CN102691087A - Surface treatment method for improving bioactivity of medical beta-type titanium alloy surface - Google Patents
Surface treatment method for improving bioactivity of medical beta-type titanium alloy surface Download PDFInfo
- Publication number
- CN102691087A CN102691087A CN2011100727135A CN201110072713A CN102691087A CN 102691087 A CN102691087 A CN 102691087A CN 2011100727135 A CN2011100727135 A CN 2011100727135A CN 201110072713 A CN201110072713 A CN 201110072713A CN 102691087 A CN102691087 A CN 102691087A
- Authority
- CN
- China
- Prior art keywords
- titanium alloy
- treatment method
- surface treatment
- layer
- oxidation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Abstract
The invention relates to the technical field of surface treatment and especially relates to a surface treatment method for improving bioactivity of a medical beta-type titanium alloy surface. The surface treatment method is characterized in that through anodic oxidation, hydro-thermal treatment and heating treatment on a titanium alloy, a composite oxide coating is formed on the surface of the titanium alloy; an inner layer is an oxide nanotube layer; the contents and element valences of Ti, Nb and Zr oxides of the inner layer change gradually; the diameter of the inner layer is in a range of 30 to 310nm; the thickness of the inner layer is in a range of 0 to 20 microns; and an outer layer is a calcium titanate layer having the thickness of 0 to 1 microns. The surface treatment method is suitable for a beta-type medical titanium alloy rich in Nb, Zr and the like. A gradient coating prepared by the surface treatment method has an integrated crystal form, has a high bone hydroxyapatite layer formation induction capacity and a high cell absorption and proliferation capacity of the surface, and has good biocompatibility. The surface treatment method can prevent the phase change and the brittle rupture caused by high temperature spaying. An oxide layer membrane is directly formed on a matrix by chemical and electrochemical principles so that the adherence between the matrix and the oxide layer membrane is improved. Through the surface treatment method, a uniform coating layer can be formed on a matrix having a complex shape without the limit of a matrix shape.
Description
Technical field
The present invention relates to technical field of surface, be specially a kind of surface treatment method that improves medical beta titanium alloy surface bioactive.
Background technology
Titanium alloy is widely used in the human body orthomorphia owing to having good mechanical property, low elastic modulus, the burn into of anti-human body fluid excellent biological compatibility.But titanium or titanium alloy still belongs to bio-inert material, with bone to combine be that a kind of machinery is sealed, combine and can not form strong chemical bond with tissue.Coenocorrelation is very complicated physics, a chemical environment; Comprise multiple factors such as the body fluid that is in contact with it, organic macromolecule, enzyme, radical, cell; Implant through long-term; Even consistency preferred metal element, it all is flagrant that the gathering of its ion stripping or abrasive particle acquires a certain degree.Therefore; Titanium alloy surface is carried out surface treatment; Adjust its surperficial chemical ingredients, surface energy and physicals etc. to improve its surface bioactive, its application in medical treatment is played crucial effects, modification is carried out on the surface of medical titanium alloy become research emphasis.
Recently, the anonizing research for preparing nanotube array oxide film has caused various countries scholars' extensive concern.But the preparation research of pure titanium and the titanium alloy surface nanotube that contains a small amount of other elements such as Al, V is devoted in great majority research; And for the β type medical titanium alloy that is rich in elements such as Nb, Zr, Sn; The growth technique of its nano surface periosteum layer and the control of growthhabit, not systematic research.
Water and titanium surface are contained more surface hydroxyl and (OH) are helped to improve the biological activity of titanium.Oxidation titanium film is carried out the hydrothermal treatment consists modification, and its effect is exactly material surface after modification and generates more hydroxyl (surface film oxide can continue the also hydration of growing when contact OH), or with the aqueous solution.When the oxidation titanium film on titanium or titanium alloy surface has abundant hydroxyl and suitable surperficial texture (like certain microvoid structure or roughness), just can have excellent biological compatibility.
