CN100551829C - A kind of preparation method of titanic oxide hollow microballoon - Google Patents
A kind of preparation method of titanic oxide hollow microballoon Download PDFInfo
- Publication number
- CN100551829C CN100551829C CNB200810025847XA CN200810025847A CN100551829C CN 100551829 C CN100551829 C CN 100551829C CN B200810025847X A CNB200810025847X A CN B200810025847XA CN 200810025847 A CN200810025847 A CN 200810025847A CN 100551829 C CN100551829 C CN 100551829C
- Authority
- CN
- China
- Prior art keywords
- titanic oxide
- oxide hollow
- hollow microballoon
- preparation
- microballoon
- 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
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 12
- 239000007788 liquid Substances 0.000 claims abstract description 12
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 12
- 239000010936 titanium Substances 0.000 claims abstract description 12
- 238000001816 cooling Methods 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims abstract description 7
- 238000001914 filtration Methods 0.000 claims abstract description 7
- 239000002994 raw material Substances 0.000 claims abstract description 7
- 238000009991 scouring Methods 0.000 claims abstract description 3
- 238000005406 washing Methods 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000012153 distilled water Substances 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 12
- 239000004408 titanium dioxide Substances 0.000 abstract description 7
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- 230000007613 environmental effect Effects 0.000 abstract description 4
- 238000003786 synthesis reaction Methods 0.000 abstract description 4
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 3
- 239000002245 particle Substances 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 3
- 238000010189 synthetic method Methods 0.000 abstract description 3
- 239000002105 nanoparticle Substances 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 20
- 229910010413 TiO 2 Inorganic materials 0.000 description 12
- 238000004519 manufacturing process Methods 0.000 description 10
- 239000000463 material Substances 0.000 description 9
- 239000012467 final product Substances 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000009776 industrial production Methods 0.000 description 4
- 239000012265 solid product Substances 0.000 description 4
- 239000004005 microsphere Substances 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229910010298 TiOSO4 Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- KADRTWZQWGIUGO-UHFFFAOYSA-L oxotitanium(2+);sulfate Chemical compound [Ti+2]=O.[O-]S([O-])(=O)=O KADRTWZQWGIUGO-UHFFFAOYSA-L 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 238000006303 photolysis reaction Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920003987 resole Polymers 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229910000349 titanium oxysulfate Inorganic materials 0.000 description 1
Images
Landscapes
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention discloses a kind of preparation method of titanic oxide hollow microballoon.This method is commercial titanium liquid to be put into have the teflon-lined autoclave, at 140～220 ℃ of following hydro-thermal reaction 4～24h, cooling after scouring, filtration, drying can obtain to pile up the particle size that the forms titanic oxide hollow microballoon at 200～300nm by nano particle.The present invention is a raw material with cheap commercial titanium liquid, does not need to add other chemical reagent, adopts hydrothermal method synthesis of titanium dioxide tiny balloon, and synthetic method is simple, compares with other wet chemical method to have environmental friendliness, low temperature, advantage such as need not calcine.
Description
Technical field
The invention belongs to the inorganic nanometer powder material preparation, be specifically related to a kind of preparation method of titanic oxide hollow microballoon.
Background technology
Titanium dioxide is a kind of widely used wide bandgap semiconductor materials, because of its good stability, nontoxic to human body, and have wet quick, pressure-sensitive, air-sensitive and good photochemical catalysis and opto-electronic conversion performance and be widely used in fields such as transmitter, photocatalyst, electronic material, material of paint and other industrial chemicals, and be expected to utilize sun power to show wide application prospect in fields such as organic synthesis, photodissociation water, environmental improvements.
Because titanic oxide hollow microballoon density is lower, specific surface area is bigger, have excellent light, electrical characteristic, thereby have broad application prospects in fields such as effective catalyst, solar cell and semi-conductors and cause domestic and international experts and scholars' attention, people have carried out some researchs to the titanic oxide hollow microballoon preparation method in recent years.Shi Keyu (catalysis journal, 2002,23 (4): 301-304) with the tetrabutyl titanate be raw material, adopt sol-gel method to prepare TiO 2 sol, then TiO 2 sol is mixed the back adds in the normal heptane dispersion medium with phenol, drip formalin again, having prepared with resol by the inverse suspension polymerization process is the titanic oxide composite microsphere of template, and having obtained diameter after the calcination processing is 200～500 μ m titania porous microspheres.This method prepares titanium dioxide microballoon sphere and exists that technological process is loaded down with trivial details, cost is higher relatively, is difficult to shortcomings such as large-scale industrial production.Chinese patent CN1824382 provides the preparation method of titanic oxide hollow microballoon: TiO 2 sol and Zeo-karb are mixed, suction filtration then, dry 8～16h can obtain titanic oxide hollow microballoon at temperature lower calcination 6～10h of 450～700 ℃ under 70～90 ℃ temperature.
In addition, synthetic hollow structure material adopts template usually, when synthesizing with template, usually earlier at the surperficial encasement layer material of mould material (being generally polymer microsphere), by sintering or dissolving removal template, obtains hollow structure again.External some reports in addition about the titanic oxide hollow microballoon preparation method, but, usually in these preparation methods, all need organism or inorganic materials as auxiliary agent and pore-forming material, and in subsequent processes, these auxiliary agents or pore-forming material removing could be generated meso-hole structure.
Take a broad view of the above-mentioned method for preparing titanium dioxide hollow ball, ubiquity the preparation process complexity, cost is higher, is difficult to shortcomings such as large-scale industrial production.
Summary of the invention
The objective of the invention is to have the shortcoming that exists in the technology of preparing now in order to overcome, provide a kind of production cost lower, technological process is simple and easy to control, energy consumption is low, environmentally safe or of reduced contamination, is fit to the preparation method of the titanic oxide hollow microballoon of suitability for industrialized production.
For realizing the object of the invention, the technical solution adopted in the present invention is as follows:
A kind of preparation method of titanic oxide hollow microballoon comprises the steps:
Adopting commercial titanium liquid is raw material, commercial titanium liquid is put into have the teflon-lined autoclave, at 140～220 ℃ of following hydro-thermal reaction 4～24h, cooling after scouring, filtration, drying get final product titanic oxide hollow microballoon.
Described hydrothermal temperature is preferably 180～200 ℃.
The described hydro-thermal reaction time is preferably 12～20h.
Described washing process adopts distilled water, absolute ethanol washing successively.
Described drying process temperature is 60～100 ℃, and be 12～24h time of drying.
Commercial titanium liquid main component is titanyl sulfate (TiOSO4) and water, and in the reaction process, they can provide oxygen.
Compared with prior art, the present invention has following advantage:
(1) the present invention is a raw material with the commercial titanium liquid of cheapness, and reaction process need not add other reagent, reduces production costs greatly.
(2) adopt hydrothermal method one-step synthesis titanic oxide hollow microballoon, synthetic method is simple, compares with other wet chemical method to have environmental friendliness, low temperature, advantage such as need not calcine.
(3) the present invention has overcome that the technological process that exists in the existing titanic oxide hollow microballoon preparation process is loaded down with trivial details, cost is higher relatively, has been difficult to problem such as large-scale industrial production, has productive rate height, advantage such as with short production cycle, is fit to suitability for industrialized production.
Description of drawings
Fig. 1 is the X-ray diffractogram of the embodiment of the invention 1～4 products obtained therefrom.
Fig. 2 is low power scanning electron microscope (SEM) figure of the embodiment of the invention 1 products obtained therefrom;
Fig. 3 is high power scanning electron microscope (SEM) figure of the embodiment of the invention 1 products obtained therefrom;
Fig. 4 is section transmission electron microscope (TEM) figure of the embodiment of the invention 1 products obtained therefrom.
Embodiment
In order better to understand the present invention, the invention will be further described below in conjunction with embodiment, but the scope of protection of present invention is not limited to the scope that embodiment represents.
With 10mL commercial titanium liquid (production of the Guangzhou titanium powder plant) capacity of putting into be 20mL have a teflon-lined autoclave, at 140 ℃ of following hydro-thermal reaction 24h, adopt distilled water, absolute ethanol washing after the cooling successively, get white solid product after the filtration, with product at 60 ℃ of following dry 24h, get final product the 1.18g titanic oxide hollow microballoon.Curve 1 is the X-ray diffractogram of present embodiment products therefrom in the accompanying drawing 1, as can be seen from the figure, and the peak position of each diffraction peak and Detitanium-ore-type TiO
2Diffraction peak on the standard card (JCPDS No.84-1286) matches, and does not have the appearance of dephasign peak, illustrates that product is pure anatase structured TiO
2Accompanying drawing 2 is the low multiple SEM figure of present embodiment products therefrom, and as can be seen from Figure 2, the particle size of gained titanium dioxide microballoon sphere is more even, between 200～300nm.Accompanying drawing 3 is the SEM figure of the high multiple of present embodiment products therefrom, and as can be seen from Figure 3 titanium dioxide surface is piled up by nano particle and formed.Accompanying drawing 4 is the section TEM figure of present embodiment products therefrom, as can be seen from Figure 4, and gained TiO
2Be hollow structure.The SEM of gained titanium dioxide microballoon sphere figure, TEM figure are similar to the present embodiment figure among the embodiment of back, explanation no longer in addition.
With 10mL commercial titanium liquid (production of the Guangzhou titanium powder plant) capacity of putting into be 20mL have a teflon-lined autoclave, at 180 ℃ of following hydro-thermal reaction 12h, adopt distilled water, absolute ethanol washing after the cooling successively, get white solid product after the filtration, with product at 80 ℃ of following dry 18h, get final product the 1.20g titanic oxide hollow microballoon.Curve 2 is the X-ray diffractogram of products therefrom in the accompanying drawing 1, as can be seen from the figure, and the peak position of each diffraction peak and Detitanium-ore-type TiO
2Diffraction peak on the standard card (JCPDS No.84-1286) matches, and does not have the appearance of dephasign peak, illustrates that product is pure anatase structured TiO
2
With 10mL commercial titanium liquid put into capacity be 20mL have a teflon-lined autoclave, at 220 ℃ of following hydro-thermal reaction 4h, adopt distilled water, absolute ethanol washing after the cooling successively, get white solid product after the filtration, with product at 100 ℃ of following dry 12h, get final product the 1.10g titanic oxide hollow microballoon.Curve 3 is the X-ray diffractogram of products therefrom in the accompanying drawing 1, as can be seen from the figure, and the peak position of each diffraction peak and Detitanium-ore-type TiO
2Diffraction peak on the standard card (JCPDS No.84-1286) matches, and does not have the appearance of dephasign peak, illustrates that product is pure anatase structured TiO
2
Embodiment 4
With 10mL commercial titanium liquid put into capacity be 20mL have a teflon-lined autoclave, at 200 ℃ of following hydro-thermal reaction 18h, adopt distilled water, absolute ethanol washing after the cooling successively, get white solid product after the filtration, with product at 90 ℃ of following dry 20h, get final product the 1.13g titanic oxide hollow microballoon.Curve 4 is the X-ray diffractogram of products therefrom in the accompanying drawing 1, as can be seen from the figure, and the peak position of each diffraction peak and Detitanium-ore-type TiO
2Diffraction peak on the standard card (JCPDS No.84-1286) matches, and does not have the appearance of dephasign peak, illustrates that product is pure anatase structured TiO
2
Can see that from the foregoing description the present invention is a raw material with cheap commercial titanium liquid, prepares titanic oxide hollow microballoon by hydro-thermal reaction, reaction process need not add other reagent, and production cost is lower.One-step synthesis titanic oxide hollow microballoon of the present invention is compared with other wet chemical method, has that synthetic method is simple, environmental friendliness, low temperature, advantage such as need not calcine; Gained titanic oxide hollow microballoon particle size distribution is more even, and the product crystal formation is intact, is suitable for use as the hyperfine material with property.In addition, the present invention overcome that the process that exists among the existing titanic oxide hollow microballoon preparation method is loaded down with trivial details, cost is higher relatively, be difficult to problem such as large-scale industrial production, has productive rate height, advantage such as with short production cycle, is fit to suitability for industrialized production.
