CN101817696A - Preparation method of nano titanium dioxide thin film materials loaded on surface of ceramic body - Google Patents
Preparation method of nano titanium dioxide thin film materials loaded on surface of ceramic body Download PDFInfo
- Publication number
- CN101817696A CN101817696A CN 201010138752 CN201010138752A CN101817696A CN 101817696 A CN101817696 A CN 101817696A CN 201010138752 CN201010138752 CN 201010138752 CN 201010138752 A CN201010138752 A CN 201010138752A CN 101817696 A CN101817696 A CN 101817696A
- Authority
- CN
- China
- Prior art keywords
- thin film
- titanium dioxide
- ceramic body
- nano titanium
- film materials
- 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
Landscapes
- Catalysts (AREA)
Abstract
The invention provides a preparation method of nano titanium dioxide thin film materials loaded on the surface of a ceramic body. The preparation method comprises the following steps of: adding the organic titanium salt to the de-ionized water and stirring the de-ionized water and adding alkali liquor to adjust the pH value to be 6 to 8; centrifuging for separating the mixed solution, and adding the separated slurry to the mixed solution of absolute ethyl alcohol and acetylacetone; adding the dispersing agent to the mixed solution, sufficiently and uniformly stirring the mixed solution till the stable titanium dioxide sol is formed; soaking the high-temperature resistance and corrosion resistance ceramic body into the titanium dioxide sol, drying and forging the ceramic body for 2 to 4 hours to form one layer of nano titanium dioxide thin film material on the surface of the ceramic body. The thin film is distributed uniformly, and the thickness of the thin film is controllable. When being applied to treating the industrial waste water, the ceramic body loaded with nano titanium dioxide thin film can be utilized repeatedly and has low cost and no secondary pollution.
Description
Technical field
The present invention relates to technical field of sewage, be specifically related to a kind of preparation technology who is carried on the nano titanium dioxide thin film materials of surface of ceramic body.
Background technology
Under the irradiation of light, nano titanium dioxide photocatalyst is hydroxyl and the active oxygen that has oxidizing power with transform light energy, and it almost can decompose all environmentally harmful organic substances, as formaldehyde, agricultural chemicals and contain phenyl ring series organic compound.Because it is photocatalyst does not participate in other chemical reactions, is the effective product of semi-permanent mould in theory, fool proof on performance, stable.Thereby photocatalyst has become present industrial and agricultural wastewater as a kind of emerging surrounding purifying material and administers the field and be subjected to one of focus that people pay close attention to most.Compare with other sewage disposal technologies, it has lot of advantages: cost is low, efficient is high, non-secondary pollution etc.The nano titanium dioxide photocatalyst material can produce the hole of highly active strong reducing property electronics and positively charged strong oxidizing property under light source activation, thereby a series of oxidation-reduction reaction takes place and with its degraded, reach the purpose of effectively purifying waste water with the organism in the solution.
Because it generally all is that nano titanium dioxide powder is scattered in the waste water solution that photocatalytic degradation is handled method for waste water, carries out the illumination degrading wastewater through organic matter again.But the problem that this method exists is that nano titanium dioxide powder is difficult for reclaiming, and the second stage employ rate is low, and cost is too high, is difficult to apply.
Summary of the invention
The objective of the invention is to overcome the deficiencies in the prior art, a kind of making method that is carried on the nano titanium dioxide thin film materials of surface of ceramic body is proposed, it is that clean corrosion-and high-temp-resistant ceramic body is soaked in the TiO 2 sol, through forming one deck nano titanium dioxide thin film materials after the high-temperature calcination, and load has the ceramic body of nano titanium dioxide thin film materials to be used for wastewater treatment, comprise sewage disposals such as petrochemical complex, day chemical industry, coatings industry, the effective organic compound in the degrading waste water, the resource of purifying waste water, method is simple, practicability and effectiveness.