Ti-24Nb-4Zr-8Sn (wt.%) is a kind of high-strength low-modulus β type medical titanium alloy of new research and development; The Young's modulus of this alloy (40-45GPa) and skeleton be complementary (10-30GPa); Have super-elasticity and the damping capacity similar with the vesicular structure bone; Characteristics such as its HS, corrosion-resistant, lifeless matter toxicity can satisfy human body and implant demand for a long time, have a good application prospect at medical field.But Ti-24Nb-4Zr-8Sn still is a bio-inert material, need carry out surface-treated to improve its bioactivation to it.
Summary of the invention
The purpose of this invention is to provide a kind of surface treatment method that improves medical beta titanium alloy surface bioactive; Its process method is simple, with low cost; Be rich in the medical beta titanium alloy surface preparation of element biological activity composite oxide coatings such as Nb, Zr, this method can improve the surface bioactive of the medical beta titanium alloys of element such as being rich in Nb, Zr greatly.
Technical scheme of the present invention is:
A kind of surface treatment method that improves medical beta titanium alloy surface bioactive; Be rich in the medical beta titanium alloy surface preparation of element biological activity combined oxidation coatings such as Nb, Zr; Comprise anodic oxidation, hydrothermal treatment consists and thermal treatment, at first, generate the nanotube oxide coatings on its surface through the titanium alloy surface oxidation is handled to titanium alloy surface; Carry out hydrothermal treatment consists then and generate the calcium titanate thin layer, heat-treat at last and stablize this composite oxide coating;
Described oxidation treatment method process is following: anodic oxidation mode, ammonium sulfate and Neutral ammonium fluoride are ionogen, and aqueous electrolyte liquid is 0.5-1.5mol/L NH
4NO
3, 0.05-0.2mol/L NH
4HF
2, voltage range is 10-80V, oxidization time is 0.5-5h.
Described anode oxidation process is following: under identical oxidization time; Along with oxidation voltage increases; The diameter of nanotube and length are all linear to be increased, and Ti, Nb, the corresponding oxide content of each element of Zr and the contained element valence of oxide compound change in nanotube in gradient; Under identical oxidation voltage, along with oxidization time increases, the vary in diameter of nanotube is little, and length increases.
Described anode oxidation process is following: at room temperature; Beta titanium alloy is done anode, and stainless steel vessel is made negative electrode, adopts the method for progressively boosting; The rate of rise under the different tests parameter is 0.3V/s-0.7V/s, and oxidization time picks up counting after boosting to setting voltage.
Described hydro-thermal treatment method process is following: solution is Ca (OH)
2Solution, strength of solution are 1M～5M, and the time is 0.5～5 hour, and in the process, envrionment temperature remains on 120-200 ℃, after the immersion, sample are cleaned with zero(ppm) water, in 40 ± 10 ℃ of air, dry then.
Described heat treatment regime is: temperature is 500～800 ℃, and soaking time is 0.5～2 hour, is 3～10 ℃/min with the stove temperature rise rate, and the type of cooling is a furnace cooling.
Among the present invention, after bakingout process, armorphous nanotube sull changes into anatase titania, and removes the poisonous element fluorine of introducing in the anode oxidation process in the nanotube, keeps the integrity of nanotube simultaneously.In addition, the amorphous state titanium-cuprum hydrochlorate that forms in the hydrothermal treatment consists process in heat treatment process also by crystallization.
Among the present invention; Under different electric chemical parameters and hydrothermal treatment consists parameter; Can generate internal layer on medical beta titanium alloy surface and be Ti, Nb, each element of Zr corresponding oxide content (comprising the contained element valence of oxide compound) change in gradient; Diameter is 30nm-310nm, and thickness can reach the oxide nano layer of 2～30 μ m, and skin is the composite oxide coating of thickness 0.5～2 μ m calcium titanate layer.
Among the present invention, medical beta titanium alloy can adopt Chinese invention patent (application number: 200410092858.1) disclosed a kind of super elasticity low modulus titanium alloy and preparation and working method.
Among the present invention, HTFX is a chamber type electric resistance furnace.
Among the present invention, anodic oxidation institute preparing electrolyte liquid agents useful for same is analytical pure.
