CN101979458A - Method for preparing CaS:Ce and Sm luminescent material - Google Patents
Method for preparing CaS:Ce and Sm luminescent material Download PDFInfo
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- CN101979458A CN101979458A CN2010105096801A CN201010509680A CN101979458A CN 101979458 A CN101979458 A CN 101979458A CN 2010105096801 A CN2010105096801 A CN 2010105096801A CN 201010509680 A CN201010509680 A CN 201010509680A CN 101979458 A CN101979458 A CN 101979458A
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- 239000000463 material Substances 0.000 title claims abstract description 24
- 238000000034 method Methods 0.000 title claims abstract description 17
- 229910052684 Cerium Inorganic materials 0.000 title claims abstract description 11
- 229910052772 Samarium Inorganic materials 0.000 title claims abstract description 11
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims abstract description 34
- 238000002360 preparation method Methods 0.000 claims abstract description 21
- FKTOIHSPIPYAPE-UHFFFAOYSA-N samarium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[Sm+3].[Sm+3] FKTOIHSPIPYAPE-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000002904 solvent Substances 0.000 claims abstract description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 42
- -1 silicon ion Chemical class 0.000 claims description 27
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 claims description 22
- 229910001424 calcium ion Inorganic materials 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 16
- 150000001875 compounds Chemical class 0.000 claims description 15
- 239000011521 glass Substances 0.000 claims description 14
- 238000005245 sintering Methods 0.000 claims description 14
- 239000000758 substrate Substances 0.000 claims description 14
- 239000011575 calcium Substances 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 11
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 10
- 229910052791 calcium Inorganic materials 0.000 claims description 10
- 238000010792 warming Methods 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- 229910052710 silicon Inorganic materials 0.000 claims description 8
- 239000010703 silicon Substances 0.000 claims description 8
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 238000003618 dip coating Methods 0.000 claims description 6
- 239000012153 distilled water Substances 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 6
- 239000000654 additive Substances 0.000 claims description 4
- 230000000996 additive effect Effects 0.000 claims description 4
- 230000032683 aging Effects 0.000 claims description 4
- 239000012467 final product Substances 0.000 claims description 4
- 150000002500 ions Chemical class 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 230000001105 regulatory effect Effects 0.000 claims description 4
- 239000011248 coating agent Substances 0.000 claims description 3
- 238000000576 coating method Methods 0.000 claims description 3
- 238000007598 dipping method Methods 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 238000004140 cleaning Methods 0.000 claims description 2
- 230000007935 neutral effect Effects 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 6
- VSGNNIFQASZAOI-UHFFFAOYSA-L calcium acetate Chemical compound [Ca+2].CC([O-])=O.CC([O-])=O VSGNNIFQASZAOI-UHFFFAOYSA-L 0.000 abstract description 3
- 235000011092 calcium acetate Nutrition 0.000 abstract description 3
- 229960005147 calcium acetate Drugs 0.000 abstract description 3
- 239000001639 calcium acetate Substances 0.000 abstract description 3
- 239000000835 fiber Substances 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 2
- 229910000420 cerium oxide Inorganic materials 0.000 abstract 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 abstract 1
- 239000002243 precursor Substances 0.000 abstract 1
- 229910001954 samarium oxide Inorganic materials 0.000 abstract 1
- 229940075630 samarium oxide Drugs 0.000 abstract 1
- 239000000047 product Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000005090 crystal field Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000005669 field effect Effects 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 238000003836 solid-state method Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
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Abstract
The invention provides a method for preparing a CaS:Ce and Sm luminescent material. The CaS:Ce and Sm luminescent material is prepared by dissolving raw materials, namely calcium acetate, thiocarbamide, cerium oxide and samarium oxide, in a solvent to generate a precursor and is prepared through sol-gel. In the preparation method, equipment and operation are simple; the reaction temperature of the material is obviously reduced; the granularity of a product is extremely low and even can reach nanoscale; at the same time, the method lays a foundation for the preparation of luminescent films, fibers and blocks in different links.
Description
Technical field
The present invention relates to a kind of preparation method of luminescent material, particularly a kind of CaS:Ce, the preparation method of Sm luminescent material.
