CN103241946B - Lead-free crystal glass and preparation method thereof - Google Patents
Lead-free crystal glass and preparation method thereof Download PDFInfo
- Publication number
- CN103241946B CN103241946B CN201310188948.XA CN201310188948A CN103241946B CN 103241946 B CN103241946 B CN 103241946B CN 201310188948 A CN201310188948 A CN 201310188948A CN 103241946 B CN103241946 B CN 103241946B
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- CN
- China
- Prior art keywords
- lead
- glass
- crystal glass
- zno
- oxide
- 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
- 239000005355 lead glass Substances 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 239000000463 material Substances 0.000 claims abstract description 19
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 14
- 239000002994 raw material Substances 0.000 claims description 14
- 239000000843 powder Substances 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 22
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 abstract description 20
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 abstract description 16
- 239000011521 glass Substances 0.000 abstract description 13
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 abstract description 10
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 abstract description 10
- 239000000377 silicon dioxide Substances 0.000 abstract description 9
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 abstract description 6
- 239000006185 dispersion Substances 0.000 abstract description 5
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 abstract description 5
- 229910000029 sodium carbonate Inorganic materials 0.000 abstract description 5
- 235000017550 sodium carbonate Nutrition 0.000 abstract description 5
- 235000010344 sodium nitrate Nutrition 0.000 abstract description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 abstract description 3
- 230000004075 alteration Effects 0.000 abstract description 3
- 231100000419 toxicity Toxicity 0.000 abstract description 3
- 230000001988 toxicity Effects 0.000 abstract description 3
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 229910004844 Na2B4O7.10H2O Inorganic materials 0.000 abstract 1
- 239000001569 carbon dioxide Substances 0.000 abstract 1
- 229910002092 carbon dioxide Inorganic materials 0.000 abstract 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 abstract 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 abstract 1
- 229910052681 coesite Inorganic materials 0.000 abstract 1
- 239000003086 colorant Substances 0.000 abstract 1
- 229910052906 cristobalite Inorganic materials 0.000 abstract 1
- 229910000464 lead oxide Inorganic materials 0.000 abstract 1
- 229910052808 lithium carbonate Inorganic materials 0.000 abstract 1
- 235000012239 silicon dioxide Nutrition 0.000 abstract 1
- 229910052682 stishovite Inorganic materials 0.000 abstract 1
- 229910052905 tridymite Inorganic materials 0.000 abstract 1
- 239000008187 granular material Substances 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000006004 Quartz sand Substances 0.000 description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 4
- 229910021538 borax Inorganic materials 0.000 description 4
- 229910000420 cerium oxide Inorganic materials 0.000 description 4
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000004317 sodium nitrate Substances 0.000 description 4
- 229940001516 sodium nitrate Drugs 0.000 description 4
- 239000004328 sodium tetraborate Substances 0.000 description 4
- 235000010339 sodium tetraborate Nutrition 0.000 description 4
- 229910052725 zinc Inorganic materials 0.000 description 4
- 239000011701 zinc Substances 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- 239000005308 flint glass Substances 0.000 description 1
- 239000003500 flue dust Substances 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Glass Compositions (AREA)
Abstract
The invention discloses lead-free crystal glass and a preparation method thereof. The lead-free crystal glass comprises the following components in percentage by weight: 57-61% of SiO2, 23-25% of Na2CO3, 5-6% of NaNO3, 2-3.5% of Na2B4O7.10H2O, 1.4-1.5% of ZnO, 4.3-5% of BaCO3, 0.7-1.5% of Li2CO3 and 0.5-1% of CeO2. According to the lead-free crystal glass, barium carbonate (BaCO3) takes the place of lead oxide, and as barium carbonate is discomposed into barium oxide (BaO) and carbon dioxide under high temperature condition of 1000 DEG C to 1500 DEG C, however, only the refractive index is improved when barium oxide (BaO) is added into glass, the dispersion coefficient is not affected. Therefore, the glass with barium oxide is low in possibility that dispersion and chromatic aberration occur. The lead-free crystal glass has the characteristics of high refraction index (n is greater than or equal to 1.54), high dispersion coefficient (vd is greater than 60) and high transparency degree, and is beneficial for reducing the pattern colors on the back side of the glass more really; a product which is produced by using the glass disclosed by the invention is high in density and has the heavy texture like lead crystal; and in addition, compared with a glass material with lead oxide (PbO), barium carbonate is low in cost and low in toxicity.
