～100 ℃ of deionized waters, soak 24～48 hours crystallization again, finish depositing of thin film, take out the titanium or the titanium alloy of the surface active modification that promptly gets surface modification.
2. the method for claim 1 is characterized in that also adding in the described pretreatment liquid H that final concentration is 0.01～0.08mol/L
2O
2, described H
2O
2H in the aqueous solution
2O
2Identical with the titanium molal quantity in the titanium salt aqueous solution, described H
2O
2Open type with aqueous solution adds.
3. the method for claim 1 is characterized in that inorganic titanium salt in the described inorganic titanium saline solution is one of following or the mixing of any several arbitrary proportions: titanyl sulfate, titanium tetrachloride, titanium tetrafluoride, tantalic chloride, hydrogen peroxide.
4. the method for claim 1 is characterized in that the organic solvent of described energy dissolved polystyrene is: oxolane, toluene, dimethylbenzene, chloroform, acetone, butanone or dimethyl formamide.
5. the method for claim 1, the deposition processes that it is characterized in that pure titanium of step (2) or titanium alloy thin films is: with pure titanium or titanium alloy as matrix, pure titanium or titanium alloy are immersed in the Treatment Solution, keep the Treatment Solution temperature at 60～100 ℃, simultaneously with irradiation under ultraviolet ray 0.25～2 hour, remove ultraviolet source, more described matrix is continued to soak in 60～100 ℃ Treatment Solution 24～48 hours; Matrix after soaking is taken out, immerse and to soak 0.5～1 hour in the organic solvent of dissolved polystyrene, after polystyrene is removed in dissolving, in 60～100 ℃ of deionized waters, soak 24～48 hours crystallization again, finish depositing of thin film, take out the titanium or the titanium alloy of the surface active modification that promptly gets surface modification.
6. the method for claim 1 is characterized in that the volume ratio of the monodisperse polystyrene microsphere of titanium salt aqueous solution and modification in the described treatment fluid is 2: 1.
7. the method for claim 1 is characterized in that described surfactant is Sodium styrene sulfonate, dodecylbenzene sodium sulfonate, dodecyl sodium sulfate, sodium lauryl sulphate, diphenylamines-4-sodium sulfonate, cetyl trimethyl ammonium bromide.
8. the method for claim 1 is characterized in that described irradiation under ultraviolet ray adopts the high voltage mercury lamp irradiation device, and power 1000W is 65 ± 5w/m in 254nm place light intensity
2, preferred 30 minutes of exposure time.
9. the method for claim 1 is characterized in that described pure titanium or titanium alloy being immersed in the Treatment Solution, keeps the Treatment Solution temperature at 100 ℃, and described is 36 hours with soaking total time in pure titanium or the titanium alloy substrate Treatment Solution.
10. the method for claim 1 is characterized in that described method after polystyrene is removed in dissolving, and soaking temperature is 80 ℃ in deionized water again, and soak time is 48 hours.
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| CN105671531A (en) * | 2016-01-20 | 2016-06-15 | 浙江工业大学 | Preparing method for in-site growth of titanium dioxide nanometer array film on surface of metal |
| CN106872344A (en) * | 2017-02-27 | 2017-06-20 | 北京科技大学 | The method for quick of combined material chip Sensitivity of Stress Corrosion |
| CN114288479A (en) * | 2021-12-30 | 2022-04-08 | 智享生物(苏州)有限公司 | Cell adhesion material based on supermolecule self-assembly and preparation method thereof |
| CN114717542A (en) * | 2022-04-02 | 2022-07-08 | 湖南理东科技有限公司 | Bowl-shaped titanium alloy surface modification method for photocatalysis and photo-thermal dual-mechanism antibiosis |
| CN114717542B (en) * | 2022-04-02 | 2024-05-03 | 理东新材料科技(山东)有限公司 | Bowl-shaped titanium alloy surface modification method with photocatalysis and photo-thermal dual mechanism antibacterial function |
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