CN1587030A - Process for preparing boron nitride nano tube - Google Patents
Process for preparing boron nitride nano tube Download PDFInfo
- Publication number
- CN1587030A CN1587030A CN 200410068824 CN200410068824A CN1587030A CN 1587030 A CN1587030 A CN 1587030A CN 200410068824 CN200410068824 CN 200410068824 CN 200410068824 A CN200410068824 A CN 200410068824A CN 1587030 A CN1587030 A CN 1587030A
- Authority
- CN
- China
- Prior art keywords
- boron nitride
- boron
- tube
- nitride nano
- nanometer
- 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
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 229910052582 BN Inorganic materials 0.000 title claims abstract description 37
- 239000002071 nanotube Substances 0.000 title claims abstract description 36
- 238000004519 manufacturing process Methods 0.000 title abstract 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 38
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 19
- 239000000843 powder Substances 0.000 claims abstract description 12
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000004327 boric acid Substances 0.000 claims abstract description 6
- 150000001639 boron compounds Chemical class 0.000 claims abstract description 5
- 238000000498 ball milling Methods 0.000 claims description 14
- 238000002360 preparation method Methods 0.000 claims description 9
- 239000002994 raw material Substances 0.000 claims description 9
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 7
- 229910052810 boron oxide Inorganic materials 0.000 claims description 6
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 claims description 6
- 229910052796 boron Inorganic materials 0.000 claims description 4
- 238000004140 cleaning Methods 0.000 claims description 3
- 238000009413 insulation Methods 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract description 11
- 239000000463 material Substances 0.000 abstract description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 abstract description 6
- 239000012153 distilled water Substances 0.000 abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 4
- 239000004065 semiconductor Substances 0.000 abstract description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 2
- 239000001257 hydrogen Substances 0.000 abstract description 2
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 2
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 2
- 229910010293 ceramic material Inorganic materials 0.000 abstract 1
- 231100000252 nontoxic Toxicity 0.000 abstract 1
- 230000003000 nontoxic effect Effects 0.000 abstract 1
- FAQYAMRNWDIXMY-UHFFFAOYSA-N trichloroborane Chemical compound ClB(Cl)Cl FAQYAMRNWDIXMY-UHFFFAOYSA-N 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 238000007669 thermal treatment Methods 0.000 description 5
- 238000001291 vacuum drying Methods 0.000 description 5
- 230000005540 biological transmission Effects 0.000 description 4
- 235000017166 Bambusa arundinacea Nutrition 0.000 description 3
- 235000017491 Bambusa tulda Nutrition 0.000 description 3
- 241001330002 Bambuseae Species 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 235000015334 Phyllostachys viridis Nutrition 0.000 description 3
- 239000011425 bamboo Substances 0.000 description 3
- 239000002086 nanomaterial Substances 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000001241 arc-discharge method Methods 0.000 description 2
- 239000002041 carbon nanotube Substances 0.000 description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000010891 electric arc Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000004098 selected area electron diffraction Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 208000037656 Respiratory Sounds Diseases 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 230000003064 anti-oxidating effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005430 electron energy loss spectroscopy Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000000608 laser ablation Methods 0.000 description 1
- 238000003701 mechanical milling Methods 0.000 description 1
- 239000002159 nanocrystal Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 230000003334 potential effect Effects 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Images
Abstract
The present invention relates to the process of preparing boron nitride nanotube, and relates to inorganic nanometer material. Non-toxic boron compound, such as boron chloride, boric acid, etc. as material is first ball ground for certain time, and then heated to over 800 deg.c in flowing ammonia or nitrogen and maintained for over 0.5 hr. The product after being cooled is cleaned in dilute hydrochloric acid, distilled water and alcohol and dried to obtain white powder as the boron nitride nanotube product. The process is simple, mild in condition and suitable for mass production, and has yield over 80 %. The prepared boron nitride nanotube is semiconductor and may be used in nanometer electronic device, nanometer structural ceramic material, hydrogen storing material, etc.
Description
Technical field
The novel method of the boron nitride nano-tube that the present invention is a preparation purity height, productive rate is big relates to inorganic nano material.
Background technology
Boron nitride nano-tube is a kind of very special nanotube-shaped material.It has stable insulativity, high thermal stability and chemical stability and special mechanical property and electric property.Received huge concern in the monodimension nanometer material field in recent years.Electronic structure calculation shows that boron nitride nano-tube is a kind of semiconductor material, has fixed bandwidth (5.5ev).Different with CNT (carbon nano-tube), its band system does not rely on the wall number of diameter, chirality feature and the nanotube of pipe.Therefore, boron nitride nano-tube has been simplified the complicacy that the 1-dimention nano pipe can be with, and make making nano level semiconductor element becomes possibility, for the research of one dimension Nano structure with the tempting prospect that provides is provided.Boron nitride nano-tube can be brought into play its potential effect at the aspects such as coating layer of nano electron device, nanostructure stupalith, storage hydrogen and anti-oxidation, has a good application prospect.
The technology of preparing of boron nitride nano-tube. report is a lot of now.Famous preparation method has arc discharge method, laser ablation method, electric arc melting method, chemical Vapor deposition process and chemical method etc.Above-mentioned these methods, what have need carry out under high temperature or condition of high voltage, and what have is very difficult when the control reaction conditions, and obtains the dispersion of boron nitride nanometer tubular construction usually, and output is few, and purity is low.Make boron nitride nano-tube be subjected to restriction to a certain degree in application facet.Ball milled is to prepare nanometer powder method commonly used, successfully prepares nanocrystal, nanoparticle and nano combined component.In mechanical milling process, because friction, collision and extruding between grinding element and the material cause the structural changes of material, as producing internal stress, viscous deformation, defective and crackle etc.Because the structural changes of material and chemical reaction are caused by mechanical energy, rather than heat energy,, and belong to non-equilibrium reaction so chemical reaction can take place at normal temperatures.Compare with the electric arc melting method with above-mentioned arc discharge method, ball milled at room temperature carries out, and annealing temperature low (＜1500 ℃).But with this method respectively the people such as also rare .YingChen of synthesis of nano pipe at room temperature respectively B powder and boron nitride powder are carried out ball milling, then it is carried out anneal, obtained boron nitride nano-tube.Because thermal treatment is carried out under flowing nitrogen, so the boron nitride nano-tube purity that they obtain is low, productive rate is not high yet.For obtaining the boron nitride nano-tube of high yield, we adopt ball milled, contain boron and avirulent boron compound is a raw material with boron oxide, boric acid etc., elder generation's ball milling regular hour, under the mobile ammonia, heat-treat then, be incubated certain hour after being heated to the temperature more than 800 ℃, after cleaning, obtained phase purity height, the boron nitride nano-tube that productive rate is big.The preparation method that we adopt, required equipment is simple, and technology is simple and easy to do, and thermal treatment temp is low, and is safe.Low cost, high yield, good, the growing controllable of purity can realize producing in batches, are more satisfactory preparation methods.Therefore the further widespread use in the nanometer field is significant for boron nitride nano-tube in the present invention.
Summary of the invention
The present invention is achieved in that and at first selects for use boron oxide, boric acid etc. to contain boron and avirulent boron compound is a raw material, more than the first ball milling 4h, is being heated under the mobile ammonia more than 800 ℃ then, more than the insulation 0.5h.Take out the cooling back, through cleaning after drying, obtains white powder and be boron nitride nano-tube.
Description of drawings:
The scanning electronic microscope shape appearance figure of accompanying drawing 1. prepared products reflects the output height of boron nitride nano-tube in the product;
The X-ray diffraction spectrogram of accompanying drawing 2. prepared products proves that product is the boron nitride crystal of pure phase, hexagonal structure;
The transmission electron microscope photo of accompanying drawing 3. cylinder pattern boron nitride nano-tubes;
The transmission electron microscope photo of accompanying drawing 4. ring pattern boron nitride nano-tubes;
Accompanying drawing 5. selected area electron diffraction style photos illustrate that the boron nitride nano-tube of preparation is a single crystal structure;
Accompanying drawing 6. high-resolution electron microscope photos, the reflection boron nitride nano-tube has good degree of crystallinity;
Accompanying drawing 7. electron energy loss spectroscopy (EELS) figure, the composition that further proves nanotube is a boron nitride.
