CN103675078B - Preparation method for acetone gas sensor - Google Patents
Preparation method for acetone gas sensor Download PDFInfo
- Publication number
- CN103675078B CN103675078B CN201310484412.2A CN201310484412A CN103675078B CN 103675078 B CN103675078 B CN 103675078B CN 201310484412 A CN201310484412 A CN 201310484412A CN 103675078 B CN103675078 B CN 103675078B
- Authority
- CN
- China
- Prior art keywords
- gas sensor
- acetone
- polypyrrole
- tin ash
- hybrid material
- 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
Abstract
The invention discloses a preparation method for an acetone gas sensor. According to the preparation method, a series of tin dioxide and polypyrrole hybrid materials with different polypyrrole mass percents are prepared by using a simultaneous reaction of a hydrothermal method and a polymer in-situ generation method; the tin dioxide and polypyrrole hybrid materials are used for coating a heater-type device structure and an aluminum oxide ceramic tube is used as a carrier to prepare the acetone gas sensor; a noble metal electrode lead wire is a platinum wire and a sensing element tube core is the aluminum oxide ceramic tube. The method disclosed by the invention is good for finishing a reaction in one step and easily purifying a product. The gas sensor prepared by the method has good gas sensing selectivity on acetone gas under a low working environment; the recovery time can be rapidly responded; meanwhile, the interferences caused by hydrogen, carbon monoxide and ammonia gas can also be eliminated.
Description
Technical field
The present invention relates to a kind of preparation method's of gas sensor, particularly a kind of acetone gas sensor preparation method, belong to gas sensing device manufacturing technology field.
Background technology
Acetone is as a kind of conventional chemical substance, mainly as the solvent in organic synthesis raw material, cosmetics, solvent and the extraction agent etc. in commercial production.Because acetone has volatile, easy intoxicating, easily causes quick-fried character, therefore it is monitored to the accuracy that can improve real-time estimate accident, constantly eliminate accident potential, minimizing accident is the generation of major accident particularly.In prior art, build for monitoring after the gas sensor of acetone waits modification by oxide by doping.Now mainly contain ZnO, SnO for the oxide of acetone vapor sensitive material
2, Ga
2o
3, CeO
2, NiO etc., made acetone gas sensor exists the defect that working temperature is higher, power consumption is larger mostly.For example, WO
3-ZnO and MoO
3the working temperature of-ZnO is 500 DEG C, CdIn
2o
4working temperature be 350 DEG C, Eu
2o
3-SnO
2working temperature is 185 DEG C.In order to meet industrial needs, finding the acetone gas sensor that a kind of working temperature is lower becomes the common problem in this field.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of acetone gas sensor, overcome the defect that acetone gas sensor working temperature is higher, power consumption is larger existing in prior art.
The object of the present invention is achieved like this.A preparation method for acetone gas sensor, comprises the following steps:
(1) prepare tin ash and polypyrrole (Er Yangization Xi ∕ Ppy) hybrid material
By 1 ~ 20mg pyrrole monomer, 80 ~ 99mg tin ash, 2.42 ~ 48.40mg anhydrous ferric trichloride, 40 ~ 60ml water (H
+concentration 1mol ∕ L), mix in proportion, after stirring, ultrasonic 30min, proceed to reactor, reactor is placed in to 140 DEG C of baking ovens, hydro-thermal reaction 8 hours, react complete, take out reactor, naturally cool to room temperature, by sedimentation and filtration, respectively with deionized water, ethanol, acetone washing several, finally product is dried in 60 DEG C of baking ovens, obtains tin ash and Ppy(bis-Yangization Xi ∕ Ppy) hybrid material, for subsequent use;
(2) clean top layer and be covered with gold electrode four jiaos and have the alumina ceramic tube of platinum electrode, dry for subsequent use;
(3) tin ash and polypyrrole hybrid material are ground, with deionized water furnishing pasty state, be coated on alumina ceramic tube, be placed in room temperature and dry for subsequent use;
(4) weld, encapsulate according to heater-type device common process, make acetone gas sensor.
