CN101891466B - Method for preparing tabular barium titanate nanometer powder - Google Patents
Method for preparing tabular barium titanate nanometer powder Download PDFInfo
- Publication number
- CN101891466B CN101891466B CN 201010232215 CN201010232215A CN101891466B CN 101891466 B CN101891466 B CN 101891466B CN 201010232215 CN201010232215 CN 201010232215 CN 201010232215 A CN201010232215 A CN 201010232215A CN 101891466 B CN101891466 B CN 101891466B
- Authority
- CN
- China
- Prior art keywords
- powder
- barium titanate
- solution
- hydrocerol
- ammoniacal liquor
- 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
Images
Landscapes
- Inorganic Compounds Of Heavy Metals (AREA)
- Compositions Of Oxide Ceramics (AREA)
Abstract
The invention discloses a method for preparing tabular barium titanate nanometer powder. The method comprises the following steps: dissolving complexing agent citric acid in an ammonia system; adding reacting raw materials tetrabutyl orthotita and barium acetate to form solution A and solution B; adding absolute ethanol and polyethylene glycol after the solution A and the solution B are mixed to prepare precursor solution; preparing dry gel after water-bath evaporation and dry foaming, and calcining the dry gel at constant temperature of between 720 and 850 DEG C to obtain the nanometer barium titanate powder. The prepared nanometer barium titanate powder is in regular tabular shape with grain size of between 40 and 150nm, and has high purity and good dispersibility without generation of BaCO3 crystalline phase.
Description
Technical field
The invention belongs to the preparing technical field of nano material, relate to a kind of preparation method of tabular Barium Titanate nano-powder.
Background technology
Barium Titanate nano-powder is a kind of nano grade titanium silicate powder material of white, has excellent electric property, like high-k and ferroelectric, piezoelectricity and positive temperature coefficient effect etc.Barium Titanate nano-powder is the important foundation raw material of electrode component, is mainly used in the manufacturing of media ceramic, sensitive ceramic, is widely used in fields such as automatic temperature-controlled Heating element, laminated ceramic capacitor, PTC themistor spare, electro-optical device.
The preparation method of Barium Titanate nano-powder comprises high temperature solid-phase sintering method, sol-gel method, coprecipitation method, hydrothermal method etc. at present.High temperature solid-state method has simple, the low cost and other advantages of technology, but have that particle diameter is big, serious agglomeration, Ti/Ba than wayward, product purity is low, yield rate is low and component is difficult to mix and cause shortcomings such as the product chemical constitution is inhomogeneous.The shortcoming of traditional sol-gel method is that cost is higher, treatment temp is higher, the easy reunion of progenitor grows up.Coprecipitation method production efficiency is lower, and product is difficult for separating controlling, and impurity is more.Hydrothermal method needs special high-tension apparatus, and wherein villaumite is prone to cause etching problem, and forms coacervate easily.
Summary of the invention
The problem that the present invention solves is to provide a kind of preparation method of tabular Barium Titanate nano-powder, and this method technology is simple, with short production cycle, required equipment is simple, can prepare the tabular preferably Barium Titanate nano-powder of regular shape, dispersiveness.
The present invention realizes through following technical scheme:
A kind of preparation method of tabular Barium Titanate nano-powder may further comprise the steps:
1) Hydrocerol A being dissolved in volumetric concentration is that the amount of ammoniacal liquor is as the criterion can dissolve Hydrocerol A, adds butyl(tetra)titanate then and fully stirs, and is mixed with solution A in 25～28% the ammoniacal liquor, and wherein, the mol ratio of butyl(tetra)titanate and Hydrocerol A is 1: 1.5～2.5;
2) Hydrocerol A being dissolved in volumetric concentration is that the amount of ammoniacal liquor is as the criterion can dissolve Hydrocerol A, adds barium acetate then and fully stirs, and is mixed with solution B in 25～28% the ammoniacal liquor, and wherein, the mol ratio of barium acetate and Hydrocerol A is 1: 1.5～2.5;
3) according to the mol ratio of butyl(tetra)titanate and barium acetate be 1: 1 ratio; With solution A and solution B thorough mixing; The absolute ethyl alcohol that adds ammoniacal liquor TV 1/3～1/2 then; And, add the polyoxyethylene glycol of Hydrocerol A total mass 1/3～1/2 again with ammoniacal liquor accent pH value to 5.0～7.0, be mixed with precursor solution;
4) with precursor solution in 80～90 ℃ of water-baths evaporation until obtaining wet gel, and then wet gel is obtained xerogel at 130～140 ℃ of dry foaming 5～7h;
5) with xerogel 720～850 ℃ of calcining at constant temperature, take out behind calcining 3～6h and obtain tabular Barium Titanate nano-powder.
The molecular weight of described polyoxyethylene glycol is 4000 or 6000.
Described wet gel carries out the drying foaming under air atmosphere.
Described xerogel carries out calcining at constant temperature under air atmosphere.
Described tabular Barium Titanate nano-powder is loose tabular Barium Titanate nano-powder, and its size is 40～100nm.
Compared with prior art, the present invention has following beneficial technical effects:
When adopting sol-gel method to prepare Barium Titanate nano-powder, in the calcination process of gel, crystalline phase TiO appears at first
2, again by crystalline phase TiO
2The Ba reaction that discharges with the burning of complex compound in the middle of the gel generates barium titanate.In the common sol-gel method, tend to occur crystalline phase BaCO
3, and BaCO
3Be converted into comparatively difficulty of barium titanate fully, so in the Barium Titanate nano-powder of processing, often have BaCO in crystalline phase
3Remnants.And the present invention has adopted the dispersion system different with prior art to process gel, in calcination process, has avoided BaCO
3The generation of crystalline phase makes that the gained powder is purer; And, show that also the present invention has avoided BaCO in the calcination process of gel to the detection of the FTIR collection of illustrative plates of differing temps gained powder in the calcination process
3Generation, the XRD figure spectrum of the Barium Titanate nano-powder of last generation detected show do not have other dephasigns in the Barium Titanate nano-powder, particularly the appearance of BaCO3 crystalline phase diffraction peak.
And the present invention is dissolved in the complexing agent Hydrocerol A in the ammoniacal liquor system, adds the raw material butyl(tetra)titanate and the barium acetate of reaction again, forms solution A, B respectively, after both mix, adds absolute ethyl alcohol and polyoxyethylene glycol again; Owing to cooperate the process of colloidal sol different, make the complex structure that forms distinguish, the particulate growth changes when making the gel calcining, thereby has caused the difference of Barium Titanate nano-powder pattern.The powder of gained of the present invention is the tabular of regular shape, and size is 40～150nm.
The preparation method of Barium Titanate nano-powder provided by the invention owing to calcium acetate, butyl(tetra)titanate complete reaction will be converted into barium titanate, does not introduce impurity such as cl ions in this preparation process, need not the suction filtration cleaning to remove impurity, can shorten preparation cycle; And the N-BUTYL ACETATE of ammoniacal liquor, Hydrocerol A, polyoxyethylene glycol and reaction gained brings into play through water-bath and removes, and all the other remain in and can be carbonized in the calcination process and remove, and the purity of prepared nano silica powder is high, good dispersivity.The preparation method of Barium Titanate nano-powder provided by the invention, it is simple also to have production technique, easy to operate, and preparation cycle is short, and productive rate is higher, and facility investment is few, the advantage that cost is low.
Description of drawings
Fig. 1 is the FTIR collection of illustrative plates of gained Barium Titanate nano-powder under the different calcining temperatures, and wherein, X-coordinate is a wave number, and ordinate zou is a transmittance, and the gel of the present invention's preparation does not all have BaCO 400 ℃, 580 ℃, 600 ℃ following calcinings
3The generation of crystalline phase.
Fig. 2 is the SEM photo of Barium Titanate nano-powder, is shown as the tabular of rule, and size is 40～150nm.
Fig. 3 is the XRD figure spectrum of Barium Titanate nano-powder, and X-coordinate is 2 θ angles, and ordinate zou is an intensity, the complete and BaTiO of the diffraction peak in the collection of illustrative plates
3Conform to, do not have other dephasigns, particularly BaCO
3The appearance of crystalline phase diffraction peak.
Embodiment
Below in conjunction with accompanying drawing and concrete embodiment the preparation method of tabular Barium Titanate nano-powder is done detailed explanation, said is to explanation of the present invention rather than qualification.
Embodiment 1
The preparation method of Barium Titanate nano-powder may further comprise the steps:
1) Hydrocerol A 192.14g (1mol) being dissolved in volumetric concentration is that the butyl(tetra)titanate that adds 1.5mol then fully stirs, and is mixed with solution A in 25% the 300ml ammoniacal liquor;
2) Hydrocerol A 192.14g (1mol) being dissolved in volumetric concentration is that the barium acetate that adds 1.5mol then fully stirs, and is mixed with solution B in 25% the 300ml ammoniacal liquor;
3) according to the mol ratio of butyl(tetra)titanate and barium acetate be 1: 1 ratio, with solution A and solution B thorough mixing, transfer pH value to 5.0 with ammoniacal liquor after adding absolute ethyl alcohol 200ml, the polyoxyethylene glycol (PEG4000) that adds 64.05g again is mixed with precursor solution;
4) with precursor solution in 80 ℃ of water-baths evaporation until obtaining wet gel, and then wet gel dry foaming 7h under 130 ℃, air atmosphere obtained xerogel;
5) xerogel is calcined under 720 ℃ of constant temperature, air atmosphere, taken out the tabular Barium Titanate nano-powder that obtains loosening behind the calcining 6h.
The gel that the present invention processes has been avoided BaCO in calcination process
3The generation of crystalline phase, and the detection of FTIR collection of illustrative plates to differing temps in the calcination process (400 ℃, 580 ℃, 600 ℃) gained powder as shown in Figure 1 has been avoided BaCO in the calcination process of this explanation gel
3Generation, and temperature independent.
The SEM photo of the Barium Titanate nano-powder of 720 ℃ of calcining gained is as shown in Figure 2, and the XRD figure spectrum is as shown in Figure 3, can see that Barium Titanate nano-powder is the plate-like shape of rule, and size is 40～150nm; And purity is high, and the diffraction peak of XRD figure spectrum shows does not have other dephasigns.
Embodiment 2
The preparation method of Barium Titanate nano-powder may further comprise the steps:
1) Hydrocerol A 192.14g (1mol) being dissolved in volumetric concentration is that the butyl(tetra)titanate that adds 2.5mol then fully stirs, and is mixed with solution A in 28% the 300ml ammoniacal liquor;
2) Hydrocerol A 192.14g (1mol) being dissolved in volumetric concentration is that the barium acetate that adds 2.5mol then fully stirs, and is mixed with solution B in 28% the 300ml ammoniacal liquor;
3) according to the mol ratio of butyl(tetra)titanate and barium acetate be 1: 1 ratio, with solution A and solution B thorough mixing, transfer pH value to 7.0 with ammoniacal liquor after adding absolute ethyl alcohol 300ml, the polyoxyethylene glycol (PEG6000) that adds 96.07g again is mixed with precursor solution;
4) with precursor solution in 90 ℃ of water-baths evaporation until obtaining wet gel, and then wet gel dry foaming 5h under 140 ℃, air atmosphere obtained xerogel;
5) xerogel is calcined under 850 ℃ of constant temperature, air atmosphere, taken out the tabular Barium Titanate nano-powder that obtains loosening behind the calcining 3h.
Embodiment 3
The preparation method of Barium Titanate nano-powder may further comprise the steps:
1) Hydrocerol A 192.14g (1mol) being dissolved in volumetric concentration is that the butyl(tetra)titanate that adds 2mol then fully stirs, and is mixed with solution A in 28% the 300ml ammoniacal liquor;
2) Hydrocerol A 192.14g (1mol) being dissolved in volumetric concentration is that the barium acetate that adds 2mol then fully stirs, and is mixed with solution B in 28% the 300ml ammoniacal liquor;
3) according to the mol ratio of butyl(tetra)titanate and barium acetate be 1: 1 ratio, with solution A and solution B thorough mixing, transfer pH value to 6.0 with ammoniacal liquor after adding absolute ethyl alcohol 250ml, the polyoxyethylene glycol (PEG4000) that adds 75g again is mixed with precursor solution;
4) with precursor solution in 85 ℃ of water-baths evaporation until obtaining wet gel, and then wet gel dry foaming 6h under 135 ℃, air atmosphere obtained xerogel;
5) xerogel is calcined under 800 ℃ of constant temperature, air atmosphere, taken out the tabular Barium Titanate nano-powder that obtains loosening behind the calcining 4h.
Embodiment 4
The preparation method of Barium Titanate nano-powder may further comprise the steps:
1) Hydrocerol A 192.14g (1mol) being dissolved in volumetric concentration is that the butyl(tetra)titanate that adds 1.8mol then fully stirs, and is mixed with solution A in 25% the 300ml ammoniacal liquor;
2) Hydrocerol A 192.14g (1mol) being dissolved in volumetric concentration is that the barium acetate that adds 1.8mol then fully stirs, and is mixed with solution B in 28% the 300ml ammoniacal liquor;
3) according to the mol ratio of butyl(tetra)titanate and barium acetate be 1: 1 ratio, with solution A and solution B thorough mixing, transfer pH value to 5.8 with ammoniacal liquor after adding absolute ethyl alcohol 280ml, the polyoxyethylene glycol (PEG6000) that adds 80g again is mixed with precursor solution;
4) with precursor solution in 86 ℃ of water-baths evaporation until obtaining wet gel, and then wet gel dry foaming 5.5h under 138 ℃, air atmosphere obtained xerogel;
5) xerogel is calcined under 750 ℃ of constant temperature, air atmosphere, taken out the tabular Barium Titanate nano-powder that obtains loosening behind the calcining 4.5h.
Embodiment 5
The preparation method of Barium Titanate nano-powder may further comprise the steps:
1) Hydrocerol A 192.14g (1mol) being dissolved in volumetric concentration is that the butyl(tetra)titanate that adds 1.6mol then fully stirs, and is mixed with solution A in 28% the 300ml ammoniacal liquor;
2) Hydrocerol A 192.14g (1mol) being dissolved in volumetric concentration is that the barium acetate that adds 1.6mol then fully stirs, and is mixed with solution B in 28% the 300ml ammoniacal liquor;
3) according to the mol ratio of butyl(tetra)titanate and barium acetate be 1: 1 ratio, with solution A and solution B thorough mixing, transfer pH value to 7.0 with ammoniacal liquor after adding absolute ethyl alcohol 260ml, the polyoxyethylene glycol (PEG6000) that adds 90g again is mixed with precursor solution;
4) with precursor solution in 82 ℃ of water-baths evaporation until obtaining wet gel, and then wet gel dry foaming 6h under 132 ℃, air atmosphere obtained xerogel;
5) xerogel is calcined under 820 ℃ of constant temperature, air atmosphere, taken out the tabular Barium Titanate nano-powder that obtains loosening behind the calcining 5h.
Claims (5)
1. the preparation method of a tabular Barium Titanate nano-powder is characterized in that, may further comprise the steps:
1) Hydrocerol A being dissolved in volumetric concentration is that the amount of ammoniacal liquor is as the criterion can dissolve Hydrocerol A, adds butyl(tetra)titanate then and fully stirs, and is mixed with solution A in 25～28% the ammoniacal liquor, and wherein, the mol ratio of butyl(tetra)titanate and Hydrocerol A is 1: 1.5～2.5;
2) Hydrocerol A being dissolved in volumetric concentration is that the amount of ammoniacal liquor is as the criterion can dissolve Hydrocerol A, adds barium acetate then and fully stirs, and is mixed with solution B in 25～28% the ammoniacal liquor, and wherein, the mol ratio of barium acetate and Hydrocerol A is 1: 1.5～2.5;
3) according to the mol ratio of butyl(tetra)titanate and barium acetate be 1: 1 ratio; With solution A and solution B thorough mixing; The absolute ethyl alcohol that adds ammoniacal liquor TV 1/3～1/2 then; And, add the polyoxyethylene glycol of Hydrocerol A total mass 1/3～1/2 again with ammoniacal liquor accent pH value to 5.0～7.0, be mixed with precursor solution;
4) with precursor solution in 80～90 ℃ of water-baths evaporation until obtaining wet gel, and then wet gel is obtained xerogel at 130～140 ℃ of dry foaming 5～7h;
5) with xerogel 720～850 ℃ of calcining at constant temperature, take out behind calcining 3～6h and obtain tabular Barium Titanate nano-powder.
2. the preparation method of tabular Barium Titanate nano-powder as claimed in claim 1 is characterized in that, the molecular weight of described polyoxyethylene glycol is 4000 or 6000.
3. the preparation method of tabular Barium Titanate nano-powder as claimed in claim 1 is characterized in that, described wet gel carries out the drying foaming under air atmosphere.
4. the preparation method of tabular Barium Titanate nano-powder as claimed in claim 1 is characterized in that, described xerogel carries out calcining at constant temperature under air atmosphere.
5. the preparation method of Barium Titanate nano-powder as claimed in claim 1 is characterized in that, described tabular Barium Titanate nano-powder is loose tabular Barium Titanate nano-powder, and its size is 40～100nm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010232215 CN101891466B (en) | 2010-07-21 | 2010-07-21 | Method for preparing tabular barium titanate nanometer powder |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010232215 CN101891466B (en) | 2010-07-21 | 2010-07-21 | Method for preparing tabular barium titanate nanometer powder |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101891466A CN101891466A (en) | 2010-11-24 |
| CN101891466B true CN101891466B (en) | 2012-12-19 |
Family
ID=43100845
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 201010232215 Expired - Fee Related CN101891466B (en) | 2010-07-21 | 2010-07-21 | Method for preparing tabular barium titanate nanometer powder |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101891466B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102432284B (en) * | 2011-08-23 | 2013-04-03 | 陕西科技大学 | Preparation method of grain boundary layer type structure ceramic membrane |
| CN102432283B (en) * | 2011-08-23 | 2013-03-20 | 陕西科技大学 | Preparation method of grain boundary layer type structure BaTiO3 composite membrane |
| CN105967748A (en) * | 2016-05-05 | 2016-09-28 | 陕西科技大学 | Preparation method of BaTiO3 porous material |
| CN106187163B (en) * | 2016-07-01 | 2019-11-29 | 北京工业大学 | A kind of high tetragonal-phase barium titanate and preparation method thereof of rare earth neodymium doping |
| CN113372111B (en) * | 2021-07-09 | 2022-12-13 | 湖南省新化县鑫星电子陶瓷有限责任公司 | Preparation method of ceramic substrate |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007099541A (en) * | 2005-09-30 | 2007-04-19 | Nippon Chemicon Corp | Method of manufacturing dielectric ceramic composition, and ceramic capacitor using the manufactured dielectric ceramic composition |
| CN101633520A (en) * | 2009-08-25 | 2010-01-27 | 陕西科技大学 | Method for preparing barium titanate nano-powder |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1061764A (en) * | 1990-11-23 | 1992-06-10 | 南开大学 | The preparation of ultra-micropowder of high purity barium titanate |
| WO2001010781A1 (en) * | 1999-08-05 | 2001-02-15 | Korea Institute Of Science And Technology | METHOD FOR MANUFACTURING BaTiO3 BASED POWDERS |
| KR100434883B1 (en) * | 2001-08-14 | 2004-06-07 | 삼성전기주식회사 | A method for the manufacturing of Barium-Titanate based Powder |
| KR100489403B1 (en) * | 2002-05-30 | 2005-05-12 | 주식회사 나노 | METHOD OF PREPARING BaTiO3 POWDER |
| JP2005272295A (en) * | 2004-02-26 | 2005-10-06 | Dowa Mining Co Ltd | Tetragonal barium titanate particles, method for manufacturing the same and ceramic capacitor |
| JP2005330112A (en) * | 2004-05-18 | 2005-12-02 | Ministry Of National Defense Chung Shan Inst Of Science & Technology | Method for producing barium titanate powder |
-
2010
- 2010-07-21 CN CN 201010232215 patent/CN101891466B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007099541A (en) * | 2005-09-30 | 2007-04-19 | Nippon Chemicon Corp | Method of manufacturing dielectric ceramic composition, and ceramic capacitor using the manufactured dielectric ceramic composition |
| CN101633520A (en) * | 2009-08-25 | 2010-01-27 | 陕西科技大学 | Method for preparing barium titanate nano-powder |
Non-Patent Citations (2)
| Title |
|---|
| 侯铁翠等."改进的柠檬酸盐溶胶-凝胶法制备四方相纳米尺寸钛酸钡粉体".《航空材料学报》.2007,第27卷(第3期),第74页左栏第2段至右栏第2段，图1. |
| 侯铁翠等."改进的柠檬酸盐溶胶-凝胶法制备四方相纳米尺寸钛酸钡粉体".《航空材料学报》.2007,第27卷(第3期),第74页左栏第2段至右栏第2段,图1. * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101891466A (en) | 2010-11-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101633520A (en) | Method for preparing barium titanate nano-powder | |
| CN101891466B (en) | Method for preparing tabular barium titanate nanometer powder | |
| CN107151029B (en) | A kind of sol-gel self-combustion synthesis preparation process of tetra phase barium titanate powder | |
| CN104828858B (en) | The method that nanometer barium titanate powder is prepared based on ball milling | |
| CN104477978B (en) | A kind of method preparing perovskite nano-powder | |
| CN101767821B (en) | Synthesis method of barium zirconate titanate-based dielectric material | |
| CN102691105A (en) | Method for preparing barium titanate monocrystal nano particles of six-pin structural perovskite | |
| JP2018168504A (en) | Method for producing metal titanate fiber | |
| CN103011807B (en) | Method for preparing strontium titanate powder | |
| CN104528799A (en) | Preparation method of ultrafine magnesium-based rare earth hexaaluminate powder | |
| CN104030676B (en) | The preparation method of barium strontium titanate nano powder | |
| CN102976400A (en) | Preparation method for tetragonal phase nano barium titanate | |
| CN108530057A (en) | Sol-gel method application and preparation is in the morphology controllable CaTiO of energy storage3The method of ceramics | |
| KR102590443B1 (en) | Nano barium titanate microcrystals and method for producing the same and barium titanate powder and method for producing the same | |
| CN103449520B (en) | Rod-like niobium pentoxide template grain and preparation method thereof | |
| CN104446445B (en) | Preparation method of monodisperse nano-powdery barium titanate | |
| CN102674442A (en) | Method for preparing strontium titanate nano powder through microwave hydrothermal method | |
| CN106187163A (en) | A kind of high tetragonal-phase barium titanate of rare earth neodymium doping and preparation method thereof | |
| CN103882558B (en) | A kind of perovskite structure AgNbO 3fiber and preparation method thereof | |
| CN102249669A (en) | Preparation method of nanometer high-purity barium titanate | |
| CN104891559B (en) | With titanium dioxide for titanium source synthesis Li doping PbTiO3the method of nano-particle and product and application | |
| CN102677145A (en) | Preparation method of perovskite structure lead titanate single crystal nanoparticles | |
| CN104907062A (en) | Method for synthesizing Li-doped PbTiO3 nanoparticles, and product and application thereof | |
| CN105254295A (en) | Preparation method of neodymium doped barium titanate ceramic nano-powder | |
| CN105236474A (en) | Preparation method of submicron-scale barium titanate powder |
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 | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20121219 Termination date: 20150721 |
|
| EXPY | Termination of patent right or utility model |