Among the present invention, the required Ca of hydrothermal treatment consists (OH)
2Be analytical pure, purity is 99.9%, and equipment used is water-bath and temperature controllable heat packs, and temperature error is ± 2 ℃.
A kind of method at the medical beta titanium alloy surface preparation bio-active gradient oxide covering that is rich in elements such as Nb, Zr provided by the invention has the following advantages and beneficial effect:
1. the present invention can obtain having double-deck graded oxidation layer through the control to some influence factors in oxidising process and the hydrothermal treatment consists, and the thickness and the composition of complete each layer oxide compound of well can be controlled according to actual needs; The device simple that uses, simple to operate, anodised process does not need to stir, and does not need the recirculated water cooling, at room temperature can carry out.
2. the present invention adopts the method that anodize combines with hydrothermal treatment consists, under the prerequisite of not destroying huge specific surface area of nanotube zone of oxidation and microvoid structure, increases the biological activity of its upper layer.The hydrothermal treatment consists process approach is simple, the time spent very short (≤5 hours).
3. the heat treating method of the present invention's employing can eliminate the poisonous element fluorine of introducing owing to anodic oxidation in the nano tube structure, can make nanotube zone of oxidation and titanate layer crystallization, keeps the integrity of nanotube simultaneously.
4. the present invention does not receive the restriction of base material shape, can on complex-shaped matrix, prepare uniform coating.
5. the present invention both can be used as the method at the medical beta titanium alloy surface preparation bioactive coating that is rich in elements such as Nb, Zr, can be used for that also titanium dioxide film is carried out modification and improve its biological activity.
6. contain in the composite oxide coating of the present invention's preparation and contain the Nb oxide compound in a large number, this also has huge benefit to the antiwear property that improves titanium alloy surface.
In addition, with on other pure metal matrixes the preparation nanotube by comparison, the internal layer nanotube layer of the present invention in the composite oxide coating of the medical beta titanium alloy surface preparation that is rich in elements such as Nb, Zr has following characteristics:
1. the voltage range that generates nanotube is bigger, from 10V to 80V, can prepare the regular ordered nano-tube sull of different diameter.
2. through after 750 ℃ the high-temperature heat treatment, the nanotube of generation can also keep structural integrity not destroy.
3. in the nanotube coating of the present invention's preparation, Ti, Nb, the corresponding oxide content of each element of Zr and the contained element valence of oxide compound change in gradient.
Description of drawings
Fig. 1 adopts the present invention in identical oxidization time (1.5h), behind different oxidation voltage (10-80V), and the nanotube sull surface topography SEM figure that on medical titanium niobium zircalloy, generates.Wherein, (a) oxidation voltage of figure is 10V; (b) oxidation voltage of figure is 30V; (c) oxidation voltage of figure is 50V; (d) oxidation voltage of figure is 80V.
Fig. 2 adopts the present invention in identical oxidization time (1.5h), behind different oxidation voltage (10-80V), and the nanotube diameter that on medical titanium niobium zircalloy, generates and the graph of relation of length and oxidation voltage.
Fig. 3 adopts the present invention under identical oxidation voltage (40V), after the different oxidation time (1-5h), and the nanotube sull section S EM figure that on medical titanium niobium zircalloy, generates.Wherein, (a) oxidization time of figure is 1 hour; (b) oxidization time of figure is 2 hours; (c) oxidization time of figure is 3 hours; (d) oxidization time of figure is 5 hours.
Fig. 4 adopts the present invention under identical oxidation voltage (40V), after the different oxidation time (0.5-5h), and the nanotube length that on medical titanium niobium zircalloy, generates and the graph of relation of oxidization time.
Fig. 5 adopts the present invention on medical titanium niobium zircalloy, to generate the little grazing angle X-ray diffracting spectrum of nanotube sull.
Fig. 6 adopt nanotube sull ingredient that the present invention generates on medical titanium niobium zircalloy along thicknesses of layers distribution plan (a) and different element at the XPS of different thickness collection of illustrative plates: (b) Ti2p; (c) Nb3d; (d) Sn3d.