The method of testing of the prepared acetone gas sensor of the present invention is as follows:
At 90 DEG C, carry out air-sensitive test by voltage detection method.Pull-up resistor is 4.7M Ω, and ambient humidity is 60%.Response (recovery) time is for being changed to │ V from gas sensor contact (disengaging) tested gas to its magnitude of voltage
a-V
g90% time used of │ value, sensitivity directly represents with voltage.V
g, V
athe steady state voltage value of representation element in test atmosphere and pure air respectively.
The present invention obtains following beneficial effect: the present invention utilizes hydro-thermal method to react with polymer in situ method of formation is simultaneous, can prepare tin ash and the polypyrrole hybrid material of a series of different polypyrrole massfractions.The method is conducive to react that a step completes, product is easy to purifying; It can have good air-sensitive selectivity to acetone gas prepared gas sensor under lower working temperature, and response recovery time faster can also be got rid of the interference of hydrogen, carbon monoxide and ammonia simultaneously.
Brief description of the drawings
Fig. 1 is the infrared spectrogram of polypyrrole, tin ash and polypyrrole (3%) hybrid material and tin ash and polypyrrole (20%) hybrid material..
In Fig. 1, the characteristic absorption peak of polypyrrole is: 1560cm
-1, 1470cm
-1, 1398cm
-1, 1298cm
-1, 1211cm
-1, 1047 cm
-1, 930 cm
-1and 790cm
-1.1560cm
-1the stretching vibration that is C=C absorbs, 1298cm
-1the stretching vibration that is C-C absorbs, 1211cm
-1the stretching vibration that is C-N absorbs, and 1470,1398,1047,930,790 cm
-1the absorption peak at place represents the characteristic absorption of pyrrole ring.Except 790,930cm
-1outward, above-mentioned characteristic peak can be seen in hybrid material.In polypyrrole 790 and 930cm
-1absorption peak not do not occur in hybrid material, is because Sn-O absorption of vibrations in tin ash is at～660cm
-1there is wide and strong peak in place, thus covered pyrrole ring 790,930cm
-1the absorption peak at place causes.In addition, tin ash and polypyrrole (3%) hybrid material and tin ash and polypyrrole (20%) hybrid material all～2923,2853cm
-1occurred-CH of place
2c-H stretching vibration absorption peak, illustrate that isomerization has occurred pyrrole ring, some two keys place occurred saturated due to (as
).
Fig. 2 is the transmission electron microscope photo of tin ash and polypyrrole (20%) hybrid material.
As shown in Figure 2, in the time that the massfraction of polypyrrole in hybrid material is 20%, particle presents random profile, and homogeneity is slightly poor, and this and polypyrrole content increase, and amorphous substance increases relevant.Some particle edges are fuzzy, and the lattice line of tin ash almost be can't see, this be due to tin ash coated outside due to polypyrrole.
Fig. 3 is the electronic diffraction picture photographing from TEM border.
This is the electronic diffraction picture of typical rutile-type tin ash crystal.Fig. 3 illustrates that some tin ash particle surfaces are exposed, and the particle surface of other has just wrapped up skim polypyrrole.
Fig. 4 is tin ash and polypyrrole (1%) hybrid material (4-1), tin ash and polypyrrole (3%) hybrid material (4-2), tin ash and the response recovery curve of polypyrrole (5%) hybrid material (4-3) to variable concentrations acetone gas.
From Fig. 4-1, Fig. 4-2, Fig. 4-3 see that tin ash and polypyrrole hybrid material are 20 ~ 25s to the acetone response time of variable concentrations, release time <10s.
Embodiment
Following examples are used for illustrating the present invention, but protection scope of the present invention is not limited to this.
The preparation method of a kind of acetone gas sensor of embodiment
This acetone gas sensor adopts heater-type device architecture, and taking alumina ceramic tube as carrier, noble metal electrode lead-in wire is platinum filament, and sensitive element tube core is alumina ceramic tube, outer tin ash and the polypyrrole hybrid material of being coated with of pipe.