Description
Technical field
The present invention relates to a kind of frit and production technique thereof, especially a kind of unleaded crystal glass material and preparation method thereof.
Background technology
Existing glass production technology uses traditional flint glass material mostly, and through production practice long-term both at home and abroad, prove the crystal glass transparency of lead tolerance 24% and specific refractory power higher.
Plumbous oxide (PbO), as the important component of traditional crystal glass, not only can improve the specific refractory power of glass, also improve dispersive power.The dispersive power of glass is higher, and abbe number (Abbe number) is lower, and dispersion and the aberration degree of light are larger, and purple boundary, green limit more easily appear in the band color pattern seen through glass, cause color distortion.
Meanwhile, plumbous oxide (PbO) toxicity is very large, has carcinogenic effect.In process of production, it relies on high-temperature flue gas and dust can be distributed in air, causes detrimentally affect to the healthy of workman; In use, it can precipitate in food and drink as time goes by, causes secondary pollution.European Union and the content of the many clients of America and Europe to plumbous and plumbous compound explicitly call for, the lead content in US-legislation restriction family product, and portions of client is expressly provided and do not allowed in the product to use plumbous and plumbous compound.
Summary of the invention
The object of this invention is to provide and a kind of there is the high and unleaded crystal glass material of safety non-pollution and preparation method thereof of high refractive index, high abbe number, transparency.
The present invention solves the technical scheme that prior art problem adopts: a kind of unleaded crystal glass material, comprises each component of following weight percentage: SiO
2: 57%-61%, Na
2cO
3: 23%-25%, NaNO
3: 5%-6%, Na
2b
4o
710H
2o:2%-3.5%, ZnO:1.4%-1.5%, BaCO
3: 4.3%-5%, Li
2cO
3: 0.7%-1.5%, CeO
2: 0.5%-1%.
The weight percentage of described each component is: SiO
2: 57.000%, Na
2cO
3: 24.981%, NaNO
3: 5.831%, Na
2b
4o
710H
2o:3.347%, ZnO:1.482%, BaCO
3: 4.941%, Li
2cO
3: 1.433%, CeO
2: 0.985%.
The weight percentage of described each component is: SiO
2: 59.000%, Na
2cO
3: 24.123%, NaNO
3: 5.482%, Na
2b
4o
710H
2o:3.147%, ZnO:1.450%, BaCO
3: 4.517%, Li
2cO
3: 1.397%, CeO
2: 0.884%.
The weight percentage of described each component is: SiO
2: 61.000%, Na
2cO
3: 23.225%, NaNO
3: 5.102%, Na
2b
4o
710H
2o:2.918%, ZnO:1.412%, BaCO
3: 4.837%, Li
2cO
3: 0.981%, CeO
2: 0.525%.
A preparation method for unleaded crystal glass material, is characterized in that, comprise the steps:
A, batching:
According to the mass percent of each component, calculate the quality of corresponding raw material and take each raw material;
B, raw material stoving:
The moisture in nature oven dry and each raw material of electric oven capable person is utilized to be reduced to less than 8%;
C, mix and blend:
By dry after prepared using supper micron mill and mixer mix and blend be powder shape.
Beneficial effect of the present invention is: unleaded crystal glass material of the present invention is with SiO
2, Na
2cO
3, NaNO
3, Na
2b
4o
710H
2o, ZnO, BaCO
3, Li
2cO
3, CeO
2for raw material, above-mentioned raw materials obtains through oven dry and mix and blend granulation.The present invention uses barium carbonate (BaCO
3) substitute plumbous oxide, because barium carbonate can be decomposed into barium oxide (BaO) and carbonic acid gas under the hot conditions of 1000 DEG C-1500 DEG C.And barium oxide (BaO) adds in glass and only improves specific refractory power, abbe number is not affected.Therefore add barytic glass and occur that the degree of dispersion and aberration can be lower.The glasswork utilizing frit of the present invention to obtain has high refractive index, high abbe number, feature that transparency is higher, contributes to the pattern color reduced more really in glass back; The product density utilizing frit of the present invention to produce is higher, has the heavy texture of similar lead water crystalline substance.In addition, relatively add the frit matter of plumbous oxide (PbO), barium carbonate cost is lower and toxicity is less.
Embodiment
Below in conjunction with specific embodiment, the present invention will be described:
A kind of unleaded crystal glass material, comprises each component of following weight percentage: SiO
2(ground silica, quartz sand): 57%-61%, Na
2cO
3(soda ash): 23%-25%, NaNO
3(SODIUMNITRATE): 5%-6%, Na
2b
4o
710H
2o(borax): 2%-3.5%, ZnO(one-level zinc): 1.4%-1.5%, BaCO
3(barium carbonate): 4.3%-5%, Li
2cO
3(Quilonum Retard): 0.7%-1.5%, CeO
2(cerium oxide): 0.5%-1%.
Wherein SiO
2main source from ground silica, owing to having impurity in the ground silica under state of nature, the therefore preferred acid washed silica powder that granule content is following after pickling:
More than 20 orders: granule content is 0.03%; 20 order-40 orders: granule content is 12%; 40 order-80 orders: granule content is 65.17%; 80 order-120 orders: granule content is 16.07%; 120 order-200 orders: granule content is 5.5%; Below 200 orders: granule content is 1.23%.Iron level 0.0049%-0.0095%.Wherein granule content is the result of the weighted average sample calculation to acid washed silica powder.
Below provide several preferred implementation of the present invention:
Embodiment 1:
A kind of unleaded crystal glass material, preferably includes each component of following weight percentage: SiO
2(ground silica, quartz sand): 57.000%, Na
2cO
3(soda ash): 24.981%, NaNO
3(SODIUMNITRATE): 5.831%, Na
2b
4o
710H
2o(borax): 3.347%, ZnO(one-level zinc): 1.482%, BaCO
3(barium carbonate): 4.941%, Li
2cO
3(Quilonum Retard): 1.433%, CeO
2(cerium oxide): 0.985%.
Embodiment 2:
A kind of unleaded crystal glass material, preferably includes each component of following weight percentage: SiO
2(ground silica, quartz sand): 59.000%, Na
2cO
3(soda ash): 24.123%, NaNO
3(SODIUMNITRATE): 5.482%, Na
2b
4o
710H
2o(borax): 3.147%, ZnO(one-level zinc): 1.450%, BaCO
3(barium carbonate): 4.517%, Li
2cO
3(Quilonum Retard): 1.397%, CeO
2(cerium oxide): 0.884%.
Embodiment 3:
A kind of unleaded crystal glass material, preferably includes each component of following weight percentage: SiO
2(ground silica, quartz sand): 61.000%, Na
2cO
3(soda ash): 23.225%, NaNO
3(SODIUMNITRATE): 5.102%, Na
2b
4o
710H
2o(borax): 2.918%, ZnO(one-level zinc): 1.412%, BaCO
3(barium carbonate): 4.837%, Li
2cO
3(Quilonum Retard): 0.981%, CeO
2(cerium oxide): 0.525%.
A preparation method for unleaded crystal glass material, comprises the steps:
The first step, batching:
According to the weight percentage of each component of embodiment 1-3, calculate the quality of corresponding raw material and take each raw material.
Second step, raw material stoving:
The moisture in nature oven dry and each raw material of electric oven capable person is utilized to be reduced to less than 8%.
3rd step, mix and blend:
By dry after prepared using supper micron mill and mixer mix and blend be powder shape.
Obtain the unleaded crystal glass material of powder shape through above-mentioned steps, this frit is conventionally melted making and production for can carry out further glassy product after glass metal through steps such as feeding, mould molding, annealing.
The refractive index n of the glasswork that the frit obtained with the proportioning of embodiment 1 obtains is 1.55, vd is 60.6
The refractive index n of the glasswork that the frit obtained with the proportioning of embodiment 2 obtains is 1.56, and abbe number vd is 60.5
The refractive index n of the glasswork that the frit obtained with the proportioning of embodiment 3 obtains is 1.545, and abbe number vd is 60.4
Generally speaking, refractive index n >=1.54 of the glasswork utilizing frit of the present invention to obtain, abbe number vd > 60.
Above content is in conjunction with concrete optimal technical scheme further description made for the present invention, can not assert that specific embodiment of the invention is confined to these explanations.For general technical staff of the technical field of the invention, without departing from the inventive concept of the premise, some simple deduction or replace can also be made, all should be considered as belonging to protection scope of the present invention.
Claims (5)
1. a unleaded crystal glass material, is characterized in that, comprises each component of following weight percentage: SiO
2: 57%-61%, Na
2cO
3: 23%-25%, NaNO
3: 5%-6%, Na
2b
4o
710H
2o:2%-3.5%, ZnO:1.4%-1.5%, BaCO
3: 4.3%-5%, Li
2cO
3: 0.7%-1.5%, CeO
2: 0.5%-1%.
2. the unleaded crystal glass material of one according to claim 1, is characterized in that, the weight percentage of described each component is: SiO
2: 57.000%, Na
2cO
3: 24.981%, NaNO
3: 5.831%, Na
2b
4o
710H
2o:3.347%, ZnO:1.482%, BaCO
3: 4.941%, Li
2cO
3: 1.433%, CeO
2: 0.985%.
3. the unleaded crystal glass material of one according to claim 1, is characterized in that, the weight percentage of described each component is: SiO
2: 59.000%, Na
2cO
3: 24.123%, NaNO
3: 5.482%, Na
2b
4o
710H
2o:3.147%, ZnO:1.450%, BaCO
3: 4.517%, Li
2cO
3: 1.397%, CeO
2: 0.884%.
4. the unleaded crystal glass material of one according to claim 1, is characterized in that, the weight percentage of described each component is: SiO
2: 61.000%, Na
2cO
3: 23.225%, NaNO
3: 5.102%, Na
2b
4o
710H
2o:2.918%, ZnO:1.412%, BaCO
3: 4.837%, Li
2cO
3: 0.981%, CeO
2: 0.525%.
5. the preparation method of a kind of unleaded crystal glass material described in any one of claim 1-4, is characterized in that, comprise the steps:
A, batching:
According to the mass percent of each component, calculate the quality of corresponding raw material and take each raw material;
B, raw material stoving:
The moisture in nature oven dry and each raw material of electric oven capable person is utilized to be reduced to less than 8%;
C, mix and blend:
By dry after prepared using supper micron mill and mixer mix and blend be powder shape.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310188948.XA CN103241946B (en) | 2013-05-21 | 2013-05-21 | Lead-free crystal glass and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310188948.XA CN103241946B (en) | 2013-05-21 | 2013-05-21 | Lead-free crystal glass and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103241946A CN103241946A (en) | 2013-08-14 |
| CN103241946B true CN103241946B (en) | 2015-02-11 |
Family
ID=48921857
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310188948.XA Expired - Fee Related CN103241946B (en) | 2013-05-21 | 2013-05-21 | Lead-free crystal glass and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103241946B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103936280A (en) * | 2014-03-27 | 2014-07-23 | 大连卡莎慕玻璃艺术有限公司 | Formula and process of lead-free color coated glass and glass product prepared from lead-free color coated glass |
| CN104829130B (en) * | 2015-05-04 | 2018-01-02 | 东华大学 | A kind of unleaded barium-free environment-friendly type water crystal glass and preparation method thereof |
| CN108383380A (en) * | 2018-04-18 | 2018-08-10 | 韩东 | Synthetic quartz gravestone |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100325194B1 (en) * | 2000-01-21 | 2002-02-21 | 윤철섭 | composition of crystal glass |
| EP2022767B1 (en) * | 2006-05-19 | 2011-04-06 | Toyo-sasaki Glass Co., Ltd. | Crystal glass article |
| CZ2009373A3 (en) * | 2009-06-10 | 2010-10-13 | Preciosa, A. S. | High-lead glass |
| GB201108052D0 (en) * | 2011-05-13 | 2011-06-29 | Nazeing Glass Works Ltd | Non-toxic crystal glass |
-
2013
- 2013-05-21 CN CN201310188948.XA patent/CN103241946B/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN103241946A (en) | 2013-08-14 |
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| TA01 | Transfer of patent application right |
Effective date of registration: 20141210 Address after: 116000, Liaoning province Dalian Pu Wan New Area fort town horse furnace Village Applicant after: DALIAN CASAMOTION GLASS CRAFT CO., LTD. Address before: 1211, room 158, 116001 Friendship Road, Zhongshan District, Dalian, Liaoning, China Applicant before: Ariamotion (Dalian) Co., Ltd. |
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Address after: 116000, Liaoning province Dalian Pu Wan New Area fort town horse furnace Village Patentee after: Dalian Casamu glass art Limited by Share Ltd Address before: 116000, Liaoning province Dalian Pu Wan New Area fort town horse furnace Village Patentee before: DALIAN CASAMOTION GLASS CRAFT CO., LTD. |
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| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20150211 Termination date: 20190521 |