Background technology
Alkaline-earth metal class sulfide CaS makes that with its comparatively simple cubic structure and tangible crystal field effects it shows at luminous host fluorescence, film, research field of long-afterglow material is subjected to very big attention.Rare earth ion Ce, Sm activated CaS fluorescent material by irradiation such as X ray, gamma-rays, high-energy electrons after, electronics on the valence band is excited to conduction band, captured by trap level in the forbidden band, after infrared light irradiation that material is subjected to certain wavelength excites, transition of electron is to conduction band in the trap, luminescence center in the last and forbidden band is compound, sends the fluorescent photon of certain wavelength region.
The method of traditional such luminescent material of preparation is a high temperature solid-state method, promptly at high temperature adopt carbon reduction or sulphur method of reducing, the temperature of reaction height of solid phase method, long reaction time at the bottom of the big and productive rate of product granularity, have limited such Development of Materials to a certain extent.
Summary of the invention
Technical problem to be solved by this invention provides a kind of CaS:Ce, the preparation method of Sm luminescent material, preparation method and operating equipment are simple, obviously reduced the temperature of reaction of material, the granularity of product is very little, even reach nano level, simultaneously, be that the preparation of light-emitting film, fiber and block provides the foundation in different links.
For achieving the above object, the invention provides a kind of CaS:Ce, the preparation method of Sm luminescent material is an object ion with calcium containing compound and thiocarbamide, and ethylene glycol is solvent, tetraethoxy is an additive, after mixing, leave standstill, remove upper strata organic solution, mix six water cerous nitrate and Samarium trioxides again, make even colloidal sol; Get glass substrate, after cleaning up, adopt dip-coating method, above-mentioned even colloidal sol is coated on the glass substrate, sintering gets final product under nitrogen atmosphere at last, and wherein, the mol ratio of calcareous compound and thiocarbamide and ethylene glycol is 1: 2: 2, the mol ratio of calcium ion and silicon ion is 7: 3, and the mol ratio of the mol ratio of calcium ion and cerium ion and calcium ion and samarium ion is 1: 0.1.
The present invention provides a kind of CaS:Ce again, and the preparation method of Sm luminescent material is an object ion with calcium containing compound and thiocarbamide, and ethylene glycol is solvent, tetraethoxy is an additive, after mixing, leaves standstill, remove upper strata organic solution, mix six water cerous nitrate and Samarium trioxides again, make even colloidal sol; At last, with even colloidal sol oven dry, after making xerogel, sintering gets final product under nitrogen atmosphere, wherein, the mol ratio of calcareous compound and thiocarbamide and ethylene glycol is 1: 2: 2, and the mol ratio of calcium ion and silicon ion is 7: 3, and the mol ratio of the mol ratio of calcium ion and cerium ion and calcium ion and samarium ion is 1: 0.1.
The present invention provides a kind of CaS:Ce again, and the preparation method of Sm luminescent material gets calcium containing compound and thiocarbamide and is dissolved in the distilled water, described distilled water is advisable with dissolving calcium containing compound and thiocarbamide, fully after the dissolving, to wherein adding ethylene glycol, after stirring, to wherein adding tetraethoxy, after fully stirring, leave standstill, centrifugal, remove upper strata organic solution, wherein, the mol ratio of calcium containing compound and thiocarbamide and ethylene glycol is 1: 2: 2, and the mol ratio of calcium ion and silicon ion is 7: 3; Then, mix six water cerous nitrate and Samarium trioxides in the mixture of getting rid of upper strata organic solution, wherein, the mol ratio of the mol ratio of calcium ion and cerium ion and calcium ion and samarium ion is 1: 0.1, and after stirring, it is neutral regulating pH; Then, after 2 hours, ageing 24 hours makes even colloidal sol 40 ℃ of stirred in water bath; At last, adopt dip-coating method to be coated on the glass substrate even colloidal sol, after sintering light-emitting film again into or even colloidal sol made xerogel under nitrogen atmosphere, sintering under nitrogen atmosphere grinds to form luminescent powder at last.
As the preferred embodiments of the present invention, when adopting dip-coating method to be coated in even colloidal sol on the glass substrate, pull rate is 2cm/min, and coating times is 2～3 times, and dipping time is 10 seconds.
As the preferred embodiments of the present invention, after each plated film is finished, after in air, drying naturally, carry out plated film next time again.
As the preferred embodiments of the present invention, described even colloidal sol is coated in before the glass substrate, at first with glass substrate successively with the ultrasonic washing of washing composition, ultrasonic washing, ethanol is ultrasonic washed each 15 minutes.
As the preferred embodiments of the present invention, the sintering method of described light-emitting film is: at first be warming up to 300 ℃ in the speed with 2 ℃/min from 25 ℃, then, be incubated 60 minutes, then, be warming up to 500 ℃ with the speed of 5 ℃/min, then, be incubated 120 minutes, last, under nitrogen atmosphere, cool to room temperature with the furnace.
As the preferred embodiments of the present invention, the sintering method of described luminescent powder is: at first being warming up to 500 ℃ with the speed of 2 ℃/min from 25 ℃, then, be incubated 120 minutes, at last, cool to room temperature with the furnace under nitrogen atmosphere.
Compared with prior art, the present invention has the following advantages at least: 1. in the beginning of reaction, each raw material is to introduce system with the form of molecule, therefore, still keep its physical properties and chemical property, so the ratio reciprocal of each component is controlled, can reach on the molecular level evenly; 2. need equipment fairly simple; Temperature of reaction is lower, is generally room temperature or high-temperature slightly, can reach energy-saving effect, and owing to do not relate to pyroreaction, therefore can avoid inducing one of impurity, can guarantee the purity of the finished product; 3. the reaction times is lacked only 1 hour; 4. the particle diameter of the product that makes can reach nano level; 5. can prepare some with this method even adopt the firing process of complexity and the material that smelting process also can't prepare, such as fiber or film.
Description of drawings
Fig. 1 is CaS:Ce of the present invention, the XRD figure of Sm luminescent powder;
Fig. 2 is CaS:Ce of the present invention, the surface topography map of Sm light-emitting film;
Fig. 3 is CaS:Ce of the present invention, the emmission spectrum figure of Sm luminescent material;
Fig. 4 is CaS:Ce of the present invention, the exciting light spectrogram of Sm luminescent material.
Embodiment
CaS:Ce of the present invention, the preparation method of Sm luminescent material may further comprise the steps:
Embodiment 1:
(1) the evenly preparation of colloidal sol
A: get the calcium acetate of 1mol and the thiocarbamide of 2mol and be dissolved in the distilled water of 50ml, after the dissolving, add the ethylene glycol of 2mol fully, after stirring, add tetraethoxy, the mol ratio of described calcium ion and silicon ion is 7: 3, after fully stirring, leaves standstill;
B: centrifugation, to remove the unnecessary organic solution in upper strata;
C: in above-mentioned solution after centrifugal, add six water cerous nitrate and Samarium trioxides, the mol ratio of the mol ratio of described calcium ion and cerium ion and calcium ion and samarium ion is 1: 0.1, after stirring, adds ammoniacal liquor or nitric acid, and regulating pH is 9;
D: then, after 2 hours, ageing 24 hours promptly gets even colloidal sol, and is standby 40 ℃ stirred in water bath.
(2) CaS:Ce, the preparation of Sm light-emitting film
A: get glass substrate, successively with the ultrasonic washing of washing composition 15 minutes, ultrasonic washing 15 minutes, ethanol is ultrasonic washed 15 minutes, clean finish after, dry up with nitrogen;
B: employing lifts the plated film instrument and apply even colloidal sol on glass substrate, and with plated film, wherein, pull rate is 2cm/min, and coating times is 2～3 times, and dipping time is 10 seconds, after each plated film is finished, after drying naturally, carries out plated film next time again in air;
C: after plated film was finished, sintering under nitrogen atmosphere at first, under 25 ℃ temperature, was warming up to 300 ℃ with the speed of 2 ℃/min, then, be incubated 60 minutes, then, be warming up to 500 ℃ with the speed of 5 ℃/min, be incubated 120 minutes again, last, continue under nitrogen atmosphere, to cool to 25 ℃ with the furnace.
In the preparation process of the light-emitting film of present embodiment, natural flash-off time that can be by changing each plated film and when changing each plated film the add-on of even colloidal sol control the viscosity of colloidal sol, thereby, the thickness of control film.
Embodiment 2:
(1) the evenly preparation of colloidal sol
A: get the calcium acetate of 1mol and the thiocarbamide of 2mol and be dissolved in the distilled water of 50ml, after the dissolving, add the ethylene glycol of 2mol fully, after stirring, add tetraethoxy, the mol ratio of described calcium ion and silicon ion is 7: 3, after fully stirring, leaves standstill;
B: centrifugation, to remove the unnecessary organic solution in upper strata;
C: in above-mentioned solution after centrifugal, add six water cerous nitrates and Samarium trioxide (n (Ca
2+): n (Ce
3+)=1: 0.1; N (Ca
2+): n (Sm
3+)=1: 0.1), after stirring, add ammoniacal liquor or nitric acid, regulating pH is 9;
D: then, after 2 hours, ageing 24 hours promptly gets even colloidal sol, and is standby 40 ℃ stirred in water bath.
(2) CaS:Ce, the preparation of Sm luminescent powder
The even colloidal sol that obtains in step (1) is passed in the baking oven, under 75 ℃ temperature, dry, thereby, xerogel made, then, xerogel is carried out sintering under nitrogen atmosphere, at first with xerogel under 25 ℃ temperature, be warming up to 500 ℃ with the speed of 2 ℃/min, then, be incubated 120 minutes, last, continue under nitrogen atmosphere, to cool to 25 ℃ with the furnace.
Also can learn that from Fig. 1 and Fig. 2 the granularity of product is a nano level, less than 100nm.
The above only is one embodiment of the present invention, it or not whole or unique embodiment, the conversion of any equivalence that those of ordinary skills take technical solution of the present invention by reading specification sheets of the present invention is claim of the present invention and contains.
Claims (8)
1. CaS:Ce, the preparation method of Sm luminescent material is characterized in that: with calcium containing compound and thiocarbamide is object ion, ethylene glycol is solvent, tetraethoxy is an additive, after mixing, leaves standstill, remove upper strata organic solution, mix six water cerous nitrate and Samarium trioxides again, make even colloidal sol; Get glass substrate, after cleaning up, adopt dip-coating method, above-mentioned even colloidal sol is coated on the glass substrate, sintering gets final product under nitrogen atmosphere at last, and wherein, the mol ratio of calcareous compound and thiocarbamide and ethylene glycol is 1: 2: 2, the mol ratio of calcium ion and silicon ion is 7: 3, and the mol ratio of the mol ratio of calcium ion and cerium ion and calcium ion and samarium ion is 1: 0.1.
2. CaS:Ce, the preparation method of Sm luminescent material is characterized in that: with calcium containing compound and thiocarbamide is object ion, ethylene glycol is solvent, tetraethoxy is an additive, after mixing, leaves standstill, remove upper strata organic solution, mix six water cerous nitrate and Samarium trioxides again, make even colloidal sol; At last, with even colloidal sol oven dry, after making xerogel, sintering gets final product under nitrogen atmosphere, wherein, the mol ratio of calcareous compound and thiocarbamide and ethylene glycol is 1: 2: 2, and the mol ratio of calcium ion and silicon ion is 7: 3, and the mol ratio of the mol ratio of calcium ion and cerium ion and calcium ion and samarium ion is 1: 0.1.
3. CaS:Ce, the preparation method of Sm luminescent material is characterized in that: get calcium containing compound and thiocarbamide and be dissolved in the distilled water, described distilled water is advisable with dissolving calcium containing compound and thiocarbamide, fully after the dissolving, to wherein adding ethylene glycol, after stirring, to wherein adding tetraethoxy, after fully stirring, leave standstill, centrifugal, remove upper strata organic solution, wherein, the mol ratio of calcium containing compound and thiocarbamide and ethylene glycol is 1: 2: 2, and the mol ratio of calcium ion and silicon ion is 7: 3; Then, mix six water cerous nitrate and Samarium trioxides in the mixture of getting rid of upper strata organic solution, wherein, the mol ratio of the mol ratio of calcium ion and cerium ion and calcium ion and samarium ion is 1: 0.1, and after stirring, it is neutral regulating pH; Then, after 2 hours, ageing 24 hours makes even colloidal sol 40 ℃ of stirred in water bath; At last, adopt dip-coating method to be coated on the glass substrate even colloidal sol, after sintering light-emitting film again into or even colloidal sol made xerogel under nitrogen atmosphere, sintering under nitrogen atmosphere grinds to form luminescent powder at last.
4. method as claimed in claim 3 is characterized in that: when adopting dip-coating method to be coated in even colloidal sol on the glass substrate, pull rate is 2cm/min, and coating times is 2～3 times, and dipping time is 10 seconds.
5. method as claimed in claim 4 is characterized in that: after each plated film is finished, after drying naturally, carry out plated film next time again in air.
6. method as claimed in claim 5 is characterized in that: even colloidal sol is coated in before the glass substrate, at first with glass substrate successively with the ultrasonic washing of washing composition, ultrasonic washing, ethanol is ultrasonic washed each 15 minutes.
7. method as claimed in claim 3, it is characterized in that: the sintering method of described light-emitting film is: at first be warming up to 300 ℃ in the speed with 2 ℃/min from 25 ℃, then, be incubated 60 minutes, then, be warming up to 500 ℃ with the speed of 5 ℃/min, then, be incubated 120 minutes, last, under nitrogen atmosphere, cool to room temperature with the furnace.
8. method as claimed in claim 3 is characterized in that: the sintering method of described luminescent powder is: at first being warming up to 500 ℃ with the speed of 2 ℃/min from 25 ℃, then, be incubated 120 minutes, at last, cool to room temperature with the furnace under nitrogen atmosphere.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114195103A (en) * | 2021-12-30 | 2022-03-18 | 北京科技大学 | Preparation method of alkali metal and alkaline earth metal sulfide |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101101930A (en) * | 2007-08-01 | 2008-01-09 | 上海芯光科技有限公司 | An efficient solar battery light wave conversion nano compound material |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101101930A (en) * | 2007-08-01 | 2008-01-09 | 上海芯光科技有限公司 | An efficient solar battery light wave conversion nano compound material |
Non-Patent Citations (2)
| Title |
|---|
| K. CHAKRABARTI ET. AL.: "Charge trapping and mechanism of stimulated luminescence in CaS:Ce, Sm", 《JOURNAL OF APPLIED PHYSICS》, vol. 65, no. 5, 1 March 1989 (1989-03-01), pages 2021 - 2023 * |
| MOHAMMAD SYUHAIMI AB-RAHMAN ET. AL.: "Fabrication of ZnS:Mn Nanocrystals by Sol Gel-Self Assembly technique", 《PROCEEDINGS OF 2009 IEEEE STUDENT CONFERENCE ON RESEARCH AND DEVELOPMENT(SCORED 2009)》, 5 April 2010 (2010-04-05), pages 537 - 539 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114195103A (en) * | 2021-12-30 | 2022-03-18 | 北京科技大学 | Preparation method of alkali metal and alkaline earth metal sulfide |
| CN114195103B (en) * | 2021-12-30 | 2022-08-30 | 北京科技大学 | Preparation method of alkali metal and alkaline earth metal sulfide |
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Effective date of registration: 20201217 Address after: 224000 southeast Industrial Park, Yandong Town, Tinghu District, Yancheng City, Jiangsu Province (19) Patentee after: YANCHENG CITY RONGYILAI TEXTILE MACHINERY Co.,Ltd. Address before: 518000 No.6 Qinglong Road, Qinglong Road, Qinghua community, Longhua street, Longhua District, Shenzhen City, Guangdong Province Patentee before: Shenzhen Pengbo Information Technology Co.,Ltd. Effective date of registration: 20201217 Address after: 518000 No.6 Qinglong Road, Qinglong Road, Qinghua community, Longhua street, Longhua District, Shenzhen City, Guangdong Province Patentee after: Shenzhen Pengbo Information Technology Co.,Ltd. Address before: No. 1, Weiyang District university garden, Xi'an, Shaanxi Province, Shaanxi Patentee before: SHAANXI University OF SCIENCE & TECHNOLOGY |
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| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20130724 |