One, tin ash and polypyrrole hybrid material is synthetic
1, synthetic method one
Get 50ml distilled water, regulate its H with hydrochloric acid
+concentration be about 1mol ∕ L, add 1mg pyrroles, by ultrasonic solution dispersion 30min.Add again 95mg tin ash.By after potpourri stirring, ultrasonic each 30min, proceed to reactor, then add 2.42mg ferric trichloride.Reactor is placed in to 140 DEG C of baking ovens, and hydro-thermal reaction 8 hours, reacts complete, takes out reactor, naturally cools to room temperature, by sedimentation and filtration, with deionized water, ethanol, acetone washing several, finally product is dried in 60 DEG C of baking ovens respectively.Obtain tin ash and polypyrrole (1%) hybrid material.
2, synthetic method two
Get 50ml distilled water, regulate its H with hydrochloric acid
+concentration be about 1mol ∕ L, add 3mg pyrroles, by ultrasonic solution dispersion 30min.Add again 97mg tin ash.By after potpourri stirring, ultrasonic each 30min, proceed to reactor, then add 7.26mg ferric trichloride.Reactor is placed in to 140 DEG C of baking ovens, and hydro-thermal reaction 8 hours, reacts complete, takes out reactor, naturally cools to room temperature, by sedimentation and filtration, with deionized water, ethanol, acetone washing several, finally product is dried in 60 DEG C of baking ovens respectively.Obtain tin ash and polypyrrole (3%) hybrid material.The infrared spectrogram of tin ash and polypyrrole (3%) hybrid material as shown in Figure 1.
3, synthetic method three
Get 50ml distilled water, regulate its H with hydrochloric acid
+concentration be about 1mol ∕ L, add 20mg pyrroles, by ultrasonic solution dispersion 30min.Add again 80mg tin ash.By after potpourri stirring, ultrasonic each 30min, proceed to reactor, then add 48.4mg ferric trichloride.Reactor is placed in to 140 DEG C of baking ovens, and hydro-thermal reaction 8 hours, reacts complete, takes out reactor, naturally cools to room temperature, by sedimentation and filtration, with deionized water, ethanol, acetone washing several, finally product is dried in 60 DEG C of baking ovens respectively.Obtain tin ash and polypyrrole (20%) hybrid material.The transmission electron microscope picture of tin ash and polypyrrole (20%) hybrid material as shown in Figure 2.
Two, the preparation of acetone gas sensor
1, preparation method one
Preparation method's step is as follows:
(1) take tin ash and polypyrrole (1%) hybrid material that the synthetic method one of about 6mg obtains, grind, add deionized water furnishing pasty state, be evenly coated on above-mentioned alumina ceramic tube, sensitive layer thickness is micron number magnitude.
(2) selecting internal diameter is 1.6mm, and external diameter is 2mm, and the alumina ceramic tube that is about 8mm is carrier, and its top layer is covered with forked gold electrode, and there is platinum filament extraction electrode at two ends.Clean with deionized water, dry for subsequent use.
(3) alumina ceramic tube in (1) being placed in to room temperature dries for subsequent use.
(4) a nickel chromium triangle heater strip is put into above-mentioned tube core, weld according to heater-type device common process, platinum filament lead-in wire and nickel chromium triangle heater strip on electrode are welded in respectively on the relevant position of base, finally explosion-proof net is fixed on to encapsulated moulding on base, packaged sensor is carried out to electricity aging 48 hours.
Performance by the gas sensor made from HW-30A type air-sensitive tester test gas-sensitive sensor device, test atmosphere adopts static distribution method to test.Definition sensitivity is the voltage of gas sensor in certain density detection gas.
In 90 DEG C of operating temperature ranges, acetone gas sensor is exposed in the acetone test gas of variable concentrations, test its response recovery characteristics, as shown in Figure 4, acetone gas sensor is response-recovery curve in variable concentrations acetone, corresponding acetone concentration 50,100,150, when 200,250ppm, the sensitivity of this acetone gas sensor is respectively 0.77,1.08,1.47,1.89,2.17 mV, response time is 20 ~ 25s, release time <10s.
