CN103436937A - Preparation method of double-layer titanium dioxide nanotube thin film with pear-shaped structure - Google Patents
Preparation method of double-layer titanium dioxide nanotube thin film with pear-shaped structure Download PDFInfo
- Publication number
- CN103436937A CN103436937A CN2013103157240A CN201310315724A CN103436937A CN 103436937 A CN103436937 A CN 103436937A CN 2013103157240 A CN2013103157240 A CN 2013103157240A CN 201310315724 A CN201310315724 A CN 201310315724A CN 103436937 A CN103436937 A CN 103436937A
- Authority
- CN
- China
- Prior art keywords
- anodic oxidation
- titanium dioxide
- titanium
- preparation
- double
- 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
Landscapes
- Prostheses (AREA)
- Materials For Medical Uses (AREA)
Abstract
The invention relates to a preparation method of a double-layer titanium dioxide nanotube thin film with a pear-shaped structure. The double-layer titanium dioxide nanotube thin film is prepared by immersing medical titanium in an ethanediol electrolyte solution containing 0.1 to 0.9wt% of NH4F and 0 to 10vol% of H2O for one-step in-situ boost anodic oxidation. The preparation method comprises following steps: firstly, an anodic oxidation voltage is raised from 0V to 20-40V, and is kept for 80min to 6h; then the anodic oxidation voltage is continuously raised to 50-90V, and is kept for 10min to 1h; and at last the double-layer titanium dioxide nanotube thin film with the pear-shaped structure is formed on the surface of the medical titanium. The preparation method is simple and quick, is convenient for operation, is possible to be used in the fields of surface modification of titanium-based implants used in orthopaedics, dentistry, plastic surgery departments, and is capable of reducing risks of failure after implanting and increasing osseointegration ability of the implants.
Description
Technical field
The present invention relates to medical titanium is carried out to the Electrochemical surface modification processing, boost anodic oxidation treatment technique at its surperficial two-layer titanium dioxide nano-tube film with pyriform structure that forms by a step original position, be expected to be applied in orthopaedics, dentistry, or the surface modification field of plastic surgery titanium base implant, lower and implant rear failed risk, improve the bone integration ability of implant.
Background technology
Titanium or titanium alloy, because have good machining property, physiologically acceptable performance, stronger corrosion resistance and lower Young's modulus, is widely used in the sclerous tissueses such as orthopaedics and dentistry and replaces field, is also common cardiovascular embedded material in addition.And the titanium material very easily forms the titanium dioxide oxide film of one deck densification and shows biologically inert in generating manufacturing processed: titanium metal can not form with bone on every side or soft tissue the combination of chemical in vivo; usually can generate one deck fibrous tissue packing between material and tissue, cause implant chronic frustration in vivo.Therefore, need to carry out necessary surface modification, improve the bone conformability of titanium metal.On the other hand, after implant surgery, needs of patients is accepted the pharmacological agent in 6-8 week usually, to prevent bacterium, infects, controls blood coagulation, reduces inflammation.Yet, transmit medicine by traditional system approach, as oral or intravenous injection, side effect is large and efficiency is lower, and medicine is difficult for arriving " focus " position and plays a role.Therefore to other position nontoxicity and the high drug conveying mode of local drug concentration receives publicity, preferably medicine just can be released at the implant place.
Generate the layer of titanium dioxide nanotube layer on the titanium surface by the anonizing original position, be expected to solve above-mentioned two problems simultaneously.Quantity research shows greatly, and the titania nanotube of appropriate size can increase protein adsorption quantity, helps the grappling of bone forming relevant cell, promotes its adhesion, propagation and differentiation, thereby improves the bone conformability of titanium metal.And the hollow structure of one end opening can be used as the nanoscale memory on titanium implants surface, allow loading and the release of related drugs.Popat etc. should be used as a kind of brand-new drug release platform by titania nanotube first in 2007; and proved that titania nanotube can load different pharmaceutical; and can control by length, diameter and the thickness of pipe of titania nanotube release [Popat KC, the Small.2007 of medicine; 11:1878-81.].
At present, it is less that the drug release of titania nanotube is applied in domestic research, and have early stage prominent release serious and sustained drug short shortcoming time of releasing.For addressing these problems, the present invention wishes to prepare a kind of two-layer titanium dioxide nanotube of pyriform structure of novelty, and " belly " large by lower floor loads more medicine, and the little opening in upper strata is controlled the release of drug slow ground.
Prepare bilayer or the multilayer titania nanotube adopts the multistep anodic oxidation method more.By electrolyzer temperature [Mohapatra SK, the Mater. Lett.2008 that controls each step; 62:1772-74] or use different electrolytic solution [Macak JM, Electrochem. Solid State Lett.2007 in different step; 10:K28-31] realize.Yet this procedure is comparatively complicated, and caliber is difficult for accurately controlling.Chen etc. prepare caliber and customizable layering titanic oxide nano tube thin-film [Chen B, the Langmiur.2012 with up big and down small branched structure of branches by regulating anodic oxidation voltage; 28:2937-43].But up to the present on " valve metal " substrate, prepare the nano-tube film with pyriform constructional feature and have no report.The present invention is summing up on the basis of previous work, proposed to process the method for medical titanium metal by the step original position anonizing of boosting, and has obtained the two-layer titanium dioxide nano-tube film of the pyriform structure that the little lower floor of upper strata caliber caliber is large.By the regulation and control of electrochemical parameter, the pyriform structure is controlled within the specific limits.
Summary of the invention
The purpose of this invention is to provide a kind of step original position of utilizing and boost anodic oxidation treatment technique in the surperficial method for preparing the two-layer titanium dioxide nano-tube film with pyriform structure of medical titanium.
The concrete technology step is:
(1) pre-treatment of titanium-based metal material process mechanical grinding, oil removing and ultrasonic cleaning before anodic oxidation, take titanium or titanium alloy as anode in anodic oxidation device, take stainless steel, platinum or titanium as negative electrode, carry out the step original position anodic oxidation treatment of boosting in the moisture organic electrolysis solution of 10 ~ 40 ℃, in anode oxidation process, keep stirring, stirring velocity is 300 ~ 500 r/min.
(2) moisture organic electrolyte employing ethylene glycol is solvent, and other effective constituent is: water 0 ~ 10 vol%(volume percent), and Neutral ammonium fluoride 0.1 ~ 0.9 wt% (mass percent).
The anodic oxidation of boosting of (3) one step original positions is divided into two stages by the anodic oxidation voltage applied.The first stage anodic oxidation voltage is elevated to 20 ~ 40 V from 0 V, keeps 80 min ~ 6 h; After the subordinate phase anodic oxidation voltage continues to be elevated to 50 ~ 90 V, keep 10 min ~ 1 h.
(4) process of boosting can adopt direct current staged boost mode, also can adopt the linear boost mode of direct current.Rate of pressure rise is 2 ~ 15V/min.
(5), after anodic oxidation treatment, dehydrated alcohol and deionized water ultrasonic cleaning for sample, be deposited on surperficial particle to remove in anode oxidation process.
(6) clean rear sample through Overheating Treatment, in retort furnace, from room temperature, rise to 400 ~ 600 ℃, be incubated 1 ~ 2.5 h, furnace cooling.
(7) obtain having the two-layer titanium dioxide nano-tube film of pyriform structure.As shown in Figure 3.
The invention has the advantages that:
1. the step anonizing of boosting
Belonging to electrochemical reaction method, in reaction process, can not produce the material that environment is had to pollution, is a kind of environment-friendly method.And relatively traditional multistep anodic oxidation treatment process obtains titanium-based surface two-layer titanium dioxide nanotube layer, a step anonizing is easy and simple to handle, simple economy, and the method for boosting can accurately be controlled the caliber of two-layer pipe simultaneously, is easy to apply.
2. the two-layer titanium dioxide nanotube of pyriform structure
The two-layer titanium dioxide nanotube of pyriform structure is except the characteristics of the hollow structure that has retained straight nanotube one end opening of conventional monolayers, and the nanotube of the nanotube of its upper strata pipe with small pipe diameter and lower floor's Large Diameter Pipeline can be controlled respectively the slow release of medicine and store more medicine.The nanoporous pattern of surperficial ordered distribution can help the cell grappling simultaneously, promotes osteoblastic adhesion, growth and differentiation, is conducive to new bone forming.By regulating electrochemical parameter, the neck structure of levels nanotube caliber and pipe range and two-layer pipe junction is controlled within the specific limits, can need to be designed according to clinical application.
The accompanying drawing explanation
Fig. 1 is the exterior view with two-layer titanium dioxide nano-tube film of pyriform structure.
Fig. 2 is the cross section panorama sketch with two-layer titanium dioxide nano-tube film of pyriform structure.
Fig. 3 is place, the bed interface enlarged view with two-layer titanium dioxide nano-tube film of pyriform structure.
Specific embodiments
The specific examples provided below in conjunction with the contriver, be described in further detail invented technique.It should be noted that, the present invention is not limited to these embodiment, for those skilled in the art, in the category provided in the present invention, carries out interpolation and the replacement of technical characterictic, all belongs to protection scope of the present invention.
embodiment 1:the pure titanium sheet (TA2) that is of a size of 10 * 10 * 1 mm is used 400# successively, 600#, and 800#, 1000# abrasive paper for metallograph sanding and polishing, and then use acetone, and dehydrated alcohol, deionized water is ultrasonic cleaning 5 min respectively; Containing 0.3 wt% NH
4f, 2 vol% H
2in the ethylene glycol electrolytic solution of O, sample is carried out to the following step original position anodic oxidation treatment of boosting: apply voltage and keep 80 min from 0 V is raised to 40 V, then keep 40 min from 40 V are raised to 80 V.The process of boosting adopts direct current staged boost mode, and rate of pressure rise is chosen as 2 V/min; Walking journey is 2 V, keeps 1 min under each voltage conditions.After electrolysis completes, sample is successively through dehydrated alcohol, deionized water ultrasonic cleaning, 500 ℃ of thermal treatment 2 h, furnace cooling.Scanning electron microscopic observation oxide film surface is compact arranged, the open mouth of pipe that external diameter is 120 nm; The section photo shows that resulting its upper strata nanotube external diameter of two-layer titanium dioxide nano-tube film with pyriform structure is 120 nm, pipe range 2.75 μ m, and lower floor's nanotube external diameter is 192 nm, pipe range 8.74 μ m.X-ray diffraction analysis shows that surface film oxide is comprised of anatase titanium dioxide.
embodiment 2:the pure titanium sheet (TA1) that diameter is 15 mm is used 400# successively, 600#, and 800#, 1000# abrasive paper for metallograph sanding and polishing, and then use acetone, and dehydrated alcohol, deionized water is ultrasonic cleaning 5 min respectively; Containing 0.2 wt% NH
4f, 6 vol% H
2in the ethylene glycol electrolytic solution of O, sample is carried out to the following step original position anodic oxidation treatment of boosting: apply voltage and keep 3.5 h from 0 V is raised to 20 V, then keep 50min from 20 V are elevated to 50 V.The process of boosting adopts the linear boost mode of direct current, and rate of pressure rise is chosen as 15 V/min.After electrolysis completes, sample is successively through dehydrated alcohol, deionized water ultrasonic cleaning, 450 ℃ of thermal treatment 2.5 h, furnace cooling.Scanning electron microscopic observation oxide film surface is compact arranged, the open mouth of pipe that external diameter is 80 nm; The section photo shows that resulting its upper strata nanotube external diameter of two-layer titanium dioxide nano-tube film with pyriform structure is 80 nm, pipe range 0.61 μ m, and lower floor's nanotube external diameter is 160 nm, pipe range 0.7 μ m.X-ray diffraction analysis shows that surface film oxide is comprised of anatase titanium dioxide.
Claims (2)
1. the preparation method with two-layer titanium dioxide nano-tube film of pyriform structure, it is characterized in that comprising the steps and processing condition: the pre-treatment of titanium-based metal material process mechanical grinding, oil removing and ultrasonic cleaning before anodic oxidation treatment, take titanium or titanium alloy as anode in anodic oxidation device, take stainless steel, platinum or titanium as negative electrode, at 0.1 ~ 0.9 wt% NH that contains of 10 ~ 40 ℃
4f, 0 ~ 10 vol% H
2carry out the step original position anodic oxidation treatment of boosting in the ethylene glycol electrolytic solution of O, at first anodic oxidation voltage is elevated to 20 ~ 40 V from 0 V, after keeping 80 min ~ 6 h, continuation is increased to 50 ~ 90 V by voltage, keep 10 min ~ 1 h, the process of boosting adopts direct current staged boost mode or the linear boost mode of direct current, and rate of pressure rise is 2 ~ 15 V/min, in anode oxidation process, keep stirring, stirring velocity is 300 ~ 500 r/min.
2. according to the described method of right 1, it is characterized in that resulting titanic oxide nano tube thin-film is the two-layer titanium dioxide nano-tube film with pyriform structure.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2013103157240A CN103436937A (en) | 2013-07-25 | 2013-07-25 | Preparation method of double-layer titanium dioxide nanotube thin film with pear-shaped structure |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2013103157240A CN103436937A (en) | 2013-07-25 | 2013-07-25 | Preparation method of double-layer titanium dioxide nanotube thin film with pear-shaped structure |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN103436937A true CN103436937A (en) | 2013-12-11 |
Family
ID=49690649
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2013103157240A Pending CN103436937A (en) | 2013-07-25 | 2013-07-25 | Preparation method of double-layer titanium dioxide nanotube thin film with pear-shaped structure |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103436937A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106978619A (en) * | 2017-04-10 | 2017-07-25 | 四川理工学院 | A kind of enhancing titania nanotube is to visible light-responded preparation method |
| CN111110916A (en) * | 2020-01-09 | 2020-05-08 | 西北工业大学 | 3D printing porous titanium surface antibacterial and osteogenesis promoting controllable drug release system and preparation method |
| CN114432500A (en) * | 2022-01-20 | 2022-05-06 | 南京医科大学附属口腔医院 | CeO (CeO)2Modified TiO2Bionic porous titanium stent of variable nanotube array and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01240696A (en) * | 1988-03-18 | 1989-09-26 | Nkk Corp | Anodic oxidation for titanium or titanium alloy |
| 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 |
| 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 |
| CN102776543A (en) * | 2012-05-07 | 2012-11-14 | 中国科学院合肥物质科学研究院 | Preparation method of large-area smooth-surface uncracked anodic oxidation titanium dioxide nanometer tube arrays |
-
2013
- 2013-07-25 CN CN2013103157240A patent/CN103436937A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01240696A (en) * | 1988-03-18 | 1989-09-26 | Nkk Corp | Anodic oxidation for titanium or titanium alloy |
| 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 |
| 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 |
| CN102776543A (en) * | 2012-05-07 | 2012-11-14 | 中国科学院合肥物质科学研究院 | Preparation method of large-area smooth-surface uncracked anodic oxidation titanium dioxide nanometer tube arrays |
Non-Patent Citations (1)
| Title |
|---|
| 管东升等: ""阳极氧化TiO2纳米管阵列的制备与掺杂"", 《化学进展》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106978619A (en) * | 2017-04-10 | 2017-07-25 | 四川理工学院 | A kind of enhancing titania nanotube is to visible light-responded preparation method |
| CN111110916A (en) * | 2020-01-09 | 2020-05-08 | 西北工业大学 | 3D printing porous titanium surface antibacterial and osteogenesis promoting controllable drug release system and preparation method |
| CN114432500A (en) * | 2022-01-20 | 2022-05-06 | 南京医科大学附属口腔医院 | CeO (CeO)2Modified TiO2Bionic porous titanium stent of variable nanotube array and preparation method thereof |
| CN114432500B (en) * | 2022-01-20 | 2022-09-16 | 南京医科大学附属口腔医院 | CeO (CeO) 2 Modified TiO 2 2 Bionic porous titanium stent of variable nanotube array and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Liu et al. | Nano-modified titanium implant materials: a way toward improved antibacterial properties | |
| Tan et al. | Review of titania nanotubes: Fabrication and cellular response | |
| CN101871118B (en) | Method for preparing titanium dioxide layer with multi-level pore structure on surface of medicinal titanium | |
| Swami et al. | Titania nanotubes: novel nanostructures for improved osseointegration | |
| CN1974876B (en) | Bioactive film on titanium metal surface and its sand blasting-micro arc oxidizing compounding process | |
| CN105177670B (en) | In the method for the titanium base material surface in situ growing nano-tube of three-dimensional porous structure | |
| CN102743789B (en) | Artificial tooth root with micro-nano hierarchical topologic surface structure and preparation method of artificial tooth root | |
| CN104975335B (en) | A kind of preparation method of titanium alloy dental implant surface composite coating | |
| CN104593850B (en) | Method for preparing composite bioactive coating based on titanium surface hierarchical pore structure | |
| CN105597157B (en) | One kind can promote vascularization and anti-infection bio active coating and its preparation method and application | |
| CN102286767B (en) | Composite coating on surface of magnesium alloy biological implant material and preparation method thereof | |
| CN101537208A (en) | Biological active coating on surface of titanium or titanium alloy and preparation method thereof | |
| CN106267342A (en) | A kind of dentistry implant and preparation method thereof | |
| CN103361703A (en) | Preparation method of titanium surface multilevel porous structure | |
| CN103469284A (en) | Preparation method of carbon nanotube/titania nanotube bio-composite coat material | |
| CN103436937A (en) | Preparation method of double-layer titanium dioxide nanotube thin film with pear-shaped structure | |
| Wu et al. | Nano-hydroxyapatite coated TiO2 nanotubes on Ti-19Zr-10Nb-1Fe alloy promotes osteogenesis in vitro | |
| CN104258459A (en) | Medical titanium implant and preparation method thereof | |
| CN103290455A (en) | Titanium micro/nanometer double-structured dioxide thin film with high biological activity and preparation method thereof | |
| CN100553691C (en) | The preparation method of composite coating material containing hydroxyapatite embedded in titanium oxide nanotube array | |
| CN106902384A (en) | A kind of method for preparing class bone structure film layer on titanium surface | |
| Chopra et al. | Random, aligned and grassy: Bioactivity and biofilm analysis of Zirconia nanostructures as dental implant modification | |
| CN103007347B (en) | Method for loading gentamicin by using TiO2 nanotube coating in situ synthesized on Ti surface | |
| CN102304746A (en) | Polypyrrole calcium phosphate/magnesium oxide bioceramic coating and preparation method thereof | |
| CN102691087A (en) | Surface treatment method for improving bioactivity of medical beta-type titanium alloy surface |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into 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: 20131211 |