CN103668390A - Titanium or titanium-alloy material with micron-nano coarse-structure surface and preparation method thereof - Google Patents
Titanium or titanium-alloy material with micron-nano coarse-structure surface and preparation method thereof Download PDFInfo
- Publication number
- CN103668390A CN103668390A CN201410000589.5A CN201410000589A CN103668390A CN 103668390 A CN103668390 A CN 103668390A CN 201410000589 A CN201410000589 A CN 201410000589A CN 103668390 A CN103668390 A CN 103668390A
- Authority
- CN
- China
- Prior art keywords
- titanium
- alloy material
- titanium alloy
- preparation
- anodic 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.)
- Granted
Links
Images
Abstract
The invention relates to a titanium or titanium-alloy material with a micron-nano coarse-structure surface and a preparation method thereof. According to the material, micron-scale concave-convex structures are distributed on the surface of the titanium or titanium-alloy material, and nano-scale spur structures are distributed on the surfaces of the micron-scale concave-convex structures. The preparation method comprises the steps of sanding, polishing and cleaning the surface of the titanium or titanium-alloy material, and then, carrying out electrochemical anodizing in an electrolyte containing hydrofluoric acid and an acid additive, so as to form a microscopic coarse structure, which is formed by multiple micron-nano concave-convex structures, on the surface of the titanium or titanium-alloy material. The material has the advantages that the combination with a titanium substrate is firm, the falling off is difficult, the biological activity, surface area and surface energy are higher, the material can be applied to a wide range of fields of photocatalysts, solar cells, bio-implants and the like, a better effect can be obtained, and the preparation method is low in cost and is simple and convenient in operation.
Description
Technical field
The present invention relates to a kind of titanium with micro-nano rough structure surface or titanium alloy material and preparation method thereof.
Background technology
Titanium or titanium alloy is because having good biocompatibility, mechanical property, lower features such as Young's modulus, and it is applied for many years tooth-planting is clinical.But because titanium and alloy thereof are bio-inert materials, implanting for a long time may cause osseointegration intensity to reduce making planting body become flexible, come off, finally cause the failure of operation.At present, to the surface activation process of titanium or its alloy, can comprise alligatoring and two kinds of modes of coating.By after the roughening treatment of titanium (and alloy) material surface, can make titanium surface tension and surface increase, can promote the immediate union at osteoblastic absorption, differentiation, amplification, interface, in cytologic experiment, obtained good effect.At titanium or its alloy material surface, carry out coating type processing, especially will there is biological conductive nanometer hydroxyapatite and be compound in the surface of titanium or its alloy material, also can improve the biological activity of planting body, increase the bonding strength of planting body-bone interface.Therefore, the surface of titanium and alloy material thereof being processed accordingly, make its surface form one deck and have bioactive material, to realize the formation of inducing osseous tissue and the object that reaches biological chemistry combination, is a current focus of research both at home and abroad.
Titanium or the titanium alloy using as planting body of take is example, coarsing processing method currently reported and/or that adopt mainly contains: on titanium material bodies surface, with sintering processing, be accompanied by the particulate state coating of about 300 μ m, its main drawback is the thick and skewness of sinter fuse coating, during use, can affect its physical strength, with tissue bond intensity; Hydroxyapatite powder is sent in plasma flame to melting high-velocity jet to rapid solidification on metallic matrix and formed coating, therefore it is difficult to keep the original composition of hydroxyapatite and crystalline network, and coating and matrix Physical Properties Difference are larger, interfacial stress is concentrated, reduced the bonding strength with titanium matrix, thereby soluble absorption causes the loosening operative failure that causes of planting body under longer physiological environment; Also having with titanium slurry sprayed surface of employing the same manner, its complex process, and found in the last few years that the peri-implant of titanium slurry spraying is with the existence of titanium particle, easily caused local inflammation; Adopt at normal temperatures silicon carbide or TiO
2particle high-velocity jet is at the sand-blast of titanium implant surface, and it exists impurity element to pollute and the problem such as microtexture is inhomogeneous; Adopt hydrochloric acid, sulfuric acid, nitric acid or the mixed solution of hydrofluoric acid and the acid etching of planting body effect certain hour, on its surface, form the pit of definite shape size, but the roughness that its method is processed is limited, often also need to process in conjunction with other method for coarsening surface.Therefore, all there is different defects in conventional method for coarsening surface at present.
Summary of the invention
For above-mentioned situation, the invention provides a kind of titanium or its alloy material with new surface coarsening structure, particularly there is titanium or the titanium alloy material on micro-nano rough structure surface, and the preparation method of titanium or the titanium alloy material of this coarse surface structure is further provided.
The present invention has titanium or the titanium alloy material on micro-nano rough structure surface, is that the surface arrangement at titanium or titanium alloy material has micron-sized concaveconvex structure, on the surface of concaveconvex structure and be distributed with nano level bur structure.Wherein, said micron order concaveconvex structure at least should be coated on the full surface of the application site of titanium or titanium alloy material.Described titanium alloy material, when as medical product, can be generally the titanium alloys such as Ti-13Zr-13Nb, the Ti-6Al-7Nb of at present existing wide coverage and use, Ti-12Mo-6Zr-2Fe, Ti-35Nb-7Zr-5Ta, Ti-15Mo, Ti-16Nb-10Hf, wherein preferably Ti-13Zr-13Nb(be that Ti, Zr, Nb atomic molar are than being 1:13:13) or Ti-6Al-7Nb(be that Ti, Al, Nb atomic molar are than being 1:6:7) alloy.
The above-mentioned basic preparation method with titanium or the titanium alloy material on micro-nano rough structure surface of the present invention, can carry out in the following manner:
1) keeping away titanium dry under oxygen condition or titanium alloy material after any surface finish being processed and removed oxidation film layer and dirt, under 0 ℃ ~ 80 ℃ and the positive pulse voltage of 50 ~ 250V and the condition of 1000 ~ 5000Hz frequency, using above-mentioned dry titanium or titanium alloy material as anode, graphite or platinum are as negative electrode, in containing the aqueous electrolysis liquid that massfraction is 0.05 ~ 0.5% HF and acids additive, carry out electrochemical anodic oxidation, acids additive is wherein for accounting for the acetic acid of electrolytic solution total mass 80 ~ 85wt%, the H of 5 ~ 10wt%
2sO
4or the H of 10 ~ 20wt%
3pO
4; Electrolytic solution is preferably mass content and is respectively 0.2% HF and 85% vinegar aqueous acid, 0.05% HF and 5% H
2sO
4the aqueous solution or 0.1% HF and 10% H
3pO
4the aqueous solution.Experiment shows, the overtension while carrying out electrochemical anodic oxidation or too low can cause formed dietary fibres structure, state irregular, or be difficult for forming; Too high or too low for temperature, can affect the composition of electrolytic solution and/or the speed of electrochemical reaction; The time length of electrochemical anodic oxidation, thickness, form that can formed surface roughness layer, overlong time even also can cause established surface roughness that different caving in, destroy occurs;
2) after the electrolytic solution on the titanium after anodic oxidation or titanium alloy material surface is removed totally, be stored in dehydrated alcohol and (avoid contacting with oxygen oxidized).
On the basis of above-mentioned basic skills, to some concrete operations modes wherein, following optimal way is selected to adopt in separately all right or arbitrary combination ground:
Optimal way one, in above-mentioned preparation method, oxidation film layer is processed and removed to any surface finish of said titanium or titanium alloy material, after can adopting the physics modes such as conventional mechanical grinding and/or polishing to process, then uses by the HF of 10 ~ 15wt% and the HNO of 25 ~ 35wt%
3the aqueous solution forming, with the oxidation film layer on chemical rightenning mode Ex-all surface.Wherein, to become the content of HF be 12wt% and HNO to the preferred group of this chemical polishing soln
3content is 33wt%.
Optimal way two, to cleaning of the titanium after Ex-all surface oxidation film or titanium alloy material surface contaminants, adopts under the ul-trasonic irradiation that is 100 ~ 400W at power and with acetone, second alcohol and water, cleans successively, and preferred ultrasonic power is 250W.Different cleaning solvents can have different dirt-removing functions.For example, acetone can effectively dissolve the organism such as greasy dirt, and volatile, can be cleaner so clean with acetone, and quick; Ethanol can clean the organic contamination layer on titanium surface; Deionized water can clean the dirt impurity of other non-fat-soluble classes such as dust on titanium surface.Experiment shows, the cleaning of employing under ul-trasonic irradiation, because hyperacoustic frequency is high, wavelength is short, propagation direction property is good and penetrativity is strong, with and cavatition, acceleration effect and direct flow effect in liquid liquid and dirt are produced directly/indirect action, can make crud layer realize by effectively dispersion, emulsification, peel off, the object of can reach for general 10 ~ 40 minutes fast, thoroughly cleaning.
Optimal way three, keeping away being dried under oxygen condition, adopts the lyophilize under vacuum condition after titanium or the polishing of titanium alloy material surface finish Ex-all surface oxidation film and surface cleaning, or at isolated air or N
2deng being dried under the conditions such as inert gas environment.
Optimal way four, the electrochemical anodic oxidation time that titanium or titanium alloy material surface are carried out is 10 minutes ~ 12 hours.
Optimal way five, two interelectrode spacing≤10 centimetre when electrochemical anodic oxidation is carried out in titanium or titanium alloy material surface, between two electrodes, preferred spacing is 4 centimetres.Experimental result shows, while carrying out electrochemical anodic oxidation, two interelectrode spacing should keep suitably, the too small meeting of spacing because of local ion too concentrated, cause the ion distribution in electrolytic solution inhomogeneous, and electrolytic solution flowing in gap is not smooth and/or overheated vaporization and affect reaction; The excessive consumption that can make resistance increase and increase electric energy of spacing.
Optimal way six, titanium or titanium alloy material after anodic oxidation, under the ul-trasonic irradiation that is 100 ~ 400W at power, with the electrolytic solution of washed with de-ionized water Ex-all material surface, preferred ultrasonic power is 250W.Scavenging period generally can complete in 3 ~ 10 minutes.Scavenging period is oversize can't bring more benefit, even likely makes that formed micron-nanometer is coarse to be damaged.
Optimal way eight is preserved 48 ~ 72 hours through anodic oxidation titanium or the titanium alloy material removed after clean surface electrolytic solution in dehydrated alcohol.
To the present invention is above-mentioned, there is the titanium on micro-nano rough structure surface or the Scanning Electron Microscope photos reveal on titanium alloy material surface, on the surface of material by mastoid process or the lamella of the coralliform pitting of multiple micron order structure and hillock and the orderly flat branched structure of nano level of the arrangement of covering with again on its surface, and between the pit of micron order and nanometer and the membranaceous coarse structure of tectum of the common formation of projection, and be closely as one with the substrate of titanium or titanium alloy material.Be combined firmly with titanium matrix, this multiple micro-rough structure of difficult drop-off, can have higher biological activity, surface-area and surface can, can be widely used in the fields such as photocatalyst, solar cell, biological planting body, can obtain better effect, and its preparation cost is low, easy and simple to handle.For example it can enlarge markedly specific surface area and surface energy as medical science planting body, can promote sticking of biomacromolecule, protein, enzyme, cell etc., thereby can promote increment and the differentiation of cell, be conducive to strengthen the mortise of planting body and bone and guide osteogenesis.
Below in conjunction with the embodiment of accompanying drawing illustrated embodiment, foregoing of the present invention is described in further detail again.But this should be interpreted as to the scope of the above-mentioned theme of the present invention only limits to following example.Without departing from the idea case in the present invention described above, various replacements or the change according to ordinary skill knowledge and customary means, made, all should comprise within the scope of the invention.
Accompanying drawing explanation
Fig. 1 is the stereoscan photograph of the multiple micro-nano rough structure of titanium material surface of the present invention.
Fig. 2 is the stereoscan photograph of nano level bur structure in the micron order hillock shape convex surfaces in Fig. 1.
Fig. 3 is the partial sweep electromicroscopic photograph of nano level bur structure on the micron order pitting shape surface in Fig. 1.
Fig. 4 is the surface sweeping electromicroscopic photograph on the pure titanium of embodiment 2 surface.
Fig. 5 is the stereoscan photograph of the multiple micro-nano rough structure on titanium alloy material surface.
Fig. 6 is the partial sweep electromicroscopic photograph of nano level bur structure on the micron order pitting shape surface in Fig. 5.
Embodiment
Pure titanium material surface is used after the sand papering of 400#～1200# different size successively, in chemical rightenning mode, with containing 12wt% HF and 33%HNO
3aqueous solution soaking after 30 seconds, use successively acetone, second alcohol and water ultrasonic cleaning 30min(ultrasonic power in 100 ~ 400W, to adjust, preferably 250W), vacuum lyophilization 24h.
Then adopt and take two electrode systems that titanium sheet is negative electrode as anode, graphite, in the aqueous electrolysis liquid that contains 0.05wt% HF and 85wt% acetic acid, under 20 ℃ and voltage 100V/2000Hz condition, carry out electrochemical anodic oxidation, two interelectrode distances are to be 1h the 4cm time.Titanium sheet after electrochemical anodic oxidation is processed cleans 5min(ultrasonic power in deionized water for ultrasonic and can in 100 ~ 400W, adjust, preferably 250W), electrolytic solution is cleaned up, put into dehydrated alcohol and preserve 48h.