2, preparation method two
(1) take tin ash and polypyrrole (3%) hybrid material that the synthetic method two of about 6mg obtains, grind, add deionized water furnishing pasty state, be evenly coated on above-mentioned alumina ceramic tube, sensitive layer thickness is micron number magnitude.
(2) selecting internal diameter is 1.6mm, and external diameter is 2mm, and the alumina ceramic tube that is about 8mm is carrier, and its top layer is covered with forked gold electrode, and there is platinum filament extraction electrode at two ends.Clean with deionized water, dry for subsequent use.
(3) alumina ceramic tube in (1) being placed in to room temperature dries for subsequent use.
(4) a nickel chromium triangle heater strip is put into above-mentioned tube core, weld according to heater-type device common process, platinum filament lead-in wire and nickel chromium triangle heater strip on electrode are welded in respectively on the relevant position of base, finally explosion-proof net is fixed on to encapsulated moulding on base, packaged sensor is carried out to electricity aging 48 hours.
Performance by the gas sensor made from HW-30A type air-sensitive tester test gas-sensitive sensor device, test atmosphere adopts static distribution method to test.Definition sensitivity is the voltage of gas sensor in certain density detection gas.
In 90 DEG C of operating temperature ranges, acetone gas sensor is exposed in the acetone test gas of variable concentrations, test its response recovery characteristics, as shown in Figure 4, acetone gas sensor is response-recovery curve in variable concentrations acetone, corresponding acetone concentration 50,100,150, when 200,250ppm, the sensitivity of this acetone gas sensor is respectively 0.45,0.57,0.69,0.85,0.96 mV, response time is 20 ~ 25s, release time <10s.
3, preparation method three
(1) take tin ash and polypyrrole (20%) hybrid material that the synthetic method three of about 6mg obtains, grind, add deionized water furnishing pasty state, be evenly coated on above-mentioned alumina ceramic tube, sensitive layer thickness is micron number magnitude.
(2) selecting internal diameter is 1.6mm, and external diameter is 2mm, and the alumina ceramic tube that is about 8mm is carrier, and its top layer is covered with forked gold electrode, and there is platinum filament extraction electrode at two ends.Clean with deionized water, dry for subsequent use.
(3) alumina ceramic tube in (1) being placed in to room temperature dries for subsequent use.
(4) a nickel chromium triangle heater strip is put into above-mentioned tube core, weld according to heater-type device common process, platinum filament lead-in wire and nickel chromium triangle heater strip on electrode are welded in respectively on the relevant position of base, finally explosion-proof net is fixed on to encapsulated moulding on base, packaged sensor is carried out to electricity aging 48 hours.
Test above-mentioned acetone gas sensor at 90 DEG C the change of sensitivity situation in the hydrogen to variable concentrations, carbon monoxide, ammonia.Result shows, this acetone gas sensor is to the equal non-responsiveness of these gases, and the tin ash in this explanation the present invention carries out selective response with polypyrrole hybrid material is capable to the low concentration acetone gas in environment.
As mentioned above, tin ash in the present invention and polypyrrole hybrid material can have higher sensitivity to acetone under lower working temperature, in the situation that other interference gas exist, acetone is carried out to selective response, response recovers rapid and stability is better.Therefore, this material is well suited for, as acetone air-sensitive material, can be applicable to the acetone in environment to monitor.
Claims (1)
1. a preparation method for acetone gas sensor, is characterized in that comprising the following steps:
(1) prepare tin ash and polypyrrole hybrid material
By 1mg pyrrole monomer, 95mg tin ash, 2.42mg anhydrous ferric trichloride, 50ml H
+concentration is 1mol/L water, mixes in proportion, after stirring, ultrasonic 30min, proceed to reactor, reactor is placed in to 140 DEG C of baking ovens, hydro-thermal reaction 8 hours, react complete, take out reactor, naturally cool to room temperature, by sedimentation and filtration, respectively with deionized water, ethanol, acetone washing several, finally product is dried in 60 DEG C of baking ovens, obtain tin ash and polypyrrole hybrid material, for subsequent use;
(2) clean top layer and be covered with gold electrode four jiaos and have the alumina ceramic tube of platinum electrode, dry for subsequent use;
(3) tin ash and polypyrrole hybrid material are ground, with deionized water furnishing pasty state, be coated on alumina ceramic tube, be placed in room temperature and dry for subsequent use;
(4) weld, encapsulate according to heater-type device common process, make acetone gas sensor, concrete operations are as follows:
A nickel chromium triangle heater strip is put into described ceramic pipe tube core, weld according to heater-type device common process, platinum filament lead-in wire and nickel chromium triangle heater strip on electrode are welded in respectively on the relevant position of base, finally explosion-proof net is fixed on to encapsulated moulding on base, packaged sensor is carried out to electricity aging 48 hours, obtain described acetone gas sensor.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310484412.2A CN103675078B (en) | 2013-12-11 | 2013-12-11 | Preparation method for acetone gas sensor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310484412.2A CN103675078B (en) | 2013-12-11 | 2013-12-11 | Preparation method for acetone gas sensor |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103675078A CN103675078A (en) | 2014-03-26 |
| CN103675078B true CN103675078B (en) | 2014-12-10 |
Family
ID=50313275
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310484412.2A Expired - Fee Related CN103675078B (en) | 2013-12-11 | 2013-12-11 | Preparation method for acetone gas sensor |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103675078B (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104502418B (en) * | 2015-01-10 | 2016-11-23 | 吉林大学 | Based on ZnO/ α-Fe2o3acetone gas sensor of composite oxide semiconductor and preparation method thereof |
| CN104965008B (en) * | 2015-06-30 | 2018-12-21 | 江西师范大学 | A kind of acetone gas sensor and preparation method thereof |
| CN108822292B (en) * | 2018-07-03 | 2020-09-08 | 山东交通学院 | Preparation method and application of PbS point reinforced polypyrrole-based composite material |
| CN109133176B (en) * | 2018-07-31 | 2020-07-31 | 漯河医学高等专科学校 | ZnO-CeO2-WO3-Al2O3Preparation method of sensor material and acetone cyanohydrin gas sensor |
| CN109459469A (en) * | 2018-11-07 | 2019-03-12 | 西安交通大学 | A kind of virtual sensors array and preparation method thereof |
| CN112326741A (en) * | 2020-09-17 | 2021-02-05 | 上海大学 | MEMS (micro-electromechanical system) diabetes exhaled breath detection sensor and preparation method and application thereof |
| CN112798661B (en) * | 2020-12-31 | 2023-03-14 | 广东电网有限责任公司电力科学研究院 | SO (SO) 2 F 2 Detection method of (2) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102818880A (en) * | 2012-07-30 | 2012-12-12 | 中国科学院微电子研究所 | Method of preparation of sensitive materials for sensor |
| CN103115946A (en) * | 2013-03-05 | 2013-05-22 | 济南大学 | Preparation method and application of n-p junction type ferrum-copper based oxide gas sensitive element |
-
2013
- 2013-12-11 CN CN201310484412.2A patent/CN103675078B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102818880A (en) * | 2012-07-30 | 2012-12-12 | 中国科学院微电子研究所 | Method of preparation of sensitive materials for sensor |
| CN103115946A (en) * | 2013-03-05 | 2013-05-22 | 济南大学 | Preparation method and application of n-p junction type ferrum-copper based oxide gas sensitive element |
Non-Patent Citations (2)
| Title |
|---|
| 徐红燕，李梅等.水热处理对SnO2厚膜气敏传感器性能的影响.《功能材料》.2005,第36卷(第9期),1415-1417. * |
| 范红青，周建萍，刘志雷.聚吡咯/SnO2复合材料气敏性能研究.《化工新型材料》.2012,第40卷(第5期),139-141. * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103675078A (en) | 2014-03-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103675078B (en) | Preparation method for acetone gas sensor | |
| Song et al. | Fabrication of highly sensitive and selective room-temperature nitrogen dioxide sensors based on the ZnO nanoflowers | |
| Pang et al. | A room temperature ammonia gas sensor based on cellulose/TiO2/PANI composite nanofibers | |
| Jang et al. | Selectivity enhancement of SnO2 nanofiber gas sensors by functionalization with Pt nanocatalysts and manipulation of the operation temperature | |
| Rout et al. | Hydrogen sensors based on ZnO nanoparticles | |
| Chen et al. | CO2 sensing properties and mechanism of PrFeO3 and NdFeO3 thick film sensor | |
| Wang et al. | One-dimensional porous Co3O4 rectangular rods for enhanced acetone gas sensing properties | |
| Cheng et al. | Porous ZnAl2O4 spinel nanorods: High sensitivity humidity sensors | |
| Grigorieva et al. | Synthesis, structure, and sensor properties of vanadium pentoxide nanorods | |
| CN105092658B (en) | Nano combined resistor-type material sensors of polyaniline/zinc oxide and preparation method thereof | |
| CN101581687B (en) | Cadmium sulfide coating carbon nano tube gas-sensitive material and manufacture method of gas-sensitive element | |
| CN104569080A (en) | Acetone gas sensor based on hollow spherical ZnFe2O4 nano material and preparation method thereof | |
| CN103713019A (en) | Zinc oxide/polypyrrole nano composite resistance-type film gas sensor and production method thereof | |
| Wang et al. | Construction of hierarchical α‐Fe2O3/SnO2 nanoball arrays with superior acetone sensing performance | |
| CN107164839B (en) | Formaldehyde sensitive material CdGa2O4 and preparation method thereof with hypersensitivity and selectivity | |
| Cheng et al. | Boosting TEA sensing performance of ZnO porous hollow spheres via in situ construction of ZnS-ZnO heterojunction | |
| Sun et al. | Highly sensitive and lower detection-limit NO2 gas sensor based on Rh-doped ZnO nanofibers prepared by electrospinning | |
| Chen et al. | Coaxial electrospinning Fe2O3@ Co3O4 double-shelled nanotubes for enhanced ethanol sensing performance in a wide humidity range | |
| CN103293197B (en) | The preparation method of the titania-doped base film acetone gas sensor of tin ash | |
| Luo et al. | Effect of calcination temperature on the humidity sensitivity of TiO2/graphene oxide nanocomposites | |
| CN108007978A (en) | One kind is based on rGO-Co3O4The room temperature NO of compound2Sensor and preparation method thereof | |
| Zhang et al. | Ionic liquid-assisted synthesis of tungsten oxide nanoparticles with enhanced NO2 sensing properties at near room temperature | |
| CN114839231B (en) | Anti-interference gas-sensitive coating for semiconductor combustible gas sensor and preparation method and application thereof | |
| CN108844999A (en) | For detecting the utilization g-C of VOCs3N4The synthetic method of the porous zinc bloom nanometer sheet composite air-sensitive material of modification | |
| Cheng et al. | Modification of Bi2O3 on ZnO porous nanosheets-assembled architecture for ultrafast detection of TEA with high sensitivity |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C53 | Correction of patent for invention or patent application | ||
| CB03 | Change of inventor or designer information |
Inventor after: Xu Guangjun Inventor after: Wang Xijun Inventor after: Geng Lina Inventor after: Xu Zhonghua Inventor after: Rong Wenhui Inventor after: Wang Zhiling Inventor before: Xu Guangjun Inventor before: Wang Zhiling Inventor before: Geng Lina Inventor before: Xu Zhonghua Inventor before: Rong Wenhui |
|
| COR | Change of bibliographic data |
Free format text: CORRECT: INVENTOR; FROM: XU GUANGJUN WANG ZHILING GENG LINA XU ZHONGHUA RONG WENHUI TO: XU GUANGJUN WANG XIJUN GENG LINA XU ZHONGHUA RONG WENHUI WANG ZHILING |
|
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20141210 Termination date: 20171211 |