Fig. 7 adopts the nanotube pattern TEM figure of the present invention after the nanotube that generates on the medical titanium niobium zircalloy is through hydrothermal treatment consists and 750 ℃ of thermal treatment.
Fig. 8 adopts EDX figure (a) and the FTIR collection of illustrative plates (b) of the present invention after the nanotube that generates on the medical titanium niobium zircalloy is through hydrothermal treatment consists and thermal treatment.
Fig. 9 is the surface topography after soaking 3 days in the SBF dissolving of titanium niobium zircalloy surface after the technical finesse of the present invention at 37 ℃; (a) low power Win 40350 pattern; (b) high power Win 40350 pattern.
Figure 10 (a)-Figure 10 (b) is the scleroblast absorption (a) and propagation (b) situation on titanium niobium zircalloy surface after technical finesse of the present invention.
Figure 11 adopts the present invention in identical oxidization time (1.5h), behind different oxidation voltage, and the nanotube sull surface topography SEM figure that on the titanium niobium alloy, generates.Wherein, (a) oxidation voltage of figure is 30V; (b) oxidation voltage of figure is 40V;
Figure 12 adopts the present invention in the oxidization time of setting (1.5h), through behind the oxidation voltage of 30V, and nanotube sull surface that on titanium-zirconium alloy, generates and section S EM figure.Wherein, (a) figure is nanotube sull surface; (b) figure is nanotube sull cross section.
Embodiment
With diameter be 10mm, thickness be the Ti-24Nb-4Zr-8Sn sample of 1mm after polishing step by step with 800#, 1200#SiC sand paper on the pre-grinding machine, with acetone, absolute ethyl alcohol and deionized water ultrasonic cleaning each ten minutes, in air, dry up.
Described oxidation treatment method process is following: anodic oxidation mode, aqueous electrolyte liquid are 1 mol NH
4NO
3, 0.15 mol NH
4HF
2, the pH value of solution value is about 6-7.
At room temperature, titanium niobium zircalloy (Ti-24Nb-4Zr-8Sn) is done anode, stainless steel vessel is made negative electrode, adopts the method for progressively boosting, and the rate of rise under the different tests parameter is 0.5V/s, and oxidization time picks up counting after boosting to setting voltage.After oxidation is intact, use washed with de-ionized water.
Set identical oxidization time (1.5h), as shown in Figure 1 through the nanotube sull that different oxidation voltage (10-80V) back generates, wherein: (a) figure sull diameter is about 30nm, the about 2 μ m of thickness; (b) figure sull diameter is about 110nm, the about 7.3 μ m of thickness; (c) figure sull diameter is about 190nm, the about 8.7 μ m of thickness; (d) figure sull diameter is about 310nm, the about 11 μ m of thickness.Fig. 2 demonstrates the linear relationship of nanotube diameter and length and oxidation voltage.Set identical oxidation voltage (40V), as shown in Figure 3 through the nanotube sull that different oxidation time (0.5-5h) back generates, wherein: (a) figure sull diameter is about 164nm, the about 6 μ m of thickness; (b) figure sull diameter is about 168nm, the about 10.2 μ m of thickness; (c) figure sull diameter is about 160nm, the about 11.5 μ m of thickness; (d) figure sull diameter is about 162nm, the about 13.7 μ m of thickness.Fig. 4 demonstrates the similar linear relationship between nanotube length and the oxidization time.The nanotube sull that generates is armorphous, is shown as the β peak of matrix on the little grazing angle X-ray diffracting spectrum, and is as shown in Figure 5.The composition of sull is TiO
2, Ti
2O
3, TiO, Nb
2O
5, Nb
2O, NbO, SnO
2, ZrO
2, the pairing valence state of each constituent content and oxide compound changes in gradient, and is as shown in Figure 6.
Ti-24Nb-4Zr-8Sn sample after the oxide treatment is immersed in the Ca (OH) of 3mol/L
2In the aqueous solution, maintain the temperature at 150 ℃, soak time is 1～5h.Distilled water flushing subsequently, 40 ℃ of dryings, generating thickness is the calcium titanate thin layer of～1 μ m.
Ti-24Nb-4Zr-8Sn sample after the hydrothermal treatment consists is heated to 750 ℃ in chamber type electric resistance furnace, is incubated furnace cooling after 1.5 hours.Temperature rise rate is 3 ℃/min.
To pass through sample after anodic oxidation and the hydrothermal treatment consists, in chamber type electric resistance furnace, to be heated to 750 ℃ of nanotube patterns after the thermal treatment as shown in Figure 7, and nano tube structure does not have destruction.EDX and FTIR collection of illustrative plates through the composite oxide coating after anodic oxidation, hydrothermal treatment consists and the thermal treatment are as shown in Figure 8.By figure visible after three steps handled alloy surface oxide compound generations such as calcium titanate are arranged.
In SBF solution, soak after 3 days; Soaking specimen surface through anodic oxidation, hydrothermal treatment consists and heat treated Ti-24Nb-4Zr-8Sn sample has Win 40350 to generate (Fig. 9); And an alloy surface undressed and only process anodize does not have the Win 40350 generation; Show alloy surface after three steps handled, the spatial induction Win 40350 forms ability and obviously improves, and its surface biological consistency improves.
To carry out cell culture experiments through anodic oxidation, hydrothermal treatment consists and heat treated Ti-24Nb-4Zr-8Sn sample, the result shows alloy after three steps handled, and the cell of cell surface adsorbs and multiplication capacity is significantly improved (Figure 10).
Be with embodiment 1 difference:
The Ti-25Nb sample that with diameter for 10mm thickness is 1mm with acetone, absolute ethyl alcohol and deionized water ultrasonic cleaning each ten minutes, dries up in air after polishing step by step with 800#, 1200#SiC sand paper on the pre-grinding machine.
Described oxidation treatment method process is following: anodic oxidation mode, aqueous electrolyte liquid are 1.5 mol NH
4NO
3, 0.15 mol NH
4HF
2, the pH value of solution value is about 6-7.
At room temperature, (Ti-25Nb) does anode with the titanium niobium alloy, and stainless steel vessel is made negative electrode, adopts the method for progressively boosting, and the rate of rise under the different tests parameter is 0.5V/s, and oxidization time picks up counting after boosting to setting voltage.Use washed with de-ionized water after oxidation is intact.Set identical oxidization time (1.5h), shown in figure 11 through the nanotube sull that generates behind the different oxidation voltage, wherein: (a) figure sull diameter is about 115nm, the about 4.2 μ m of thickness; (b) figure sull diameter is about 160nm, the about 5.5 μ m of thickness.
Be with embodiment 1 difference:
The Ti-25Zr sample that with diameter for 10mm thickness is 1mm with acetone, absolute ethyl alcohol and deionized water ultrasonic cleaning each ten minutes, dries up in air after polishing step by step with 800#, 1200#SiC sand paper on the pre-grinding machine.
Described oxidation treatment method process is following: anodic oxidation mode, aqueous electrolyte liquid are 1.5 mol NH
4NO
3, 0.15 mol NH
4HF
2, the pH value of solution value is about 6-7.
At room temperature, (Ti-25Zr) does anode with titanium-zirconium alloy, and stainless steel vessel is made negative electrode, adopts the method for progressively boosting, and the rate of rise under the different tests parameter is 0.5V/s, and oxidization time picks up counting after boosting to setting voltage.Use washed with de-ionized water after oxidation is intact.Set oxidization time (1.5h), shown in figure 12 through the nanotube sull surface and the cross section that generate behind the oxidation voltage of 30V, wherein: (a) figure sull diameter is about 90nm; (b) the about 19 μ m of figure oxide thickness.
The result shows; The present invention adopts anodic oxidation, hydrothermal treatment consists and heat treatment phase bonded technology; Prepare composite oxide coating at Ti-24Nb-4Zr-8Sn (wt.%) alloy surface; This gradient cladding internal layer is diameter 30nm-310nm, thickness can reach～and the oxide nano layer of 20 μ m, skin is thickness～1 μ m calcium titanate layer.Its internal layer nanotube zone of oxidation is compared with the nanotube coating that pure titanium and conventional titanium alloy (like Ti6Al4V) anodize obtain; The nanotube zone of oxidation forming process that generates on the β type medical titanium alloy surface of being rich in elements such as Nb, Zr, Sn is different, and Ti, Nb, the corresponding oxide content of each element of Zr and the contained element valence of oxide compound change in gradient in the nanotube layer.The composite oxide coating of the present invention's preparation is rich in elements such as Nb, Zr, Sn to raising β type medical titanium alloy surfaces for biocompatibility has great promotion meaning.
In addition, the present invention also is suitable for the β type medical titanium alloy that is imbued with elements such as containing Nb, Zr, the gradient cladding complete in crystal formation of preparation, and the surface has the very high bone hydroxyapatite layer of inducing and forms ability, cell absorption and multiplication capacity, has good biocompatibility; Simultaneously, this technology equipment used is simple and easy, simple to operate, can prepare the gradient cladding of different thickness according to actual needs through control anodised working hour, WV and hydrothermal treatment process parameter etc.; Temperature remains at below 40 ℃ in the oxidising process, phase transformation and the embrittlement that can avoid pyrolytic coating to cause, and the oxidation tunic directly is created on matrix through chemistry and electrochemical principle, helps strengthening the bonding force between matrix and zone of oxidation; Do not receive the restriction of base material shape, can on complex-shaped matrix, prepare uniform coating.Therefore, the gradient bioactivation coating that generates of the present invention will have very big promoter action to the application of the β type medical titanium alloy that is rich in elements such as Nb, Zr.
Claims (6)
1. surface treatment method that improves medical beta titanium alloy surface bioactive; It is characterized in that: through beta titanium alloy is carried out anodic oxidation, hydrothermal treatment consists and thermal treatment; On medical beta titanium alloy surface, prepare composite oxide coating; Internal layer is that Ti, Nb, the corresponding oxide content of each element of Zr and the contained element valence of oxide compound change in gradient; Diameter is 30nm～310nm, and the oxide nano layer of thickness 2～30 μ m, skin are the composite oxide coating of thickness 0.5～2 μ m calcium titanate layer.
2. according to the surface treatment method of the medical beta titanium alloy surface bioactive of the described raising of claim 1; It is characterized in that; The standard of described oxide treatment is: anodic oxidation mode, ammonium sulfate and Neutral ammonium fluoride are ionogen, and aqueous electrolyte liquid is 0.5-1.5mol/L NH
4NO
3, 0.05-0.2mol/L NH
4HF
2, voltage range is 10-80V, oxidization time is 0.5-5h.
3. according to the surface treatment method of the medical beta titanium alloy surface bioactive of the described raising of claim 2; It is characterized in that described anode oxidation process is following: at room temperature, beta titanium alloy is done anode; Stainless steel vessel is made negative electrode; Adopt the method for progressively boosting, the rate of rise under the different tests parameter is 0.3-0.7V/s, and oxidization time picks up counting after boosting to setting voltage.
4. according to the surface treatment method of the medical beta titanium alloy surface bioactive of the described raising of claim 2; It is characterized in that; Under identical oxidization time; Along with oxidation voltage increases, the diameter of nanotube and length are all linear to be increased, and Ti, Nb, the corresponding oxide content of each element of Zr and the contained element valence of oxide compound change in gradient in the nanotube layer; Under identical oxidation voltage, along with oxidization time increases, the vary in diameter of nanotube is little, and length increases.
5. according to the surface treatment method of the medical beta titanium alloy surface bioactive of the described raising of claim 1, it is characterized in that, the titanium alloy surface after the oxidation is carried out hydrothermal treatment consists, generating thickness on its surface is the calcium titanate thin layer of 0.5～2 μ m; Solution is Ca (OH)
2Solution, strength of solution are 1M～5M, and the time is 0.5～5 hour, and in the process, envrionment temperature remains on 120-200 ℃, after the immersion, sample are cleaned with zero(ppm) water, in 40 ± 10 ℃ of air, dry then.
6. according to the surface treatment method of the medical beta titanium alloy surface bioactive of the described raising of claim 1; It is characterized in that; Described heat treatment regime is: temperature is 500～800 ℃; Soaking time is 0.5～2 hour, is 3～10 ℃/min with the stove temperature rise rate, and the type of cooling is a furnace cooling.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011100727135A CN102691087A (en) | 2011-03-24 | 2011-03-24 | Surface treatment method for improving bioactivity of medical beta-type titanium alloy surface |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011100727135A CN102691087A (en) | 2011-03-24 | 2011-03-24 | Surface treatment method for improving bioactivity of medical beta-type titanium alloy surface |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102691087A true CN102691087A (en) | 2012-09-26 |
Family
ID=46856817
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2011100727135A Pending CN102691087A (en) | 2011-03-24 | 2011-03-24 | Surface treatment method for improving bioactivity of medical beta-type titanium alloy surface |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102691087A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105420785A (en) * | 2015-11-13 | 2016-03-23 | 西南交通大学 | Method for improving TC4 titanium alloy damping property through anodizing rapid-film-forming surface treatment |
| CN108941552A (en) * | 2018-01-11 | 2018-12-07 | 中南大学 | A kind of the Ti/Ti6Al4V composite material and preparation method of the variation of component continuous gradient |
| CN110129785A (en) * | 2019-06-12 | 2019-08-16 | 重庆理工大学 | A kind of surface treatment method of TiNb alloy |
| CN112301399A (en) * | 2020-07-20 | 2021-02-02 | 江苏燕园精英医疗科技有限公司 | Surface treatment method for dental implant |
| CN114344561A (en) * | 2022-01-13 | 2022-04-15 | 中国矿业大学 | Metastable beta titanium alloy intelligent system material and preparation method and application thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007090433A2 (en) * | 2006-02-09 | 2007-08-16 | Plus Orthopedics Ag | Purified oxides with novel morphologies formed from ti-alloys |
| KR20090080776A (en) * | 2008-01-22 | 2009-07-27 | 성균관대학교산학협력단 | Preparation method for titanium dioxide nanotube, titanium dioxide nanotube, photoelectrochemical cell using the same, and hydrogen production method using the photoelectrochemical cell |
| CN101491692A (en) * | 2009-03-03 | 2009-07-29 | 福建师范大学 | Preparation method of calcium titanate nano-tube array biological coatings |
| CN101671840A (en) * | 2008-09-10 | 2010-03-17 | 中国科学院金属研究所 | Method for generating nanotube array oxide film on medical titanium and titanium alloy surface |
| CN101781788A (en) * | 2010-04-22 | 2010-07-21 | 兰州大学 | Method for preparing specially-shaped titanium dioxide nano-tube films |
-
2011
- 2011-03-24 CN CN2011100727135A patent/CN102691087A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007090433A2 (en) * | 2006-02-09 | 2007-08-16 | Plus Orthopedics Ag | Purified oxides with novel morphologies formed from ti-alloys |
| KR20090080776A (en) * | 2008-01-22 | 2009-07-27 | 성균관대학교산학협력단 | Preparation method for titanium dioxide nanotube, titanium dioxide nanotube, photoelectrochemical cell using the same, and hydrogen production method using the photoelectrochemical cell |
| CN101671840A (en) * | 2008-09-10 | 2010-03-17 | 中国科学院金属研究所 | Method for generating nanotube array oxide film on medical titanium and titanium alloy surface |
| CN101491692A (en) * | 2009-03-03 | 2009-07-29 | 福建师范大学 | Preparation method of calcium titanate nano-tube array biological coatings |
| CN101781788A (en) * | 2010-04-22 | 2010-07-21 | 兰州大学 | Method for preparing specially-shaped titanium dioxide nano-tube films |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105420785A (en) * | 2015-11-13 | 2016-03-23 | 西南交通大学 | Method for improving TC4 titanium alloy damping property through anodizing rapid-film-forming surface treatment |
| CN105420785B (en) * | 2015-11-13 | 2018-03-20 | 西南交通大学 | The method that the surface treatment of anodic oxidation fast filming improves TC4 titanium alloy damping capacities |
| CN108941552A (en) * | 2018-01-11 | 2018-12-07 | 中南大学 | A kind of the Ti/Ti6Al4V composite material and preparation method of the variation of component continuous gradient |
| CN108941552B (en) * | 2018-01-11 | 2019-11-08 | 中南大学 | A kind of Ti/Ti6Al4V composite material of component continuous gradient variation |
| CN110129785A (en) * | 2019-06-12 | 2019-08-16 | 重庆理工大学 | A kind of surface treatment method of TiNb alloy |
| CN110129785B (en) * | 2019-06-12 | 2021-03-23 | 重庆理工大学 | Surface treatment method of TiNb alloy |
| CN112301399A (en) * | 2020-07-20 | 2021-02-02 | 江苏燕园精英医疗科技有限公司 | Surface treatment method for dental implant |
| CN114344561A (en) * | 2022-01-13 | 2022-04-15 | 中国矿业大学 | Metastable beta titanium alloy intelligent system material and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101671840A (en) | Method for generating nanotube array oxide film on medical titanium and titanium alloy surface | |
| CN101545109B (en) | Titanium or titanium alloy with surface bioactive layer and preparation method thereof | |
| CN102732898B (en) | Method for preparing micro-nano composite structure on surface of medical titanium or titanium alloy | |
| CN102908661B (en) | Medical titanium with a trace element slow-release function or titanium alloy implant material as well as preparation method and application of same | |
| CN103014814B (en) | Electrochemical treatment method of increasing corrosion resistance of medical beta-type titanium alloy surface | |
| CN104593850B (en) | Method for preparing composite bioactive coating based on titanium surface hierarchical pore structure | |
| CN105274603B (en) | Composite modified coating of magnesium or Mg alloy surface carbon nanotubes and preparation method thereof | |
| CN102691087A (en) | Surface treatment method for improving bioactivity of medical beta-type titanium alloy surface | |
| CN103908699B (en) | A kind of HA/TiO of titanium alloy surface2Layer and preparation method thereof | |
| CN108079381A (en) | A kind of preparation method of medical titanium alloy surface biological Piezoelectric anisotropy coating | |
| CN100430099C (en) | Bioactive coating on surface of Titanium or titanium alloy and its preparing method | |
| CN102330086A (en) | Titanium dioxide-hydroxyapatite gradient coating of medical titanium or titanium alloy surface and preparation method | |
| CN103388173A (en) | Method for constructing micro-nano ordered structure on titanium and titanium alloy surface | |
| CN103924278A (en) | Method for preparing titanium-based titanium dioxide nanotube/nano hydroxyapatite composite coating | |
| CN108486631A (en) | A method of improving titanium-base alloy resistance to high temperature oxidation | |
| CN108815571B (en) | Preparation method of silver modified crystal form titanium dioxide nanotube layer | |
| CN107998445A (en) | A kind of surface modification porous tantalum biomaterial and preparation method thereof | |
| CN100553691C (en) | The preparation method of composite coating material containing hydroxyapatite embedded in titanium oxide nanotube array | |
| CN101491692A (en) | Preparation method of calcium titanate nano-tube array biological coatings | |
| CN103290455A (en) | Titanium micro/nanometer double-structured dioxide thin film with high biological activity and preparation method thereof | |
| CN101565824A (en) | Ultraviolet light irradiation method for increasing surface biological activity of titanium or alloy thereof | |
| CN105671531A (en) | Preparing method for in-site growth of titanium dioxide nanometer array film on surface of metal | |
| CN101773412A (en) | Surface activation method of dental implant | |
| CN105420786A (en) | Preparation method for nano-sodium silicotitanate/titanium dioxide bio-coatings on titanium surfaces | |
| CN103628112A (en) | Preparation method of titanium-base titanium oxide-silver chloride composite coating material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20120926 |