Be explained as follows with the specific embodiment by reference to the accompanying drawings:
1. contain boron element and avirulent boron compound as raw material, more than the first ball milling 4h take boron oxide, boric acid etc.
2. the raw material behind the ball milling is heated under the mobile ammonia, when temperature reached more than 800 ℃, constant temperature kept more than half hour.
The present invention passes through first to the raw material behind the ball milling, and thermal treatment in the mobile ammonia has obtained purified boron nitride nano-tube.Preparation technology of the present invention is simple, and the reaction conditions gentleness can realize producing in batches.Gordian technique is:
1. proper raw material, and ball milling is more than 4h.
2. thermal treatment is carried out under the mobile ammonia atmosphere, and the temperature of heating is more than 800 ℃, and the time of insulation is more than 0.5h;
The effective scanning electricity of the boron nitride nanometer of preparing, X-ray diffraction, means such as transmission electron microscope, selected area electron diffraction, high-resolution-ration transmission electric-lens and energy loss spectroscopy characterize its composition and structure.The result shows, the boron nitride nano-tube better crystallinity degree of preparation is the monocrystalline of the hexagonal structure of pure phase, patterns such as cylindrical or ring, its diameter minimum be several nanometers, maximum about 200 nanometers, length reaches about 10 microns.
Advantage of the present invention is: required equipment is simple, and technology is simple and easy to do, and thermal treatment temp is low, and is safe.Low cost, high yield, purity are good, can realize producing in batches, and be more satisfactory preparation method.The present invention provides further convenience to boron nitride nano-tube in the application of association area, has great practical value.
Embodiment
Embodiment 1: with purity is that 99.8% boron powder is a raw material, and ball milling feeds the mobile ammonia and heats in vacuum tube furnace after the regular hour, and the flow velocity of ammonia is 100ml/min, the 10 ℃/min of speed of intensification.When temperature reached 1000 ℃, constant temperature kept 6h again.With dilute hydrochloric acid, distilled water and ethanol sample is carried out after several cleans, vacuum drying oven in obtain the powder of white after the oven dry, be prepared bamboo joint structure boron nitride nano-tube.
Embodiment 2: with purity is that 99.8% boron powder is a raw material, and ball milling feeds the mobile ammonia and heats in vacuum tube furnace after the regular hour, and the flow velocity of ammonia is 100ml/min, the 10 ℃/min of speed of intensification.When temperature reached 1200 ℃, constant temperature kept 6h again.Obtain the powder of white, being prepared is the boron nitride nano-tube of a small amount of bamboo joint structure of advocating peace with cylindrical structural.
Embodiment 3
With a certain proportion of boron powder (purity 99.8%) and Fe
2O
3Feed the mobile ammonia behind (analytical pure) ball milling and heat in vacuum tube furnace, the flow velocity of ammonia is 100ml/min, the speed 6-10 of intensification ℃/min.When temperature reached 1300 ℃, constant temperature kept 3h again.With dilute hydrochloric acid, distilled water and ethanol sample is carried out after several cleans, vacuum drying oven in obtain the powder of white after the oven dry, be prepared boron nitride nano-tube.
Embodiment 4:
With the mixture of a certain proportion of boric acid (purity 99.8%) with gac, will in vacuum tube furnace, feed the mobile ammonia and heat behind the ball milling, the flow velocity of ammonia is 150ml/min, the 6 ℃/min of speed of intensification.When temperature reached 1300 ℃, constant temperature kept more than the 0.5h again.After with dilute hydrochloric acid, distilled water and ethanol sample being cleaned, in vacuum drying oven, obtain the powder of white after the oven dry, be prepared boron nitride nano-tube.