Claims (5)
1, a kind of preparation method of titanic oxide hollow microballoon, it is characterized in that: with commercial titanium liquid is raw material, raw material put into have the teflon-lined autoclave, at 140～220 ℃ of following hydro-thermal reaction 4～24h, cooling after scouring, filtration, drying can obtain titanic oxide hollow microballoon.
2, the preparation method of titanic oxide hollow microballoon according to claim 1 is characterized in that, hydrothermal temperature is 180～200 ℃.
3, the preparation method of titanic oxide hollow microballoon according to claim 1 is characterized in that, the hydro-thermal reaction time is 12～20h.
4, the preparation method of titanic oxide hollow microballoon according to claim 1 is characterized in that, washing process adopts distilled water and absolute ethanol washing successively.
5, the preparation method of titanic oxide hollow microballoon according to claim 1 is characterized in that, drying temperature is 60～100 ℃, and be 12～24h time of drying.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB200810025847XA CN100551829C (en) | 2008-01-16 | 2008-01-16 | A kind of preparation method of titanic oxide hollow microballoon |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB200810025847XA CN100551829C (en) | 2008-01-16 | 2008-01-16 | A kind of preparation method of titanic oxide hollow microballoon |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101215000A CN101215000A (en) | 2008-07-09 |
| CN100551829C true CN100551829C (en) | 2009-10-21 |
Family
ID=39621521
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB200810025847XA Expired - Fee Related CN100551829C (en) | 2008-01-16 | 2008-01-16 | A kind of preparation method of titanic oxide hollow microballoon |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100551829C (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102838162B (en) * | 2011-06-21 | 2014-07-30 | 中国科学院过程工程研究所 | Porous titanium dioxide hollow sphere, its preparation and method for adsorbing Cr(VI) |
| CN102765754B (en) * | 2012-07-20 | 2014-01-22 | 中国科学院金属研究所 | Method for preparing porous TiO2 quasi-monodispersed micron hollow spheres |
| KR101567388B1 (en) * | 2013-07-02 | 2015-11-10 | 한국과학기술연구원 | Metal oxides composite including hollow core and porous shell layer and the fabrication method thereof |
| CN108314080B (en) * | 2017-01-18 | 2020-08-07 | 天津大学 | Method for rapidly preparing titanium dioxide hollow nanospheres |
| CN107512732A (en) * | 2017-09-14 | 2017-12-26 | 西北师范大学 | A kind of yellow titanium dioxide nanocrystalline and preparation method thereof |
| CN113772722A (en) * | 2021-10-28 | 2021-12-10 | 中国科学院合肥物质科学研究院 | TiO with special hollow structure2Preparation method of micro-spheres |
-
2008
- 2008-01-16 CN CNB200810025847XA patent/CN100551829C/en not_active Expired - Fee Related
Non-Patent Citations (7)
| Title |
|---|
| Mesoporous Titania Spheres with Tunable ChamberStuctureand Enhanced Photocatalytic Activity. Hexing Li, et al.Journal of the american chemical society,Vol.129 No.27. 2007 |
| Mesoporous Titania Spheres with Tunable ChamberStuctureand Enhanced Photocatalytic Activity. Hexing Li,et al.Journal of the american chemical society,Vol.129 No.27. 2007 * |
| One-step Fabrication and High Photocatalytic Activity ofPorous TiO2 Hollow Aggregates by Using a Low-TemperatureHydrothermal Method Withour Templates. Zhaoyang Liu, et al.Chem. Eur. J.,Vol.13 . 2006 |
| One-step Fabrication and High Photocatalytic Activity ofPorous TiO2 Hollow Aggregates by Using a Low-TemperatureHydrothermal Method Withour Templates. Zhaoyang Liu,et al.Chem.Eur.J.,Vol.13. 2006 * |
| Synthesis of Mesoporous TiO2 from Industrial TiOSO4Solution under Potential Outfield. Tiao，congxue，，et，al.稀有金属材料与工程，第26卷第增3期. 2007 |
| Synthesis of Mesoporous TiO2 from Industrial TiOSO4Solution under Potential Outfield. Tiao,congxue,et,al.稀有金属材料与工程，第26卷第增3期. 2007 * |
| 大孔及中空二氧化钛结构材料研究进展. 李宏宇等.高分子通报，第6期. 2007 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101215000A (en) | 2008-07-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101215001B (en) | Method for preparing rutile-type titanium dioxide micro-sphere | |
| CN100551829C (en) | A kind of preparation method of titanic oxide hollow microballoon | |
| CN101941736B (en) | Preparation method of single/double layer cavity structure and echinoid titanium dioxide microspheres | |
| CN102515246B (en) | Preparation method of porous nano zinc oxide (ZnO) | |
| CN105819502A (en) | Preparation method of ultrathin B phase titanium dioxide nano sheet | |
| CN102600880B (en) | Preparation method of visible light-response titanium dioxide photocatalytic liquid | |
| CN103691433B (en) | A kind of Ag doped Ti O 2material, and its preparation method and application | |
| CN105217676B (en) | Titania aerogel with nanometer sheet and nano-porous structure and preparation method thereof | |
| CN101811733A (en) | Visible light-responded basic bismuth bromide nanostructured microsphere material and preparation method thereof | |
| CN109012731A (en) | Sea urchin shape CoZnAl-LDH/RGO/g-C3N4Z-type hetero-junctions and its preparation method and application | |
| Wang et al. | Room temperature one-step synthesis of microarrays of N-doped flower-like anatase TiO2 composed of well-defined multilayer nanoflakes by Ti anodization | |
| CN107572582A (en) | A kind of preparation method of titanium dioxide nano thread | |
| CN1810356A (en) | Prepn process of nanometer crystal titania aerogel with high photocatalysis activity | |
| CN103663548B (en) | Preparation method for anatase titanium dioxide nanocrystalline mesoporous microsphere | |
| CN105056927A (en) | TiO2 nanotube composite SiO2 aerogel-based photocatalytic material and preparation method thereof | |
| CN102718256B (en) | Preparation method for titania microspheres with adjustable grain sizes | |
| CN104772149B (en) | Bi2O3/BiFeO3/TiO2 nano-flower photocatalytic material and preparation method thereof | |
| CN102070191A (en) | Two kinds of ordered porous titanium dioxide as well as preparation method and applications thereof | |
| CN101177299A (en) | Method for preparing porous TiO2 particle | |
| CN101319405B (en) | Production method of TiO2 nanotube and/or TiO2 nano-whisker | |
| CN103130266A (en) | Preparation method of titanium dioxide hollow ball constructed by nano slices | |
| CN102161506A (en) | Method for preparing C-N-codoped nano-TiO2 powder | |
| CN104649319B (en) | A kind of TiO 2(B) preparation method of nanosponges | |
| CN103601239A (en) | Preparation method of anatase and brookite mixed crystal TiO2 nanowire | |
| CN108017086A (en) | A kind of preparation method of bismuthyl carbonate-stannic oxide/graphene nano composite |
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: 20091021 Termination date: 20140116 |