Titanium material surface after above-mentioned processing, can form the multiple ultra micro micro-nano structure of " film " shape of combining closely with titanium substrate.The stereoscan photograph of this multiple micro-nano rough structure and part is respectively as shown in Fig. 1 ~ Fig. 3.
embodiment 2
After sand papering for mode (or with mechanical polishing) by the surface of pure titanium sheet with embodiment 1, in chemical rightenning mode, with containing 10wt% HF and 35%HNO
3aqueous solution soaking after 30 seconds, by embodiment 1 mode, use successively acetone, second alcohol and water ultrasonic cleaning 30min, vacuum lyophilization 24h.
Then adopt and take two electrode systems that titanium sheet is negative electrode as anode, platinum, take and contain 0.05wt%HF and 85wt% vinegar aqueous acid is electrolytic solution, under 80 ℃ and voltage 100V/2000Hz condition, carry out electrochemical anodic oxidation, two interelectrode distances are 5cm, and the time is 2h.Titanium sheet after anodic oxidation cleans 5min by embodiment 1 mode with deionized water for ultrasonic, and electrolytic solution is cleaned up, and puts into dehydrated alcohol and preserves 48h.The same multiple micro-nano rough structure of combining closely as Fig. 4 form and the substrate of titanium sheet that forms on the surface of titanium sheet.
embodiment 3
By pure titanium material surface with after sand papering or mechanical polishing, in chemical rightenning mode, with containing 15wt% HF and 30% HNO
3aqueous solution soaking after 30 seconds, by embodiment 1 mode, use successively acetone, second alcohol and water ultrasonic cleaning 30min, vacuum lyophilization 24h.
Then adopt and take two electrode systems that titanium sheet is negative electrode as anode, graphite, take and contain 0.5wt%HF and 85wt% vinegar aqueous acid is electrolytic solution, under 40 ℃ and voltage 150V/2000Hz condition, carry out electrochemical anodic oxidation, two interelectrode distances are 5cm, and the time is 4h.Titanium sheet after electrochemical anodic oxidation is processed is pressed embodiment 1 mode, in deionized water for ultrasonic, cleans 5min, and electrolytic solution is cleaned up, and puts into dehydrated alcohol and preserves 48h.
embodiment 4
By after pure titanium sand for surface paper polishing, in chemical rightenning mode, with containing 15wt% HF and 25%HNO
3aqueous solution soaking after 30 seconds, by embodiment 1 mode, use successively acetone, second alcohol and water ultrasonic cleaning 30min, vacuum lyophilization 24h.
Then adopt and take two electrode systems that titanium sheet is negative electrode as anode, graphite, take and contain 0.5wt%HF and 85wt% vinegar aqueous acid is electrolytic solution, under 0 ℃ and voltage 250V/5000Hz condition, carry out electrochemical anodic oxidation, two interelectrode distances are 3cm, and the time is 12h.Titanium sheet after electrochemical anodic oxidation is processed is pressed embodiment 1 mode, in deionized water for ultrasonic, cleans 5min, and electrolytic solution is cleaned up, and puts into dehydrated alcohol and preserves 48h.
By after the polishing of Ti-Zr-Nb Type Titanium Alloy (Ti, Zr and Nb atomic molar are than 1:13:13) sand for surface paper or mechanical polishing, in chemical rightenning mode, with containing 10wt% HF and 35%HNO
3aqueous solution soaking after 30 seconds, by embodiment 1 mode, use successively acetone, second alcohol and water ultrasonic cleaning 30min, vacuum lyophilization 24h.
Then adopt and take two electrode systems that titanium sheet is negative electrode as anode, platinum, to contain 0.1wt% HF and 10%H
3pO
4the aqueous solution be electrolytic solution, under 20 ℃ and voltage 50V/1000Hz condition, carry out electrochemical anodic oxidation, two interelectrode distances are 6cm, the time is 1h.Titanium sheet after electrochemical anodic oxidation is processed is pressed embodiment 1 mode, in deionized water for ultrasonic, cleans 5min, and electrolytic solution is cleaned up, and puts into dehydrated alcohol and preserves 48h.The same multiple micro-nano rough structure of combining closely with the substrate of titanium alloy sheet that forms on titanium alloy material surface, the stereoscan photograph of the multiple micro-nano rough structure on its surface and part respectively as shown in Figure 5 and Figure 6.
embodiment 6
By after the polishing of Ti-Al-Nb Type Titanium Alloy (Ti, Al and Nb atomic molar are than 1:6:7) sand for surface paper, in chemical rightenning mode, with containing 15wt% HF and 25%HNO
3aqueous solution soaking after 30 seconds, by embodiment 1 mode, use successively acetone, second alcohol and water ultrasonic cleaning 30min, vacuum lyophilization 24h.
Then adopt and take two electrode systems that titanium sheet is negative electrode as anode, graphite, to contain 0.05wt% HF and 5% H
2sO
4the aqueous solution be electrolytic solution, under 50 ℃ and voltage 50V/1000Hz condition, carry out electrochemical anodic oxidation, two interelectrode distances are 4cm, the time is 10min.Titanium sheet after electrochemical anodic oxidation is processed is pressed embodiment 1 mode, in deionized water for ultrasonic, cleans 5min, and electrolytic solution is cleaned up, and puts into dehydrated alcohol and preserves 48 ~ 72h.The same multiple micro-nano rough structure of combining closely as Fig. 4 form and the substrate of titanium sheet that forms on titanium alloy material surface.
Claims (10)
1. titanium or the titanium alloy material with micro-nano rough structure surface, is characterized in that there is micron-sized concaveconvex structure in the surface arrangement of titanium or titanium alloy material, in the surface arrangement of concaveconvex structure, has nano level bur structure.
2. titanium as claimed in claim 1 or titanium alloy material, is characterized in that application site that said micron order concaveconvex structure is at least coated on titanium or titanium alloy material surface entirely.
3. the preparation method described in claim 1 or 2 with titanium or the titanium alloy material on micro-nano rough structure surface, is characterized in that carrying out in the following manner:
1) keeping away titanium dry under oxygen condition or titanium alloy material after any surface finish being processed and removed oxidation film layer and dirt, under 0 ℃ ~ 80 ℃ and the positive pulse voltage of 50 ~ 250V and the condition of 1000 ~ 5000Hz frequency, using above-mentioned dry titanium or titanium alloy material as anode, graphite or platinum are as negative electrode, in containing the aqueous electrolysis liquid that massfraction is 0.05 ~ 0.5% HF and acids additive, carry out electrochemical anodic oxidation, acids additive is wherein for accounting for the acetic acid of electrolytic solution total mass 80 ~ 85wt%, the H of 5 ~ 10wt%
2sO
4or the H of 10 ~ 20wt%
3pO
4; Electrolytic solution is preferably mass content and is respectively 0.2% HF and 85% vinegar aqueous acid, 0.05% HF and 5% H
2sO
4the aqueous solution or 0.1% HF and 10% H
3pO
4the aqueous solution;
2) after the electrolytic solution on the titanium after anodic oxidation or titanium alloy material surface is removed totally, be stored in dehydrated alcohol.
4. preparation method as claimed in claim 3, is characterized in that the said any surface finish to titanium or titanium alloy material processes and remove oxidation film layer, for by after titanium or the polishing of titanium alloy material surface finish, with containing 10 ~ 15wt% HF and 25 ~ 35wt% HNO
3the aqueous solution, with the oxidation film layer on chemical rightenning mode Ex-all surface, in chemical polishing soln, preferred HF content is 12wt%, HNO
3for 33wt%.
5. preparation method as claimed in claim 3, it is characterized in that said cleaning the titanium after Ex-all surface oxidation film or titanium alloy material surface contaminants, under the ul-trasonic irradiation that employing is 100 ~ 400W at power, clean successively with acetone, second alcohol and water, preferred ultrasonic power is 250W.
6. preparation method as claimed in claim 3, is characterized in that keeping away being dried under oxygen condition, employing vacuum lyophilization after said titanium or the polishing of titanium alloy material surface finish Ex-all surface oxidation film and surface cleaning.
7. preparation method as claimed in claim 3, is characterized in that the said electrochemical anodic oxidation time to titanium or titanium alloy material surface is 10 minutes ~ 12 hours.
8. preparation method as claimed in claim 3, is characterized in that said two interelectrode spacing≤10 centimetre when electrochemical anodic oxidation is carried out in titanium or titanium alloy material surface, and between two electrodes, preferred spacing is 4 centimetres.
9. preparation method as claimed in claim 3, is characterized in that titanium or titanium alloy material after anodic oxidation, and under the ul-trasonic irradiation that is 100 ~ 400W at power, with the electrolytic solution of washed with de-ionized water Ex-all material surface, preferred ultrasonic power is 250W.
10. the preparation method as described in one of claim 3 to 9, is characterized in that in dehydrated alcohol, preserving 48 ~ 72 hours through anodic oxidation titanium or the titanium alloy material removed after clean surface electrolytic solution.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410000589.5A CN103668390B (en) | 2014-01-02 | 2014-01-02 | There is the titanium on micro-nano rough structure surface or titanium alloy material and preparation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410000589.5A CN103668390B (en) | 2014-01-02 | 2014-01-02 | There is the titanium on micro-nano rough structure surface or titanium alloy material and preparation method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103668390A true CN103668390A (en) | 2014-03-26 |
| CN103668390B CN103668390B (en) | 2016-10-26 |
Family
ID=50307144
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410000589.5A Expired - Fee Related CN103668390B (en) | 2014-01-02 | 2014-01-02 | There is the titanium on micro-nano rough structure surface or titanium alloy material and preparation method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103668390B (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104400660A (en) * | 2014-10-24 | 2015-03-11 | 成都华西一为生物植体科技有限公司 | Application of titanium alloy as dental implant sandblasting medium |
| WO2017161911A1 (en) * | 2016-03-22 | 2017-09-28 | 苏州蓝锐纳米科技有限公司 | Heat exchanger having condensate drop self-repelling function nanolayer |
| CN110373709A (en) * | 2018-04-13 | 2019-10-25 | 中国科学院金属研究所 | A kind of CTB alloy surface modifying method |
| CN111803231A (en) * | 2020-06-28 | 2020-10-23 | 深圳大学 | Bionic micro/nano antibacterial structure and manufacturing method and application thereof |
| CN111840659A (en) * | 2020-04-30 | 2020-10-30 | 中科益安医疗科技（北京）股份有限公司 | High-safety blood vessel support without nickel metal medicine elution and its making method |
| CN113481564A (en) * | 2021-06-30 | 2021-10-08 | 中国科学院金属研究所 | Titanium-based alloy with bionic super-smooth surface structure and preparation method and application thereof |
| WO2021218089A1 (en) | 2020-04-30 | 2021-11-04 | 中科益安医疗科技（北京）股份有限公司 | High-nitrogen nickel-free austenitic stainless steel seamless thin-walled tube |
| CN113897569A (en) * | 2021-09-01 | 2022-01-07 | 东北大学 | Titanium alloy surface morphology for improving cell adhesion and proliferation and preparation method thereof |
Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2600718A1 (en) * | 2005-03-21 | 2006-09-28 | Regents Of The University Of California | Controllable nanostructuring on micro-structured surfaces |
| CN101244462A (en) * | 2008-03-11 | 2008-08-20 | 西南交通大学 | Method for generating multilevel size tiny/nanostructured layer on pure titanium surface |
| CN101871118A (en) * | 2010-06-30 | 2010-10-27 | 四川大学 | Method for preparing titanium dioxide layer with multi-level pore structure on surface of medicinal titanium |
| CN102051615A (en) * | 2009-11-02 | 2011-05-11 | 中国科学院兰州化学物理研究所 | Preparation method of anti-creeping and anti-corrosive titanium or titanium alloy material |
| CN102525675A (en) * | 2012-03-02 | 2012-07-04 | 吉林大学 | Method for preparing two-stage micron-submicron microstructure on surface of titanium alloy dental implant |
| CN101919741B (en) * | 2010-09-28 | 2012-09-05 | 吉林大学 | Dental implant with micron-nanometer multi-grade micro-surface structure and preparation method |
| CN102677121A (en) * | 2012-03-31 | 2012-09-19 | 四川大学 | Preparation of multi-stage pore structure layer on surface of medical titanium by using one-step anodic oxidation method |
| CN102732882A (en) * | 2012-07-13 | 2012-10-17 | 东南大学 | Artificial joint with micro-nano graded topological surface structure and preparation method of artificial joint |
| CN102912357A (en) * | 2012-10-31 | 2013-02-06 | 厦门大学 | Method for preparing micro-nanostructure on surface of titanium implant |
| CN103290455A (en) * | 2013-06-14 | 2013-09-11 | 大连理工大学 | Titanium micro/nanometer double-structured dioxide thin film with high biological activity and preparation method thereof |
| CN103388173A (en) * | 2013-07-26 | 2013-11-13 | 厦门大学 | Method for constructing micro-nano ordered structure on titanium and titanium alloy surface |
| RU2509181C2 (en) * | 2011-04-12 | 2014-03-10 | Общество с ограниченной ответственностью "НЕЛАН-ОКСИД ПЛЮС" | Method of forming porous oxide on titanium-aluminium alloy |
-
2014
- 2014-01-02 CN CN201410000589.5A patent/CN103668390B/en not_active Expired - Fee Related
Patent Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2600718A1 (en) * | 2005-03-21 | 2006-09-28 | Regents Of The University Of California | Controllable nanostructuring on micro-structured surfaces |
| CN101244462A (en) * | 2008-03-11 | 2008-08-20 | 西南交通大学 | Method for generating multilevel size tiny/nanostructured layer on pure titanium surface |
| CN102051615A (en) * | 2009-11-02 | 2011-05-11 | 中国科学院兰州化学物理研究所 | Preparation method of anti-creeping and anti-corrosive titanium or titanium alloy material |
| CN101871118A (en) * | 2010-06-30 | 2010-10-27 | 四川大学 | Method for preparing titanium dioxide layer with multi-level pore structure on surface of medicinal titanium |
| CN101919741B (en) * | 2010-09-28 | 2012-09-05 | 吉林大学 | Dental implant with micron-nanometer multi-grade micro-surface structure and preparation method |
| RU2509181C2 (en) * | 2011-04-12 | 2014-03-10 | Общество с ограниченной ответственностью "НЕЛАН-ОКСИД ПЛЮС" | Method of forming porous oxide on titanium-aluminium alloy |
| CN102525675A (en) * | 2012-03-02 | 2012-07-04 | 吉林大学 | Method for preparing two-stage micron-submicron microstructure on surface of titanium alloy dental implant |
| CN102677121A (en) * | 2012-03-31 | 2012-09-19 | 四川大学 | Preparation of multi-stage pore structure layer on surface of medical titanium by using one-step anodic oxidation method |
| CN102732882A (en) * | 2012-07-13 | 2012-10-17 | 东南大学 | Artificial joint with micro-nano graded topological surface structure and preparation method of artificial joint |
| CN102912357A (en) * | 2012-10-31 | 2013-02-06 | 厦门大学 | Method for preparing micro-nanostructure on surface of titanium implant |
| CN103290455A (en) * | 2013-06-14 | 2013-09-11 | 大连理工大学 | Titanium micro/nanometer double-structured dioxide thin film with high biological activity and preparation method thereof |
| CN103388173A (en) * | 2013-07-26 | 2013-11-13 | 厦门大学 | Method for constructing micro-nano ordered structure on titanium and titanium alloy surface |
Non-Patent Citations (7)
| Title |
|---|
| LI XIE等: "A facile one-step anodization treatment to prepare multi-level porous titania layer on titanium", 《MATERIALS LETTERS》, vol. 72, 31 December 2011 (2011-12-31), pages 141 - 144 * |
| NAGEH K. ALLAM等: "Formation of Vertically Oriented TiO2 Nanotube Arrays using a Fluoride Free HCl Aqueous Electrolyte", 《THE JOURNAL OF PHYSICAL CHEMISTRY》, vol. 111, no. 35, 23 August 2007 (2007-08-23), pages 13028 - 13032 * |
| 孟维艳: "纯钛表面微米-纳米微结构的构建及生物学研究", 《中国博士学位论文全文数据库 医药卫生科技辑》, 15 June 2011 (2011-06-15), pages 074 - 15 * |
| 戚卫星: "多孔阳极氧化钛纳米孔道形成机理的研究", 《中国优秀硕士学位论文全文数据库 工程科技I辑》, no. 7, 15 July 2013 (2013-07-15), pages 020 - 138 * |
| 林先军等: "《前卫口腔医学荟萃》", 30 November 2003, 黄河出版社, article "钛铸件表面处理与技术", pages: 374 * |
| 潘永康等: "《现代干燥技术》", 30 September 1998, 化学工业出版社, article "真空冷冻干燥", pages: 450 * |
| 陶春虎等: "《失效分析新技术》", 30 November 2011, 国防工业出版社, article "钛合金的环境损伤", pages: 294 * |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104400660A (en) * | 2014-10-24 | 2015-03-11 | 成都华西一为生物植体科技有限公司 | Application of titanium alloy as dental implant sandblasting medium |
| WO2017161911A1 (en) * | 2016-03-22 | 2017-09-28 | 苏州蓝锐纳米科技有限公司 | Heat exchanger having condensate drop self-repelling function nanolayer |
| CN110373709A (en) * | 2018-04-13 | 2019-10-25 | 中国科学院金属研究所 | A kind of CTB alloy surface modifying method |
| CN111840659A (en) * | 2020-04-30 | 2020-10-30 | 中科益安医疗科技（北京）股份有限公司 | High-safety blood vessel support without nickel metal medicine elution and its making method |
| WO2021218089A1 (en) | 2020-04-30 | 2021-11-04 | 中科益安医疗科技（北京）股份有限公司 | High-nitrogen nickel-free austenitic stainless steel seamless thin-walled tube |
| CN111840659B (en) * | 2020-04-30 | 2022-02-08 | 中科益安医疗科技（北京）股份有限公司 | High-safety blood vessel support without nickel metal medicine elution and its making method |
| CN111803231A (en) * | 2020-06-28 | 2020-10-23 | 深圳大学 | Bionic micro/nano antibacterial structure and manufacturing method and application thereof |
| CN113481564A (en) * | 2021-06-30 | 2021-10-08 | 中国科学院金属研究所 | Titanium-based alloy with bionic super-smooth surface structure and preparation method and application thereof |
| CN113897569A (en) * | 2021-09-01 | 2022-01-07 | 东北大学 | Titanium alloy surface morphology for improving cell adhesion and proliferation and preparation method thereof |
| CN113897569B (en) * | 2021-09-01 | 2022-04-01 | 东北大学 | Titanium alloy surface morphology for improving cell adhesion and proliferation and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103668390B (en) | 2016-10-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103668390A (en) | Titanium or titanium-alloy material with micron-nano coarse-structure surface and preparation method thereof | |
| CN102586786B (en) | Method for forming graded multi-hole shape on titanium surface | |
| CN101919741B (en) | Dental implant with micron-nanometer multi-grade micro-surface structure and preparation method | |
| CN102912357B (en) | Method for preparing micro-nanostructure on surface of titanium implant | |
| CN102921037A (en) | Method for preparing multistage micron structure on titanium implant surface | |
| Szesz et al. | Electrochemical and morphological analyses on the titanium surface modified by shot blasting and anodic oxidation processes | |
| CN104674321A (en) | Preparation method and application of antibacterial bio-ceramic film with titanium or titanium alloy surface containing copper | |
| TWI480026B (en) | Bio-implant having screw body selectively formed with nanoporous in spiral groove and method of making the same | |
| Saharudin et al. | Surface modification and bioactivity of anodic Ti6Al4V alloy | |
| CN102677121A (en) | Preparation of multi-stage pore structure layer on surface of medical titanium by using one-step anodic oxidation method | |
| CN104032291A (en) | Method of preparing TiSrO3 coating on surface of titanium implant | |
| CN101942688A (en) | Composite oxidation technology for medicinal titanium alloy | |
| CN109680266A (en) | A kind of bioactive ceramic coating and preparation method thereof preparing tantalum atom doping in titanium alloy surface | |
| Rautray et al. | Formation of anodic TiO2 nanotubes under magnetic field | |
| CN105696054A (en) | Preparation method for forming calcium-containing nanosheet film layer on surface of sandblasted and acid-etched titanium | |
| CN103361702A (en) | Method for surface modification of dental implant | |
| CN101311328A (en) | Process for preparing titanium-based hydroxylapatite/titanium oxide nanotube composite coating | |
| CN102747405A (en) | Preparation method of composite ceramic coating for improving bioactivity of medical magnesium alloy | |
| CN107530146A (en) | The planting body on the surface with micron and nanometer composite structure and the surface treatment method of planting body | |
| Jain et al. | Surface characterization, shear strength, and bioactivity of anodized titanium prepared in mixed-acid electrolytes | |
| Huan et al. | Synthesis and characterization of hybrid micro/nano-structured NiTi surfaces by a combination of etching and anodizing | |
| CN103981523A (en) | Surface sand-blasting and acid-etching treatment method of super-hydrophilic Ti6Ai7Ni | |
| CN103290455A (en) | Titanium micro/nanometer double-structured dioxide thin film with high biological activity and preparation method thereof | |
| CN104027839B (en) | A kind of method in pure titanium surface preparation with biologically active nanometer structure | |
| CN103877618A (en) | Method of preparing silver-bearing titanium dioxide thin film on surface of medical titanium or titanium alloy |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20161026 Termination date: 20190102 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |