CN101191248B - Method for preparing titanium dioxide nano tube array on titanium-substrate material surface - Google Patents
Method for preparing titanium dioxide nano tube array on titanium-substrate material surface Download PDFInfo
- Publication number
- CN101191248B CN101191248B CN2006100223861A CN200610022386A CN101191248B CN 101191248 B CN101191248 B CN 101191248B CN 2006100223861 A CN2006100223861 A CN 2006100223861A CN 200610022386 A CN200610022386 A CN 200610022386A CN 101191248 B CN101191248 B CN 101191248B
- Authority
- CN
- China
- Prior art keywords
- titanium
- titanium dioxide
- array layer
- base material
- room temperature
- 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.)
- Expired - Fee Related
Links
Landscapes
- Catalysts (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
Abstract
The invention discloses a method by which titanium dioxide nanometer tube array layer is prepared on surface of titanium base material, wherein the titanium base materials undergo the surface pretreatment and receive the electrochemistry anodic oxidation treatment in the electrolyte containing the HF acid, the components of the mixed electrolyte are that the ammonium dihydrogen phosphate is 1 to 3mol/L and the hydrofluoric acid is 0.2 to 0.4mol/L, as a result, the amorphous form titanium dioxide nanometer tube surface structure is achieved; the subsequent heat treatment condition is that under air atmosphere, the rate of temperature rise is 3 DEG C/min, the heat is preserved for 3 hours at the temperature of 450 DEG C, the anatase titanium dioxide nanometer tube array layer is achieved after being cooled in the furnace to the room temperature. The electrolyte system prepared based on the method of the invention can control the balance of oxidation and the corrosion within a relatively long time, thereby preferably realizing the control on the shape of the titanium dioxide nanometer tube. The invention has the advantages of easy operation, low cost and orientated and order distribution of the prepared titanium dioxide nanometer tube array; moreover, the amorphous form titanium dioxide nanometer tube is generated normal to the direction of the base; the tube diameter is 80 to 100nm, the wall thickness is 18 to 21nm, the tube length is 0.7 to 2.0um, thereby the specific surface area is large.
Description
Technical field
The invention belongs to field of nanometer material technology, relate in particular to a kind of method for preparing titanium dioxide nanotube array layer at pure titanium or titanium alloy surface.
Background technology
Titanium or titanium alloy light weight, intensity height, good corrosion resistance has been widely used in fields such as aerospace, machinofacture, bio-medical material.But when using, usually need it is carried out surface modification, purpose is in order to obtain the more superior surface of performance, covers TiN, TiC and improves its hardness and wear resisting property as melting by laser; Improve the erosion resistance on titanium surface, high temperature resistant and wear resistance by the method for deposited coatings; Microtexture by making Nano surface change titanium surface improves mechanical property etc.
Titanium dioxide is a kind of important inorganic functional material.Nano titanium oxide has tiny crystalline size and unique nanometer size effect, wet quick, air-sensitive, dielectric effect, opto-electronic conversion, photochromic and superior photochemical catalysis, excellent biological compatibility and performance such as corrosion-resistant, therefore is extensive use of in fields such as transmitter, dielectric materials, photochemical catalysis, solar cell, automatically cleaning material and biomaterials.Therefore, at titanium or titanium alloy surface preparation one deck nano titanium oxide, can improve its functional performance better.
Titania nanotube is a kind of existence form of nano titanium oxide.Method at titanium or titanium alloy surface preparation nano-tube array has template and anonizing.In template, at first to prepare orderly alumina formwork of porous or polymer template, prepare titania nanotube by sol-gel method or electrochemical deposition method then, the main drawback of this method is that the titania nanotube form of complex process and preparation depends on template.Anonizing is comparatively simple, can directly form nano-tube array on the titanium surface.But in the reported method, exist the electrolytic solution cost higher usually, the shortcoming of technological operation inconvenience at present.Chinese patent application 200510125502.8 adopts the HF acid of simple substance to make electrolytic solution, and system is single, and the pH value reduces fast, and it is short that oxidation and corrosion reach balance time, is difficult to increase the length and the control nanotube pattern of nanotube.
Summary of the invention
Basic design of the present invention is to be anode with titanium or titanium alloy, titanium, platinum or graphite are negative electrode, be chosen in the suitable electrolytic solution, voltage in addition, titanium can form titanium dioxide film on the surface by oxidation, can obtain the form of nanotube by galvanic corrosion, make the surface nano-titanium dioxide crystallization by thermal treatment then.Specifically can be described as:
The method for preparing titanium dioxide nanotube array layer at the titanium substrate material surface, carrying out electrochemical anodic oxidation in the electrolytic solution of titanium base material through containing HF acid after the surface preparation handles, titanium base material after described electrochemical anodic oxidation is handled is again through thermal treatment, obtain the anatase titanium dioxide nano-tube array, adopt following step to obtain titanium dioxide nanotube array layer:
1), the titanium base material after surface finish step by step successively at acetone, ultrasonic cleaning in the distilled water; Titanium base material after cleaning acid etching in containing 6.0mol/L nitric acid and 1～3mol/L hydrofluoric acid mixing solutions does not produce to there being bubble, uses the distilled water flushing substrate surface then, dries up back titanium base material after the air at room temperature drying obtains etching fast;
2), by 1) the titanium base material is put into the mixed electrolytic solution of following composition after the etching that obtains: primary ammonium phosphate 1～3mol/L, hydrofluoric acid 0.2～0.4mol/L; Carry out the constant voltage anodic oxidation, concrete electrolytic parameter is: voltage 20V, and interelectrode distance is 2～5cm, electrolyzer temperature remains on room temperature; 3), to 2) goods with amorphous titanium dioxide nanotube surface structure that obtain heat-treat: under the air atmosphere, heat-up rate is 3 ℃/min, and 450 ℃ of insulations 3 hours are chilled to room temperature with stove then; At last at pure titanium substrate surface preparation anatase titanium dioxide nano-tube array layer.
The electrolyte system of the inventive method can reach balance in long relatively oxidation of time range inner control and corrosion, thereby can realize the control to the titania nanotube pattern preferably.The inventive method is easy and simple to handle, and cost is low, and the Nano tube array of titanium dioxide rule oriented of preparation is arranged, the amorphous titanium dioxide nanotube is producing perpendicular to the substrate direction, and caliber reaches 80～100nm, wall thickness 18～21nm, pipe range is 0.7～2.0 μ m, and specific surface area is big.
Embodiment
A kind of method for preparing the Nano tube array of titanium dioxide coating at pure titanium or titanium alloy surface of the present invention, its step is as follows: 1) with pure titanium (general impurity component content is not more than 0.5%) or titanium alloy dicing, use 280# successively, 400#, and the water-fast carborundum paper polishing of 1000#, then successively at acetone, ultrasonic cleaning in the distilled water; 2) acid etching produces to there being bubble in containing 6.0mol/L nitric acid and micro-hydrofluoric acid mixing solutions, uses the distilled water flushing sample surfaces then, again with hair dryer with etching after sample dry up fast, in air, place after at least 1 hour and just can carry out anodic oxidation; 3) preparation mixed electrolytic solution, concrete composition comprises: primary ammonium phosphate 1～3mol/L, hydrofluoric acid 0.2～0.4mol/L; Also can add an amount of inorganic or organic additive; 4) electrolysis voltage 20V, interelectrode distance is 2～5cm, and electrolyzer temperature remains on room temperature, carries out anodic oxidation treatment, and electrolytic solution should keep continuous stirring in treating processes; 5) heat-treat under air atmosphere, heat-up rate is 3 ℃/min, rises to 450 ℃ of insulation for some time from room temperature, is chilled to room temperature with stove then.
The invention will be further described below in conjunction with embodiment.
Embodiment 1:
At diameter is 15mm, and thickness is the thin titanium dioxide nanotube array layer of preparation on the pure titanium sheet of 1.5mm.
(1) be 15mm with diameter, the thin titanium sheet of thickness 1.5mm is used 280# successively, 600#, and the water-fast carborundum paper polishing of 1000#, then successively at acetone, ultrasonic cleaning 10min in the distilled water;
(2) acid etching does not produce to there being bubble in containing 6.0mol/L nitric acid and 1mol/L hydrofluoric acid mixing solutions, uses the distilled water flushing sample surfaces then, sample after the etching is dried up fast again, places in air and carries out (4) operation at least after 1 hour.
(3) preparation 100mL mixed electrolytic solution comprises that concentration is the primary ammonium phosphate of 1mol/L and the hydrofluoric acid of 0.4mol/L.
(4) voltage 20V, interelectrode distance is 4cm, electrolyzer temperature remains on room temperature, anodic oxidation treatment 60 minutes, and electrolytic solution should keep continuous stirring in treating processes.
(5) heat-treat under air atmosphere, heat-up rate is 3 ℃/min, rises to 450 ℃ of insulations 3 hours from room temperature, is chilled to room temperature with stove then.
Detected result: titania nanotube is grown on the pure titanium surface regularly, the Nano tube array of titanium dioxide rule oriented of preparation is arranged, the amorphous titanium dioxide nanotube is producing caliber size unanimity perpendicular to the substrate direction, be about 100nm, wall thickness 20～21nm, pipe range reaches 800nm～1000nm.
Embodiment 2:
At diameter is 15mm, and thickness is the thick titanium dioxide nanotube array layer of preparation on the pure titanium sheet of 1.5mm.
(1) be that the pure titanium rod of 15mm cuts into the thick thin slice of 1.5mm with diameter, use 280# successively, 600#, the water-fast carborundum paper polishing of 1000#, then successively at acetone, ultrasonic cleaning 10min in the distilled water.
(2) acid etching does not produce to there being bubble in containing 6.0mol/L nitric acid and 3mol/L hydrofluoric acid mixing solutions, uses the distilled water flushing sample surfaces then, sample after the etching is dried up fast again, places in air and carries out (4) operation at least after 1 hour.
(3) preparation 100mL mixed electrolytic solution comprises that concentration is the primary ammonium phosphate of 1mol/L and the hydrofluoric acid of 0.3mol/L.
(4) voltage 20V, interelectrode distance is 4cm, electrolyzer temperature remains on room temperature, anodic oxidation treatment 360 minutes, and electrolytic solution should keep continuous stirring in treating processes.
(5) heat-treat under air atmosphere, heat-up rate is 3 ℃/min, rises to 450 ℃ of insulations 3 hours from room temperature, is chilled to room temperature with stove then.
Detected result: titania nanotube is grown on the pure titanium surface regularly, and the caliber size is consistent, is about 100nm, and wall thickness 20～21nm, pipe range reach 1.7～1.9 μ m.
Embodiment 3:
At diameter is 15mm, and thickness is the titanium dioxide nanotube array layer of the thin and little caliber of preparation on the pure titanium sheet of 1.5mm.
(1) (2) step is with embodiment 2.
(3) prepare the 100mL mixed electrolytic solution, comprise the hydrogen peroxide of 10mL massfraction 30%, concentration is the primary ammonium phosphate of 1mol/L and the hydrofluoric acid of 0.3mol/L.
(4) voltage 20V, interelectrode distance is 4cm, electrolyzer temperature remains on room temperature, anodic oxidation treatment 60 minutes, and electrolytic solution should keep continuous stirring in treating processes.
(5) heat-treat under air atmosphere, heat-up rate is 3 ℃/min, rises to 450 ℃ of insulations 3 hours from room temperature, is chilled to room temperature with stove then.
Detected result: titania nanotube is grown on the pure titanium surface regularly, and caliber size is consistent, is about 80nm, and tube wall 18～19nm, pipe range reach 0.7～0.8 μ m, surface ratio embodiment 1 and 2 coarse.
Embodiment 4:
At diameter is 15mm, and thickness is the titanium dioxide nanotube array layer of the thick and little caliber of preparation on the pure titanium sheet of 1.5mm.
(1) (2) step is with embodiment 2.
(3) preparation 100mL mixed electrolytic solution comprises the 70mL dehydrated alcohol, and concentration is the primary ammonium phosphate of 1mol/L and the hydrofluoric acid of 0.25mol/L.
(4) voltage 20V, interelectrode distance is 4cm, electrolyzer temperature remains on room temperature, anodic oxidation treatment 360 minutes, and electrolytic solution should keep continuous stirring in treating processes.
(5) heat-treat under air atmosphere, heat-up rate is 3 ℃/min, rises to 450 ℃ of insulations 3 hours from room temperature, is chilled to room temperature with stove then.
Detected result: titania nanotube is grown on the pure titanium surface regularly, and the caliber size is consistent, is about 80nm, and tube wall 18～19nm, pipe range reach 1.8～1.9 μ m.
Embodiment 5:
At diameter is 10mm, and thickness is the thin titanium dioxide nanotube array layer of preparation on the pure titanium sheet of 1.5mm.
(1) (2) step is with embodiment 1.
(3) preparation 100mL mixed electrolytic solution comprises that concentration is the primary ammonium phosphate of 1mol/L and the hydrofluoric acid of 0.25mol/L.
(4) voltage 20V, interelectrode distance is 4cm, electrolyzer temperature remains on room temperature, anodic oxidation treatment 60 minutes, and electrolytic solution should keep continuous stirring in treating processes.
(5) heat-treat under air atmosphere, heat-up rate is 3 ℃/min, rises to 450 ℃ of insulations 3 hours from room temperature, is chilled to room temperature with stove then.
Detected result: titania nanotube is grown on the pure titanium surface regularly, and the caliber size is consistent, is about 100nm, and pipe range reaches 0.8～1.0 μ m.
Embodiment 6:
At diameter is 10mm, and thickness is the thick titanium dioxide nanotube array layer of preparation on the pure titanium sheet of 1.5mm.
(1) (2) step is with embodiment 2.
(3) preparation 100mL mixed electrolytic solution comprises that concentration is the primary ammonium phosphate of 1mol/L and the hydrofluoric acid of 0.2mol/L.
(4) voltage 20V, interelectrode distance is 4cm, electrolyzer temperature remains on room temperature, anodic oxidation treatment 360 minutes, and electrolytic solution should keep continuous stirring in treating processes.
(5) heat-treat under air atmosphere, heat-up rate is 3 ℃/min, rises to 450 ℃ of insulations 3 hours from room temperature, is chilled to room temperature with stove then.
Detected result: titania nanotube is grown on the pure titanium surface regularly, and the caliber size is consistent, is about 100nm, and pipe range reaches 1.8～2.0 μ m.
Embodiment 7:
At diameter is 15mm, and thickness is that the titanium alloy sheet (Ti6Al4V) of 1.5mm is gone up the thin titanium dioxide nanotube array layer of preparation.
(1) (2) step is with embodiment 2, and the titanium alloy rod replaces pure titanium rod.
(3) preparation 100mL mixed electrolytic solution comprises that concentration is the primary ammonium phosphate of 1mol/L and the hydrofluoric acid of 0.35mol/L.
(4) voltage 20V, interelectrode distance is 4cm, electrolyzer temperature remains on room temperature, anodic oxidation treatment 120 minutes, and electrolytic solution should keep continuous stirring in treating processes.
(5) heat-treat under air atmosphere, heat-up rate is 3 ℃/min, rises to 450 ℃ of insulations 3 hours from room temperature, is chilled to room temperature with stove then.
Detected result: titania nanotube is grown on the pure titanium surface regularly, and the caliber size is consistent, is about 100nm, and pipe range reaches 700nm～800nm.
Embodiment 8:
At diameter is 15mm, and thickness is the thick titanium dioxide nanotube array layer of preparation on the titanium alloy sheet of 1.5mm.
(1) (2) step is with embodiment 7.
(3) preparation 100mL mixed electrolytic solution comprises that concentration is the primary ammonium phosphate of 1mol/L and the hydrofluoric acid of 0.3mol/L.
(4) voltage 20V, interelectrode distance is 4cm, electrolyzer temperature remains on room temperature, anodic oxidation treatment 720 minutes, and electrolytic solution should keep continuous stirring in treating processes.
(5) heat-treat under air atmosphere, heat-up rate is 3 ℃/min, rises to 450 ℃ of insulations 3 hours from room temperature, is chilled to room temperature with stove then.
Detected result: titania nanotube is grown on the pure titanium surface regularly, and the caliber size is consistent, is about 100nm, and pipe range reaches 1.9～2.0 μ m.
Embodiment 9:
At diameter is 8mm, and thickness is the thin titanium dioxide nanotube array layer of preparation on the titanium alloy sheet of 1.5mm.
(1) (2) step is with embodiment 7.
(3) preparation 100mL mixed electrolytic solution comprises that concentration is the primary ammonium phosphate of 3mol/L and the hydrofluoric acid of 0.2mol/L.
(4) voltage 20V, interelectrode distance is 4cm, electrolyzer temperature remains on room temperature, anodic oxidation treatment 60 minutes, and electrolytic solution should keep continuous stirring in treating processes.
(5) heat-treat under air atmosphere, heat-up rate is 3 ℃/min, rises to 450 ℃ of insulations 3 hours from room temperature, is chilled to room temperature with stove then.
Detected result: titania nanotube is grown on the pure titanium surface regularly, and the caliber size is consistent, is about 90～100nm, and pipe range reaches 0.9～1.1 μ m.
The Nano tube array of titanium dioxide pattern that the inventive method prepares is regular, rule oriented is arranged, the amorphous titanium dioxide nanotube is producing caliber size unanimity perpendicular to the substrate direction, have the specific physical chemical property of nano titanium oxide, can be applied to fields such as catalytic chemistry, biomedical material, optical material and daily industry.
Claims (4)
1. method for preparing titanium dioxide nanotube array layer at the titanium substrate material surface, carrying out electrochemical anodic oxidation in the electrolytic solution of titanium base material through containing HF acid after the surface preparation handles, titanium base material after described electrochemical anodic oxidation is handled is again through thermal treatment, obtain the anatase titanium dioxide nano-tube array, it is characterized in that, adopt following step to obtain titanium dioxide nanotube array layer:
1), the titanium base material after surface finish step by step successively at acetone, ultrasonic cleaning in the distilled water; Titanium base material after cleaning acid etching in containing 6.0mol/L nitric acid and micro-hydrofluoric acid mixing solutions does not produce to there being bubble, uses the distilled water flushing substrate surface then, dries up back titanium base material after the air at room temperature drying obtains etching fast;
2), by 1) the titanium base material is put into the mixed electrolytic solution of following composition after the etching that obtains: primary ammonium phosphate 1～3mol/L, hydrofluoric acid 0.2～0.4mol/L; Carry out the constant voltage anodic oxidation, concrete electrolytic parameter is: voltage 20V, and interelectrode distance is 2～5cm, electrolyzer temperature remains on room temperature;
3), to 2) goods with amorphous titanium dioxide nanotube surface structure that obtain heat-treat: under the air atmosphere, heat-up rate is 3 ℃/min, and 450 ℃ of insulations 3 hours are chilled to room temperature with stove then; At pure titanium substrate surface preparation anatase titanium dioxide nano-tube array layer, described titania nanotube is producing perpendicular to the substrate direction at last, and caliber 80～100nm, pipe range are 0.7～2.0 μ m.
According to claim 1 described prepare the method for titanium dioxide nanotube array layer at the titanium substrate material surface, it is characterized in that described titanium base material is pure titanium or titanium alloy.
According to claim 1 described prepare the method for titanium dioxide nanotube array layer at the titanium substrate material surface, it is characterized in that adding in the mixed electrolytic solution has dehydrated alcohol.
According to claim 1 described prepare the method for titanium dioxide nanotube array layer at the titanium substrate material surface, it is characterized in that adding in the mixed electrolytic solution has hydrogen peroxide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2006100223861A CN101191248B (en) | 2006-12-01 | 2006-12-01 | Method for preparing titanium dioxide nano tube array on titanium-substrate material surface |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2006100223861A CN101191248B (en) | 2006-12-01 | 2006-12-01 | Method for preparing titanium dioxide nano tube array on titanium-substrate material surface |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101191248A CN101191248A (en) | 2008-06-04 |
| CN101191248B true CN101191248B (en) | 2011-08-10 |
Family
ID=39486446
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2006100223861A Expired - Fee Related CN101191248B (en) | 2006-12-01 | 2006-12-01 | Method for preparing titanium dioxide nano tube array on titanium-substrate material surface |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101191248B (en) |
Families Citing this family (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101404216B (en) * | 2008-11-10 | 2012-08-22 | 重庆大学 | Titanium dioxide compound film optoelectronic pole and its production method |
| CN101545129B (en) * | 2009-04-02 | 2010-08-11 | 桂林工学院 | A process for synthesizing crystalline titanic oxide nano-tubes |
| CN101625930B (en) * | 2009-06-19 | 2012-04-11 | 东南大学 | Ordered nano-tube array structure electrode material, preparation method and stored energy application |
| MY157270A (en) * | 2010-08-25 | 2016-05-31 | Univ Sains Malaysia | An apparatus and method for rapid rate of titanium dioxide (tio2) nanotubes arrays formation |
| CN101928975A (en) * | 2010-09-01 | 2010-12-29 | 西安交通大学 | Method for rapidly preparing single tube powder of titanium oxide nanotubes |
| CN102277608A (en) * | 2011-07-12 | 2011-12-14 | 大连理工大学 | Process for preparing titanium dioxide nano-tube powder |
| US9814867B2 (en) | 2011-12-05 | 2017-11-14 | Nano Precision Medical, Inc. | Device having titania nanotube membrane for drug delivery |
| CN102442632B (en) * | 2011-12-09 | 2014-10-01 | 中山大学 | Micro-nano multi-scale patterned anticoagulation composite biological material and method for preparing same |
| CN102534630B (en) * | 2012-02-08 | 2014-01-01 | 武汉科技大学 | Porous titanium nitride nanotube array film and preparation method thereof |
| CN102810462A (en) * | 2012-06-18 | 2012-12-05 | 西南交通大学 | Preparation method for semiconductor rectifying device with high breakdown voltage |
| CN103520776B (en) * | 2012-07-05 | 2015-04-22 | 北京纳通科技集团有限公司 | Medical titanium substrate material and manufacturing method thereof |
| CN103614761A (en) * | 2013-12-02 | 2014-03-05 | 天津大学 | Method for preparing highly-ordered titanium dioxide nanotube and application in dye-sensitized solar cell |
| WO2015112811A1 (en) | 2014-01-23 | 2015-07-30 | Nano Precision Medical, Inc. | Implant device for drug delivery |
| CN105013459B (en) * | 2015-06-29 | 2017-04-05 | 合肥工业大学 | A kind of Detitanium-ore-type TiO of height preferred orientation2Film of Nano tube array and preparation method thereof |
| CN105463364B (en) * | 2015-12-04 | 2018-01-19 | 中山大学 | Super hydrophilic anatase tio2 array of the ＞ orientations of ＜ 001 and preparation method and application |
| CN108166044A (en) * | 2018-03-05 | 2018-06-15 | 吉林大学 | A kind of method of the regulation and control medical TC4 titanium alloy surfaces tube diameters of 3D printing |
| CN110000991A (en) * | 2019-03-15 | 2019-07-12 | 南京大学 | The metal and its processing method and metal-resin composite and preparation method thereof of surface treatment |
| CN113456896B (en) * | 2021-05-20 | 2022-11-11 | 宁波市医疗中心李惠利医院 | Selenium-doped titanium dioxide nanotube array orthopedic anti-tumor implant |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1598075A (en) * | 2004-07-29 | 2005-03-23 | 大连理工大学 | Titanium dioxide nano tube electrode and its preparation process and application |
| EP1726567A1 (en) * | 2004-03-19 | 2006-11-29 | Nippon Oil Corporation | Nanotube-shaped titania and method for producing same |
-
2006
- 2006-12-01 CN CN2006100223861A patent/CN101191248B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1726567A1 (en) * | 2004-03-19 | 2006-11-29 | Nippon Oil Corporation | Nanotube-shaped titania and method for producing same |
| CN1598075A (en) * | 2004-07-29 | 2005-03-23 | 大连理工大学 | Titanium dioxide nano tube electrode and its preparation process and application |
Non-Patent Citations (2)
| Title |
|---|
| Andrei Ghicov,Hiroaki Tsuchiya,JanM.Macak,PatrikSchmuki.Titanium oxide nanotubes prepared inphosphateelectrolytes.ElectrochemistryCommunications 7（2005）.2005,第505页右栏倒数第3行至第506页左栏第3行，图1-3以及结论部分，尤其参见图1-2及其相应描述. |
| Andrei Ghicov,Hiroaki Tsuchiya,JanM.Macak,PatrikSchmuki.Titanium oxide nanotubes prepared inphosphateelectrolytes.ElectrochemistryCommunications 7(2005).2005,第505页右栏倒数第3行至第506页左栏第3行,图1-3以及结论部分,尤其参见图1-2及其相应描述. * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101191248A (en) | 2008-06-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101191248B (en) | Method for preparing titanium dioxide nano tube array on titanium-substrate material surface | |
| Radecka et al. | TiO2/SnO2 nanotubes for hydrogen generation by photoelectrochemical water splitting | |
| CN102674463B (en) | Tungsten-base tungsten trioxide nano film, and preparation method and application thereof | |
| CN106245091B (en) | Composite titania material and its preparation method and application | |
| CN103643219A (en) | Preparation method of boron-doped diamond film electrode taking porous titanium as matrix | |
| CN105110425A (en) | Preparation method of carbon-nanotube-modified three-dimensional porous-titanium-base lead dioxide electrode | |
| CN106555188A (en) | For the preparation method of the Ag/ Graphenes/titania nanotube composite film photo-anode of photoproduction cathodic protection | |
| CN104588021A (en) | Preparation method and application of TiO2 photocatalytic coating | |
| Yoriya | Effect of inter-electrode spacing on electrolyte properties and morphologies of anodic TiO2 nanotube array films | |
| Ito et al. | Preparation of highly photocatalytic nanocomposite films consisting of TiO2 particles and Zn electrodeposited on steel | |
| CN103602967B (en) | A kind of high catalytic activity Ti/TiO 2/ Ce-PbO 2the preparation method of electrode | |
| CN109518168A (en) | A kind of preparation method of the active titanium-matrix electrode plate of high steady coating | |
| CN105780087B (en) | The preparation method of Electric oxidative synthesis 1-dimention nano oxide structure | |
| CN102127771A (en) | Method for preparing aluminium alloy-loaded titanium dioxide nano tube film | |
| CN104532321A (en) | Method for oxidizing anode of titanium-aluminum alloy in fluoride-added ethylene glycol solution | |
| Mohamed et al. | Fabrication of titania nanotube arrays in viscous electrolytes | |
| CN108465465A (en) | A kind of semiconductive thin film and preparation method thereof | |
| CN103225104A (en) | Single crystal anatase titanium dioxide nano-tube array and preparation method thereof | |
| CN104801295B (en) | Titanium oxide/tungsten oxide nano-composite film on surface of metallic titanium, preparation and application | |
| Kim et al. | Understanding of anodization of zinc in an electrolyte containing fluoride ions | |
| Ryshchenko et al. | Electrochemical synthesis of crystalline niobium oxide | |
| CN104746129A (en) | Preparation method of immobilized single-crystal anatase TiO2 nanowire membrane layer | |
| CN107653447B (en) | A kind of mineral carbon load stannic oxide electrode and preparation method | |
| CN102691089A (en) | Electrochemical method for preparing superhydrophobic surface on copper substrates by using aqueous electrolyte | |
| Cao et al. | Designing micro-nano structure of anodized iron oxide films by metallographic adjustment on T8 steel |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | 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 | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20110810 Termination date: 20131201 |