Embodiment 5: with the mixture of a certain proportion of boron oxide and graphite, heat in the vacuum tube furnace that feeds the ammonia that flows behind the ball milling, the flow velocity of ammonia is 100ml/min, the 7 ℃/min of speed of intensification.When temperature reached 1200 ℃, constant temperature kept 6h again.With dilute hydrochloric acid, distilled water and ethanol sample is carried out after several cleans, in vacuum drying oven, obtain the powder of white after the oven dry, be prepared boron nitride nano-tube.Nanotube be bamboo joint structure by diameter for the 80-120 nanometer and on the surface and around to grow diameter be that the tiny nanotube of several nanometers is composited.
Embodiment 6: with the mixture of a certain proportion of boron oxide and gac, heat in the vacuum tube furnace that feeds the ammonia that flows behind the ball milling, the flow velocity of ammonia is 100ml/min, the 7 ℃/min of speed of intensification.When temperature reached 1200 ℃, constant temperature kept 6h again.With dilute hydrochloric acid, distilled water and ethanol sample is carried out after several cleans, in vacuum drying oven, obtain the powder of white after the oven dry, be prepared boron nitride nano-tube.
Claims (1)
1. the preparation method of a boron nitride nano-tube is characterized in that: select for use boron oxide, boric acid etc. to contain boron and avirulent boron compound is a raw material, more than the first ball milling 4h, be heated under the mobile ammonia more than 800 ℃ then, more than the insulation 0.5h.Take out the cooling back, through cleaning after drying, obtains white powder and be boron nitride nano-tube.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410068824 CN1281481C (en) | 2004-07-08 | 2004-07-08 | Process for preparing boron nitride nano tube |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410068824 CN1281481C (en) | 2004-07-08 | 2004-07-08 | Process for preparing boron nitride nano tube |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1587030A true CN1587030A (en) | 2005-03-02 |
| CN1281481C CN1281481C (en) | 2006-10-25 |
Family
ID=34604170
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200410068824 Expired - Fee Related CN1281481C (en) | 2004-07-08 | 2004-07-08 | Process for preparing boron nitride nano tube |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1281481C (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1326768C (en) * | 2005-12-20 | 2007-07-18 | 山东大学 | Method for preparing boron nitride nanometer ring and tube |
| CN100347079C (en) * | 2005-04-20 | 2007-11-07 | 中国科学院金属研究所 | Production of boron nitride nanometer tube with water as growth improver |
| CN100526217C (en) * | 2006-04-29 | 2009-08-12 | 中国科学院金属研究所 | Preparation method of quasi one-dimensional boron nitride nanostructure |
| CN101550599B (en) * | 2009-04-16 | 2011-05-11 | 山东大学 | Preparation method of boron nitride crystal whisker |
| CN102398897A (en) * | 2011-11-07 | 2012-04-04 | 北京航空航天大学 | Method for preparing two-dimensional nano boron nitride with jet flow cavitation technology |
| CN102849694A (en) * | 2012-10-20 | 2013-01-02 | 景德镇陶瓷学院 | Preparation method of batch preparation of boron nitride nanotube |
| CN102126709B (en) * | 2010-01-20 | 2013-04-03 | 中国科学院金属研究所 | Preparation method of boron nitride one-dimensional nanostructure macroscopic rope |
| CN103922295A (en) * | 2014-04-17 | 2014-07-16 | 河北工业大学 | Preparation method of boron nitride nano tube |
| CN104233454A (en) * | 2014-06-17 | 2014-12-24 | 中山大学 | Method for effectively synthesizing monocrystal hexagonal boron nitride structure by substitution reaction |
-
2004
- 2004-07-08 CN CN 200410068824 patent/CN1281481C/en not_active Expired - Fee Related
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100347079C (en) * | 2005-04-20 | 2007-11-07 | 中国科学院金属研究所 | Production of boron nitride nanometer tube with water as growth improver |
| CN1326768C (en) * | 2005-12-20 | 2007-07-18 | 山东大学 | Method for preparing boron nitride nanometer ring and tube |
| CN100526217C (en) * | 2006-04-29 | 2009-08-12 | 中国科学院金属研究所 | Preparation method of quasi one-dimensional boron nitride nanostructure |
| CN101550599B (en) * | 2009-04-16 | 2011-05-11 | 山东大学 | Preparation method of boron nitride crystal whisker |
| CN102126709B (en) * | 2010-01-20 | 2013-04-03 | 中国科学院金属研究所 | Preparation method of boron nitride one-dimensional nanostructure macroscopic rope |
| CN102398897A (en) * | 2011-11-07 | 2012-04-04 | 北京航空航天大学 | Method for preparing two-dimensional nano boron nitride with jet flow cavitation technology |
| CN102398897B (en) * | 2011-11-07 | 2013-04-24 | 北京航空航天大学 | Method for preparing two-dimensional nano boron nitride with jet flow cavitation technology |
| CN102849694A (en) * | 2012-10-20 | 2013-01-02 | 景德镇陶瓷学院 | Preparation method of batch preparation of boron nitride nanotube |
| CN103922295A (en) * | 2014-04-17 | 2014-07-16 | 河北工业大学 | Preparation method of boron nitride nano tube |
| CN103922295B (en) * | 2014-04-17 | 2015-11-04 | 河北工业大学 | A kind of preparation method of boron nitride nano-tube |
| CN104233454A (en) * | 2014-06-17 | 2014-12-24 | 中山大学 | Method for effectively synthesizing monocrystal hexagonal boron nitride structure by substitution reaction |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1281481C (en) | 2006-10-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Lu et al. | Growth of SiC nanorods at low temperature | |
| CN108545708B (en) | Preparation method of coralline hexagonal boron nitride micro-nano tube sheet composite structure | |
| Gao et al. | Synthesis, Raman scattering and defects of β-Ga 2 O 3 nanorods | |
| Ding et al. | The synthesis of titanium nitride whiskers on the surface of graphite by molten salt media | |
| Siddheswaran et al. | Preparation and characterization of ZnO nanofibers by electrospinning | |
| CN1281481C (en) | Process for preparing boron nitride nano tube | |
| Omidi et al. | Synthesis and characterization of SiC ultrafine particles by means of sol-gel and carbothermal reduction methods | |
| CN100338266C (en) | Method of synthetizing silicon carbide nano rods | |
| CN102094260A (en) | Method for preparing metal-doped silicon carbide-based fibers | |
| Shan et al. | Shape-controlled synthesis of monodispersed beta-gallium oxide crystals by a simple precipitation technique | |
| Chen et al. | Tuning the morphologies of SiC nanowires via the change of the Co x Si y melts | |
| CN101649491A (en) | Method for directionally growing SiC monocrystal nanowire array | |
| Liu et al. | Facile growth of oriented SiC nanowires arrays on carbon fiber cloth via CVD | |
| CN101177268A (en) | Method for low-temperature preparation of cubic silicon carbide nano wire | |
| CN102689904B (en) | Method for preparing SiC nanowire and array thereof | |
| JP3985044B2 (en) | Single crystal silicon nanotube and method for producing the same | |
| JP3571287B2 (en) | Method for producing silicon oxide nanowires | |
| JP4016105B2 (en) | Manufacturing method of silicon nanowires | |
| CN1834309A (en) | Method of synthetizing two kinds of different shaped silicon carbid nano wire | |
| Wu et al. | Low-temperature rapid synthesis of ultrafine hafnium carbide ceramic powders | |
| CN1327046C (en) | Monocrystalline Si3N4 nanometer belt and micro belt preparation method | |
| CN104233454A (en) | Method for effectively synthesizing monocrystal hexagonal boron nitride structure by substitution reaction | |
| JP2008100863A (en) | Silicon carbide nanostructure and its producing method | |
| CN113788464A (en) | Method for preparing boron nitride nanotube by using double transition metal oxide as catalyst | |
| Xie et al. | A simple route to large scale synthesis of crystalline αSi 3 N 4 nanowires |
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: 20061025 |