The technical scheme that realizes the object of the invention is: inorganic titanium salt is added in the deionized water, stir then, add alkali lye while stir, adjusting adds the pH to 6-8 of the solution behind the alkali lye, makes the titanium ion complete hydrolysis form precipitation.Solution centrifugal is separated, and the slurry that obtains after the separation joins in the mixing solutions of dehydrated alcohol and methyl ethyl diketone, adds dispersion agent again in the mixing solutions of slurry and dehydrated alcohol and methyl ethyl diketone, stirs until forming stable TiO 2 sol; At last clean corrosion-and high-temp-resistant ceramic body is soaked in the TiO 2 sol, soak 2-5 time, after calcine 2-4h in 500-700 ℃ of retort furnace, promptly form one deck nano titanium dioxide thin film materials at surface of ceramic body through super-dry, its crystal formation is the anatase octahedrite phase structure.
The weight ratio of inorganic titanium salt and deionized water is 1 among the above-mentioned preparation method: 200-400, inorganic titanium salt adopt a kind of in titanyl sulfate, titanium tetrachloride or the metatitanic acid.In order to prevent that foreign ion from influencing the stability of TiO 2 sol, generally adopts deionized water.
In order to improve the visible light catalysis activity of nano titanium dioxide thin film materials, a kind of as in ammoniacal liquor, urea or the bicarbonate of ammonia of the alkali lye that uses among the above-mentioned preparation method, by weight alkali lye: add the solution=40-150 behind the alkali lye: 2000, when calcination processing, can form the nano titanium dioxide thin film materials that is doped with N (nitrogen) element.
The volume ratio of dehydrated alcohol and methyl ethyl diketone is 1: 4 among the above-mentioned preparation method, and the weight ratio of the mixing solutions of slurry and dehydrated alcohol and methyl ethyl diketone is 1: 50-100,
A kind of as in Sodium dodecylbenzene sulfonate, Sodium hexametaphosphate 99 or the hydroxypropylcellulose of the dispersion agent that uses among the above-mentioned preparation method, dispersion agent accounts for the 0.5-1% of TiO 2 sol total amount by weight ratio.
Above-mentioned corrosion-and high-temp-resistant ceramic body is common solid ceramic body or hollow ceramic body.
Above-mentioned metatitanic acid is placed or heating and getting through long-time by titanic hydroxide and water.
The present invention compared with prior art, have following obvious improvement and outstanding characteristics: contain the nitrogen element in the nano titanium dioxide thin film materials of (1) the present invention preparation, under radiation of visible light, can produce higher photocatalytic activity, reach the purpose of purifying waste water.(2) adopting the corrosion-and high-temp-resistant ceramic body is carrier, and in surface of ceramic body, film is evenly distributed with the nano-titanium dioxide film uniform loading, controllable thickness.(3) adopt load to have the ceramic body of nano-titanium dioxide film to handle trade effluent, method is simple, can reuse, cost is significantly lower, and can not cause secondary pollution, solved nano titanium dioxide powder in the conventional process technology and has been difficult for the difficult problem that reclaims.
Embodiment
Embodiment one
10g titanyl sulfate powder is added in the 2000g deionized water, stir then, add ammonia soln 50g (ammoniacal liquor dilutes with deionized water earlier), the pH to 6.5 of regulator solution before stirring while stir.After the centrifugation, with slurry deionized water wash 2 times that obtain, join then among the mixing solutions 500g of dehydrated alcohol and methyl ethyl diketone, the dehydrated alcohol wherein and the volume ratio of methyl ethyl diketone are 1: 4, add the 2.5g Sodium dodecylbenzene sulfonate again, stir until forming stable TiO 2 sol, after placing 1h, then clean ceramic body is made the Ceramic Balls shape, diameter is 2cm, is soaked in the TiO 2 sol of preparation, take out after 15 minutes, and then repeat once to soak, take out Ceramic Balls, dry then, in retort furnace 500 ℃ the calcining 2h after, be cooled to room temperature, form one deck nano titanium dioxide thin film materials on the Ceramic Balls surface, its crystal formation is the anatase octahedrite phase structure.Load simultaneously has the Ceramic Balls of nano titanium dioxide thin film materials to can be used for wastewater treatment, 5 Ceramic Balls are positioned over 100ml to be contained in the waste water solution (concentration is 20mg/Kg) of toluene, behind the radiation of visible light 2h, measure its degradation rate through ultraviolet spectrophotometer method and reach 65%.
Embodiment two
8g titanyl sulfate powder is added in the 1800g deionized water, stir then, add urea granules 100g, the pH to 7 of regulator solution while stir.After the centrifugation, with slurry deionized water wash 2 times that obtain, join then among the mixing solutions 450g of dehydrated alcohol and methyl ethyl diketone, the dehydrated alcohol wherein and the volume ratio of methyl ethyl diketone are 1: 4, add the 2g Sodium dodecylbenzene sulfonate again, stir until forming stable TiO 2 sol, after placing 1h, then clean ceramic body is made the Ceramic Balls shape, diameter is 4cm, be soaked in the TiO 2 sol of preparation and take out after 15 minutes, and then repeat once to soak, take out Ceramic Balls, dry then, in retort furnace, behind 550 ℃ of calcining 2h, be cooled to room temperature, form one deck nano titanium dioxide thin film materials on Ceramic Balls surface, load simultaneously has the Ceramic Balls of nano titanium dioxide thin film materials to can be used for wastewater treatment, 6 Ceramic Balls are positioned over the waste water solution (concentration is 20mg/Kg) that 100ml contains methylene blue, behind radiation of visible light 2h, measure its degradation rate through ultraviolet spectrophotometer method and reach 75%.
Embodiment three
6g titanium tetrachloride powder is added in the 1500g deionized water, stir then, add bicarbonate of ammonia 50g, the pH to 6.5 of regulator solution while stir.After the centrifugation, with slurry deionized water wash 2 times that obtain, join then among the mixing solutions 400g of dehydrated alcohol and methyl ethyl diketone, the volume ratio of dehydrated alcohol and methyl ethyl diketone is 1: 4, add the 2g hydroxypropylcellulose again, stir until forming stable TiO 2 sol, after placing 1h, then ceramic body is made ceramic strip, diameter is 6cm, be soaked in the TiO 2 sol of preparation and take out after 15 minutes, and then repeat once to soak, take out ceramic bar, dry then, in retort furnace, behind 500 ℃ of calcining 2h, be cooled to room temperature, form one deck nano titanium dioxide thin film materials on ceramic bar surface, load simultaneously has the ceramic bar of nano titanium dioxide thin film materials to can be used for wastewater treatment, 7 ceramic bars are positioned over the waste water solution (concentration is 18mg/Kg) that 100ml contains acephatemet, behind radiation of visible light 2h, measure its degradation rate through ultraviolet spectrophotometer method and reach 60%.
Embodiment four
8g metatitanic acid powder is added in the 1600g deionized water, stir then, add urea while stir, the pH to 7 of regulator solution.After the centrifugation, with slurry deionized water wash 2 times that obtain, join then among the mixing solutions 350g of dehydrated alcohol and methyl ethyl diketone, the volume ratio of dehydrated alcohol and methyl ethyl diketone is 1: 4, add the 1.5g hydroxypropylcellulose again, stir until forming stable TiO 2 sol, after placing 1h, then ceramic body is made ceramic strip, diameter is 9cm, be soaked in the TiO 2 sol of preparation and take out after 15 minutes, and then repeat once to soak, take out ceramic bar, dry then, behind 700 ℃ of calcining 2h, be cooled to room temperature, form one deck nano titanium dioxide thin film materials on ceramic bar surface, load simultaneously has the ceramic bar of nano titanium dioxide thin film materials to can be used for wastewater treatment, and 8 ceramic bars are positioned over the waste water solution (concentration is 20mg/Kg) that 100ml contains toluene, behind radiation of visible light 2h, measure its degradation rate through ultraviolet spectrophotometer method and reach 55%.
Claims (6)
1. preparation method who is carried on the nano titanium dioxide thin film materials of surface of ceramic body, it is characterized in that: inorganic titanium salt is added in the deionized water, the weight ratio of inorganic titanium salt and deionized water is 1: 200-400, stir then, add alkali lye while stirring, adjusting adds the pH to 6-8 of the solution behind the alkali lye, make the titanium ion complete hydrolysis form precipitation, solution centrifugal is separated, the slurry that obtains after the separation joins in the mixing solutions of dehydrated alcohol and methyl ethyl diketone, the weight ratio of the mixing solutions of slurry and dehydrated alcohol and methyl ethyl diketone is 1: 50-100, in the mixing solutions of slurry and dehydrated alcohol and methyl ethyl diketone, add dispersion agent again, stir until forming stable TiO 2 sol; At last ceramic body is soaked in the TiO 2 sol, soaks 2-5 time, drying promptly forms one deck nano titanium dioxide thin film materials at surface of ceramic body after calcine 2-4h in 500-700 ℃ of retort furnace.
2. according to the described preparation method who is carried on the nano titanium dioxide thin film materials of surface of ceramic body of claim 1, it is characterized in that: described inorganic titanium salt is a kind of in titanyl sulfate, titanium tetrachloride or the metatitanic acid.
3. according to the described preparation method who is carried on the nano titanium dioxide thin film materials of surface of ceramic body of claim 1, it is characterized in that: described alkali lye is a kind of in urea, ammoniacal liquor or the bicarbonate of ammonia, by weight alkali lye: add the solution=40-150 behind the alkali lye: 2000.
4. according to the described preparation method who is carried on the nano titanium dioxide thin film materials of surface of ceramic body of claim 1, it is characterized in that: the volume ratio of described dehydrated alcohol and methyl ethyl diketone is 1: 4.
5. according to the described preparation method who is carried on the nano titanium dioxide thin film materials of surface of ceramic body of claim 1, it is characterized in that: described dispersion agent is a kind of in Sodium dodecylbenzene sulfonate, Sodium hexametaphosphate 99 or the hydroxypropylcellulose, and dispersion agent accounts for the 0.5-1% of TiO 2 sol total amount by weight ratio.
6. according to the described preparation method who is carried on the nano titanium dioxide thin film materials of surface of ceramic body of claim 1, it is characterized in that: the crystal formation of described nano titanium dioxide thin film materials is the anatase octahedrite phase structure.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010138752 CN101817696B (en) | 2010-03-29 | 2010-03-29 | Preparation method of nano titanium dioxide thin film materials loaded on surface of ceramic body |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010138752 CN101817696B (en) | 2010-03-29 | 2010-03-29 | Preparation method of nano titanium dioxide thin film materials loaded on surface of ceramic body |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101817696A true CN101817696A (en) | 2010-09-01 |
| CN101817696B CN101817696B (en) | 2013-03-06 |
Family
ID=42652997
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 201010138752 Expired - Fee Related CN101817696B (en) | 2010-03-29 | 2010-03-29 | Preparation method of nano titanium dioxide thin film materials loaded on surface of ceramic body |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101817696B (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102744109A (en) * | 2012-07-16 | 2012-10-24 | 武汉理工大学 | Environment-friendly aggregate with gas-liquid pollutant purifying function and preparation technology thereof |
| CN102806018A (en) * | 2012-07-12 | 2012-12-05 | 三达膜环境技术股份有限公司 | Method for lower-temperature sintering to prepare acid and alkali-resistant titanium dioxide ceramic ultrafiltration membrane |
| CN104195534A (en) * | 2014-09-16 | 2014-12-10 | 中国建材国际工程集团有限公司 | Method for preparing self-cleaning titanium dioxide film |
| CN106178981A (en) * | 2016-08-12 | 2016-12-07 | 三达膜科技（厦门）有限公司 | A kind of low temperature prepares the method for titanium oxide ceramics ultrafilter membrane |
| CN107055679A (en) * | 2017-06-16 | 2017-08-18 | 莆田学院 | A kind of photocatalytic degradation device and its application for water process |
| CN107349879A (en) * | 2017-07-04 | 2017-11-17 | 武汉理工大学 | The cellular compound porous method gathered materials of C A S H gel moulds of fabricated in situ |
| CN109250753A (en) * | 2018-12-10 | 2019-01-22 | 攀钢集团攀枝花钢铁研究院有限公司 | The method for preparing nano-anatase mine-titanium oxide |
| CN111925049A (en) * | 2020-07-15 | 2020-11-13 | 广东大能环保科技有限公司 | Novel ecological ditch for agricultural non-point source pollution treatment |
| CN113318720A (en) * | 2020-02-28 | 2021-08-31 | 广东粤能净环保科技有限公司 | Photocatalyst and preparation method and application thereof |
-
2010
- 2010-03-29 CN CN 201010138752 patent/CN101817696B/en not_active Expired - Fee Related
Non-Patent Citations (3)
| Title |
|---|
| 《中国优秀硕士学位论文全文数据库工程科技I辑》 20100228 卢赛喜 掺氮二氧化钛的制备及TiO_(2-x)N_x/NiO双层薄膜的光电致色特性研究 16、28 1-6 , 第2期 2 * |
| 《中国硕士学位论文全文数据库工程I辑》 20091031 张媛 纳米二氧化钛薄膜的制备及其光电性能研究 18-19 1-5 , 第10期 2 * |
| 《工业催化》 20040131 银董红 溶胶凝胶法制备二氧化钛薄膜的研究进展 1-3 6 第12卷, 第1期 2 * |
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102806018A (en) * | 2012-07-12 | 2012-12-05 | 三达膜环境技术股份有限公司 | Method for lower-temperature sintering to prepare acid and alkali-resistant titanium dioxide ceramic ultrafiltration membrane |
| CN102806018B (en) * | 2012-07-12 | 2014-11-05 | 三达膜环境技术股份有限公司 | Method for lower-temperature sintering to prepare acid and alkali-resistant titanium dioxide ceramic ultrafiltration membrane |
| CN102744109B (en) * | 2012-07-16 | 2014-05-14 | 武汉理工大学 | Environment-friendly aggregate with gas-liquid pollutant purifying function and preparation technology thereof |
| CN102744109A (en) * | 2012-07-16 | 2012-10-24 | 武汉理工大学 | Environment-friendly aggregate with gas-liquid pollutant purifying function and preparation technology thereof |
| CN104195534A (en) * | 2014-09-16 | 2014-12-10 | 中国建材国际工程集团有限公司 | Method for preparing self-cleaning titanium dioxide film |
| CN104195534B (en) * | 2014-09-16 | 2019-10-22 | 中国建材国际工程集团有限公司 | The preparation method of the self-cleaning film of titanium dioxide |
| CN106178981B (en) * | 2016-08-12 | 2018-10-26 | 三达膜科技（厦门）有限公司 | A kind of method of low temperature preparation titanium oxide ceramics ultrafiltration membrane |
| CN106178981A (en) * | 2016-08-12 | 2016-12-07 | 三达膜科技（厦门）有限公司 | A kind of low temperature prepares the method for titanium oxide ceramics ultrafilter membrane |
| CN107055679A (en) * | 2017-06-16 | 2017-08-18 | 莆田学院 | A kind of photocatalytic degradation device and its application for water process |
| CN107349879A (en) * | 2017-07-04 | 2017-11-17 | 武汉理工大学 | The cellular compound porous method gathered materials of C A S H gel moulds of fabricated in situ |
| CN107349879B (en) * | 2017-07-04 | 2020-01-14 | 武汉理工大学 | Method for in-situ synthesis of honeycomb C-A-S-H gel membrane composite porous aggregate |
| CN109250753A (en) * | 2018-12-10 | 2019-01-22 | 攀钢集团攀枝花钢铁研究院有限公司 | The method for preparing nano-anatase mine-titanium oxide |
| CN113318720A (en) * | 2020-02-28 | 2021-08-31 | 广东粤能净环保科技有限公司 | Photocatalyst and preparation method and application thereof |
| CN113318720B (en) * | 2020-02-28 | 2023-12-29 | 中科粤能净(山东)新材料有限公司 | Photocatalyst, and preparation method and application thereof |
| CN111925049A (en) * | 2020-07-15 | 2020-11-13 | 广东大能环保科技有限公司 | Novel ecological ditch for agricultural non-point source pollution treatment |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101817696B (en) | 2013-03-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101817696B (en) | Preparation method of nano titanium dioxide thin film materials loaded on surface of ceramic body | |
| Jiang et al. | Solar photocatalytic decolorization of CI Basic Blue 41 in an aqueous suspension of TiO2–ZnO | |
| CN101972653B (en) | Method for preparing anatase nano Ag/TiO2 composite material | |
| CN101549299B (en) | Non-metallic element multiple doping nano titanium dioxide photocatalyst and preparation method | |
| CN1176743C (en) | Nano titanium dioxide photocatalyst,prep. and use thereof | |
| CN101376098B (en) | Method for preparing visible light responding TiO2 mixed crystal using bergmeal as substrate | |
| Hameed et al. | Photocatalytic degradation of Acid Red 1 dye using ZnO catalyst in the presence and absence of silver | |
| CN102600822A (en) | Carbon-doped silicon dioxide and titanium dioxide composite photocatalyst and preparation method thereof | |
| CN102764667A (en) | Samarium/nitrogen-co-doped titanium dioxide catalyst capable of responding to visible light and preparation method thereof | |
| Shokri et al. | Photocatalytic degradation of ceftriaxone in aqueous solutions by immobilized TiO2 and ZnO nanoparticles: Investigating operational parameters | |
| Sivakumar et al. | Enhanced photocatalytic degradation of reactive dyes over FeTiO 3/TiO 2 heterojunction in the presence of H 2 O 2 | |
| CN111715188A (en) | Titanium dioxide-based nano composite material and preparation method and application thereof | |
| CN107537491A (en) | A kind of metallic catalyst preparation method for coking wastewater deep treatment | |
| CN102489290A (en) | Preparation method of nano bismuth vanadate photocatalyst loaded on active carbon fiber | |
| CN107649118B (en) | BiVO4Supported mixed crystalline phase TiO2Preparation method of visible light composite photocatalyst | |
| CN102698777A (en) | Method for preparing Ag/AgCl/BiMg2VO6 composite photocatalyst | |
| CN101780416B (en) | Iron and chrome co-doped nano titanium dioxide/zeolite compound photocatalyst and preparation method thereof | |
| CN112723493B (en) | Cobaltosic oxide/magnesium oxide-titanium composite electrode, preparation method and application thereof, and treatment method of ammonia nitrogen-containing wastewater | |
| CN113976103A (en) | High-activity visible-light-driven photocatalyst for wastewater treatment and preparation method thereof | |
| Shende et al. | Visible-light-driven photocatalytic activity of mixed phase CdS-flakes | |
| CN102513091A (en) | Preparation method for graphene self-assembled nanometer bismuth vanadate photocatalyst | |
| CN101947452B (en) | Preparation method of Co/TiO2 nanotube array and application thereof in degradation of sugar wastewater | |
| CN102489291B (en) | Method for preparing expanded graphite load nanometer bismuth vanadate photochemical catalyst | |
| CN109908890B (en) | Visible light nano composite catalyst and preparation and application thereof | |
| CN107537466A (en) | A kind of preparation method of photochemical catalyst |
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 | ||
| C41 | Transfer of patent application or patent right or utility model | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20151217 Address after: 510410, No. 3, No. 189, Peng Industrial Zone, south side of Peng Lu, Guangzhou Baiyun District, Guangdong, Jiahe Patentee after: Guangzhou Rita Technology Co. Ltd. Address before: 510410, Guangdong, Guangzhou Province, Baiyun District, Yongping street, Jixian Zhuang, Ma Ling Industrial Zone, A building on the third floor Patentee before: Yueyang Rita Optoelectronic Technology Co., Ltd. |
|
| DD01 | Delivery of document by public notice |
Addressee: Guangzhou Rita Technology Co. Ltd. Document name: Notification of Passing Examination on Formalities |
|
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20130306 Termination date: 20170329 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |