CN101717971A - Electrolyte for preparing fine copper powder and use method thereof - Google Patents
Electrolyte for preparing fine copper powder and use method thereof Download PDFInfo
- Publication number
- CN101717971A CN101717971A CN200910218343A CN200910218343A CN101717971A CN 101717971 A CN101717971 A CN 101717971A CN 200910218343 A CN200910218343 A CN 200910218343A CN 200910218343 A CN200910218343 A CN 200910218343A CN 101717971 A CN101717971 A CN 101717971A
- Authority
- CN
- China
- Prior art keywords
- concentration
- powder
- distilled water
- copper powder
- electrolytic solution
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 238000000034 method Methods 0.000 title claims abstract description 19
- 239000003792 electrolyte Substances 0.000 title claims abstract description 15
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000012153 distilled water Substances 0.000 claims abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 16
- 108010010803 Gelatin Proteins 0.000 claims abstract description 14
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000012964 benzotriazole Substances 0.000 claims abstract description 14
- 229920000159 gelatin Polymers 0.000 claims abstract description 14
- 239000008273 gelatin Substances 0.000 claims abstract description 14
- 235000019322 gelatine Nutrition 0.000 claims abstract description 14
- 235000011852 gelatine desserts Nutrition 0.000 claims abstract description 14
- 229910000365 copper sulfate Inorganic materials 0.000 claims abstract description 13
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims abstract description 13
- 239000000843 powder Substances 0.000 claims abstract description 13
- 238000007790 scraping Methods 0.000 claims abstract description 7
- 238000004519 manufacturing process Methods 0.000 claims abstract description 6
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 5
- 239000008151 electrolyte solution Substances 0.000 claims description 27
- 239000007788 liquid Substances 0.000 claims description 12
- 238000002360 preparation method Methods 0.000 claims description 8
- 238000013019 agitation Methods 0.000 claims description 4
- 239000000243 solution Substances 0.000 claims description 2
- 229910001220 stainless steel Inorganic materials 0.000 claims description 2
- 239000010935 stainless steel Substances 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 abstract description 8
- 230000003647 oxidation Effects 0.000 abstract description 4
- 238000007254 oxidation reaction Methods 0.000 abstract description 4
- 238000010923 batch production Methods 0.000 abstract description 3
- 229910000619 316 stainless steel Inorganic materials 0.000 abstract 1
- 238000009827 uniform distribution Methods 0.000 abstract 1
- 238000005516 engineering process Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 2
- 239000002253 acid Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- -1 contains ball milled Chemical compound 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000004108 freeze drying Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
Abstract
The invention discloses an electrolyte for preparing fine copper powder and a use method thereof. The electrolyte comprises the following components: 5g/L of copper sulfate, 400-800g/L of phosphoric acid, 200-600g/L of distilled water, 1-2g/L of gelatin and 2g/L of benzotriazole. Operation conditions of electrolysis are as follows: the interelectrode distance is 10-30cm, the temperature of the electrolyte is 5-30 DEG C, the density of cathode current is 3-8A/dm2, and a powder scraping period is 10-25min. Cathode copper is used as an anode of electrolytic production, and a 316 stainless steel plate is used as a cathode for scraping powder. Compared with a sulfuric acid electrolysis method for preparing the fine copper powder, the invention has the advantages of simple electrolyte prescription, easy control, wide technological parameter range, long service life and high batch production stability, and the prepared fine copper powder has fine and uniform distribution granularity, high purity, good forming property and strong oxidation resistance.
Description
Technical field
The present invention relates to technical field of wet metallurgy, particularly the technology of preparing of electrolytic copper powder.
Background technology
Because fine powder has the unusual performance that is different from traditional material, can show characteristics such as unique mechanical, electricity, calorifics, optics and chemistry, therefore be widely used in the fields such as manufacturing of conductive resin, electrically conducting coating and electrode materials.The preparation of fine copper powder mainly contains ball milled, laser Gaseous synthesis method, high temperature gas phase cracking process, freeze-drying, sonochemical method, oxidation reduction process etc., but these method production cost height, apparatus expensive, process complexity.The sulfuric acid electrolytic process is with a long history, technical maturity, present dominant position in occupation of the domestic and international copper powder production market requirement.But the sulfuric acid electrolytic process prepares fine copper powder, still exist process parameters range narrower, the copper powder granularity is bigger, size distribution is inhomogeneous, and the dendritic structure moulding is bad, and current efficiency is lower, and the acid mist volatile quantity in the production process is more, environmental pollution is serious, to shortcomings such as human body harm are bigger, still awaits further perfect.
Summary of the invention
The present invention is exactly at the prior art above shortcomings, and a kind of electrolytic solution and using method thereof of new preparation fine copper powder is provided.Advantage of the present invention is: electrolyte prescription is simple, is easy to control, and process parameters range is wide, long service life, batch production stability height.The fine copper powder fine size of preparing and be evenly distributed, the purity height, good moldability, resistance of oxidation is strong.
The composition of the electrolytic solution of preparation fine copper powder of the present invention is:
Copper sulfate: 5g/L; Phosphoric acid: 400～800mL/L; Distilled water: 200～600mL/L; Gelatin: 1～2g/L; Benzotriazole: 2g/L.
The present invention gives the using method of the electrolytic solution of preparation fine copper powder, it is characterized in that interpole gap: 10～30cm, and electrolyte temperature: 5～30 ℃, cathode current density: 3～8A/dm
2, scrape powder cycle: 10～25min.The cathode copper that adopts the electrolytic process acquisition adopts the 316L stainless steel as scraping the negative electrode that powder is used as anode.
The compound method of the electrolytic solution of preparation fine copper powder of the present invention is: with the copper sulfate dissolved in distilled water, form A liquid 1.; With A liquid under agitation condition, join in the quantitative phosphoric acid solution, form B liquid; 3. dissolve gelatin and benzotriazole respectively with distilled water, filter the back and under agitation condition, join respectively in the B liquid, form C liquid; 4. will be used for electrolysis behind the C liquid constant volume.
Prepare the fine copper powder technology with the sulfuric acid electrolytic process and compare, the present invention has following advantage or positively effect:
1, in the phosphoric acid system, realized the electrolytic process preparation of fine copper powder;
2, in electrolytic solution, add gelatin, reduced the granularity of fine copper powder well;
3, in electrolytic solution, add benzotriazole, obviously played the anti-variable color of raising fine copper powder, oxidation resistant effect.
4, fine copper powder purity height, good moldability, granularity are thin and be evenly distributed, and resistance of oxidation is strong;
4, electrolyte prescription is simple, is easy to control, and process parameters range is wide;
5, electrolytic solution is stable, long service life, batch production stability height.
Embodiment
The invention will be further described with embodiment below.But they are not construed as limiting the invention.
Embodiment 1:
The prescription of electrolytic solution is: copper sulfate: 5g/L; Phosphoric acid: 500mL/L; Distilled water: 500mL/L; Gelatin: 1g/L; Benzotriazole: 2g/L
Electrolytic processing condition are: interpole gap: 10cm, and electrolyte temperature: 15 ℃, cathode current density: 6A/dm
2, scrape powder cycle: 10min.
Embodiment 2:
The prescription of electrolytic solution is the same with embodiment 1, and processing condition are also substantially the same manner as Example 1, and just interpole gap is 15cm.
Embodiment 3:
The prescription of electrolytic solution is the same with embodiment 1, and processing condition are also substantially the same manner as Example 1, and just interpole gap is 20cm.
Embodiment 4:
The prescription of electrolytic solution is the same with embodiment 1, and processing condition are also substantially the same manner as Example 1, and just interpole gap is 25cm.
Embodiment 1 to embodiment 4, more as shown in table 1 between the granularity of fine copper powder, current efficiency and the power consumption.
Comparison between the granularity of table 1 fine copper powder, current efficiency and the power consumption (embodiment 1 to embodiment 4)
| The contrast index | Granularity (μ m) | Current efficiency (%) | Power consumption (degree/ton) |
| Embodiment 1 | ??2.5～5.0 | ??21.73 | ??17210 |
| Embodiment 2 | ??2.5～5.0 | ??22.56 | ??16819 |
| Embodiment 3 | ??～5.0 | ??20.56 | ??18359 |
| Embodiment 4 | ??～5.0 | ??17.12 | ??21924 |
Embodiment 5:
The prescription of electrolytic solution is: copper sulfate: 5g/L; Phosphoric acid: 400mL/L; Distilled water: 600mL/L; Gelatin: 1g/L; Benzotriazole: 2g/L
Electrolytic processing condition are: interpole gap: 10cm, and electrolyte temperature: 15 ℃, cathode current density: 6A/dm
2, scrape powder cycle: 10min.
Embodiment 6:
The prescription of electrolytic solution is substantially the same manner as Example 5, and just the addition of phosphoric acid is 600mL/L, and the addition of distilled water is 400mL/L.Processing condition are also substantially the same manner as Example 5.
Embodiment 7:
The prescription of electrolytic solution is substantially the same manner as Example 5, and just the phosphoric acid addition is 700mL/L, and the addition of distilled water is 300mL/L, and processing condition are also the same with embodiment 5.
Embodiment 5 to embodiment 7, more as shown in table 2 between the granularity of fine copper powder, current efficiency and the power consumption.
Comparison between the granularity of table 2 fine copper powder, current efficiency and the power consumption (embodiment 5 to embodiment 7)
| The contrast index | Granularity (μ m) | Current efficiency (%) | Power consumption (degree/ton) |
| Embodiment 5 | ??5.0～7.5 | ??24.78 | ??14063 |
| Embodiment 6 | ??～5.0 | ??21.57 | ??17886 |
| Embodiment 7 | ??～2.5 | ??19.32 | ??19347 |
Embodiment 8:
The prescription of electrolytic solution is: copper sulfate: 5g/L; Phosphoric acid: 500mL/L; Distilled water: 500mL/L; Gelatin: 1g/L; Benzotriazole: 2g/L
Electrolytic processing condition are: interpole gap: 10cm, and electrolyte temperature: 20 ℃, cathode current density: 6A/dm
2, scrape powder cycle: 10min.
Embodiment 9:
The prescription of electrolytic solution is the same with embodiment 9, and processing condition are also substantially the same manner as Example 9, and just electrolyte temperature is 25 ℃.
Embodiment 10:
The prescription of electrolytic solution is the same with embodiment 9, and processing condition are also substantially the same manner as Example 9, and just electrolyte temperature is 30 ℃.
Embodiment 8 to embodiment 10, more as shown in table 3 between the granularity of fine copper powder, current efficiency and the power consumption.
Comparison between the granularity of table 3 fine copper powder, current efficiency and the power consumption (embodiment 8 to embodiment 10)
| The contrast index | Granularity (μ m) | Current efficiency (%) | Power consumption (degree/ton) |
| Embodiment 8 | ??2.5～5.0 | ??27.78 | ??10427 |
| Embodiment 9 | ??～5.0 | ??36.68 | ??7426 |
| Embodiment 10 | ??5.0～7.5 | ??45.23 | ??6658 |
Embodiment 11:
The prescription of electrolytic solution is: copper sulfate: 5g/L; Phosphoric acid: 500mL/L; Distilled water: 500mL/L; Gelatin: 1g/L; Benzotriazole: 2g/L
Electrolytic processing condition are: interpole gap: 5cm, and electrolyte temperature: 15 ℃, current density: 6A/dm
2, scrape powder cycle: 10min.
Embodiment 12:
The prescription of electrolytic solution is identical with embodiment 13, and processing condition are also substantially the same manner as Example 13, and just scraping the powder cycle is 15min.
Embodiment 13:
The prescription of electrolytic solution is identical with embodiment 13, and processing condition are also substantially the same manner as Example 13, and just scraping the powder cycle is 20min.
Embodiment 11 to embodiment 13, more as shown in table 4 between the granularity of fine copper powder, current efficiency and the power consumption.
Comparison between the granularity of table 4 fine copper powder, current efficiency and the power consumption (embodiment 11 to embodiment 13)
| The contrast index | Granularity (μ m) | Current efficiency (%) | Power consumption (degree/ton) |
| Embodiment 11 | ??2.5～5.0 | ??24.23 | ??14672 |
| Embodiment 12 | ??～5.0 | ??23.09 | ??15325 |
| Embodiment 13 | ??7.5～5.0 | ??19.66 | ??19726 |
Claims (4)
1. electrolytic solution for preparing fine copper powder, it is characterized in that: the consisting of of electrolytic solution: copper sulfate, phosphoric acid, distilled water, gelatin and benzotriazole, described concentration of copper sulfate are 5g/L, phosphoric acid concentration is 400 ~ 800mL/L, distilled water concentration is 200 ~ 600mL/L, and gelatin concentration is 1 ~ 3g/L, and benzotriazole concentration is 2g/L.
2. preparation method who prepares the electrolytic solution of fine copper powder is characterized in that containing following steps: (1) forms A liquid with the copper sulfate dissolved in distilled water; (2) with A liquid under agitation condition, join in the quantitative phosphoric acid solution, form B liquid; (3) dissolve gelatin and benzotriazole respectively with distilled water, filter the back and under agitation condition, join respectively in the B liquid, form C liquid; (4) will be used for electrolysis behind the C liquid constant volume.
3. according to described a kind of preparation method who prepares the electrolytic solution of fine copper powder of claim 2, it is characterized in that: the concentration of described copper sulfate is 5g/L, concentration of phosphoric acid is 400 ~ 800mL/L, the concentration of distilled water is 200 ~ 600mL/L, the concentration of gelatin is 1 ~ 3g/L, and the concentration of benzotriazole is 2g/L.
4. using method for preparing the electrolytic solution of fine copper powder, it is characterized in that: electrolytic solution is by copper sulfate, phosphoric acid, distilled water, gelatin, benzotriazole is formed, and the concentration of copper sulfate is 5g/L, and concentration of phosphoric acid is 400 ~ 800mL/L, the concentration of distilled water is 200 ~ 600mL/L, the concentration of gelatin is 1 ~ 3g/L, and the concentration of benzotriazole is 2g/L, and operational condition is: cathode copper is as the anode of electrolysis production, the 316L stainless steel plate is as scraping the negative electrode that powder is used, interpole gap is 10 ~ 30cm, and electrolyte temperature is 5 ~ 30 ℃, and cathode current density is 3 ~ 8A/dm
2, scraping the powder cycle is 5 ~ 25min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009102183434A CN101717971B (en) | 2009-12-14 | 2009-12-14 | Electrolyte for preparing fine copper powder and use method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009102183434A CN101717971B (en) | 2009-12-14 | 2009-12-14 | Electrolyte for preparing fine copper powder and use method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101717971A true CN101717971A (en) | 2010-06-02 |
| CN101717971B CN101717971B (en) | 2012-03-21 |
Family
ID=42432609
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2009102183434A Expired - Fee Related CN101717971B (en) | 2009-12-14 | 2009-12-14 | Electrolyte for preparing fine copper powder and use method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101717971B (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102978667A (en) * | 2012-10-25 | 2013-03-20 | 烟台大学 | Preparation method for nanometer copper powder through electro-deposition |
| CN103128272A (en) * | 2011-11-28 | 2013-06-05 | 重庆华浩冶炼有限公司 | Electrolytic copper-powder-processing technique |
| CN103658637A (en) * | 2013-12-12 | 2014-03-26 | 昆明理工大学 | Method for preparing arborization fine copper powder in electrolysis mode |
| CN103862030A (en) * | 2012-12-18 | 2014-06-18 | 重庆华浩冶炼有限公司 | Copper powder composition and preparation method thereof |
| CN104928724A (en) * | 2015-07-07 | 2015-09-23 | 昆明理工大学 | Method for electrolytically preparing dendritic fine copper powder in oxalic acid |
| CN110144604A (en) * | 2019-06-17 | 2019-08-20 | 阳谷祥光铜业有限公司 | A kind of preparation process of electrodeposition copper powder |
| RU2708719C1 (en) * | 2019-07-02 | 2019-12-11 | Федеральное государственное бюджетное образовательное учреждение высшего образования "Московский автомобильно-дорожный государственный технический университет (МАДИ)" | Method of producing copper dispersed particles by electrochemical method |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BR9406043A (en) * | 1993-04-19 | 1995-12-19 | Magma Copper Co | Process for the production of metallic copper powder, copper oxides and copper foil |
| JP5004081B2 (en) * | 2007-03-06 | 2012-08-22 | 独立行政法人産業技術総合研究所 | Method for recovering high-purity copper from copper-containing waste and solution or electrolyte used therefor |
-
2009
- 2009-12-14 CN CN2009102183434A patent/CN101717971B/en not_active Expired - Fee Related
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103128272A (en) * | 2011-11-28 | 2013-06-05 | 重庆华浩冶炼有限公司 | Electrolytic copper-powder-processing technique |
| CN103128272B (en) * | 2011-11-28 | 2016-08-10 | 重庆有研重冶新材料有限公司 | The technique that a kind of electrolysis produces copper powder |
| CN102978667A (en) * | 2012-10-25 | 2013-03-20 | 烟台大学 | Preparation method for nanometer copper powder through electro-deposition |
| CN102978667B (en) * | 2012-10-25 | 2016-06-22 | 烟台大学 | A kind of method of preparing nano-bronze powder using electric deposition |
| CN103862030A (en) * | 2012-12-18 | 2014-06-18 | 重庆华浩冶炼有限公司 | Copper powder composition and preparation method thereof |
| CN103862030B (en) * | 2012-12-18 | 2017-10-27 | 重庆有研重冶新材料有限公司 | A kind of copper powder composition |
| CN103658637A (en) * | 2013-12-12 | 2014-03-26 | 昆明理工大学 | Method for preparing arborization fine copper powder in electrolysis mode |
| CN103658637B (en) * | 2013-12-12 | 2015-08-12 | 昆明理工大学 | A kind of method of electrolytic preparation dendroid fine copper powder |
| CN104928724A (en) * | 2015-07-07 | 2015-09-23 | 昆明理工大学 | Method for electrolytically preparing dendritic fine copper powder in oxalic acid |
| CN104928724B (en) * | 2015-07-07 | 2017-07-07 | 昆明理工大学 | A kind of method of the electrolytic preparation dendroid fine copper powder in ethanedioic acid |
| CN110144604A (en) * | 2019-06-17 | 2019-08-20 | 阳谷祥光铜业有限公司 | A kind of preparation process of electrodeposition copper powder |
| RU2708719C1 (en) * | 2019-07-02 | 2019-12-11 | Федеральное государственное бюджетное образовательное учреждение высшего образования "Московский автомобильно-дорожный государственный технический университет (МАДИ)" | Method of producing copper dispersed particles by electrochemical method |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101717971B (en) | 2012-03-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101717971B (en) | Electrolyte for preparing fine copper powder and use method thereof | |
| CN103658637B (en) | A kind of method of electrolytic preparation dendroid fine copper powder | |
| WO2016134618A1 (en) | New method for membrane-free electrolysis of water capable of controlling acid-base property of the electrolysed water | |
| CN110284166A (en) | A kind of electro-deposition method preparing foam nickel-molybdenum alloy | |
| CN105399423A (en) | Method for preparing nanopore graphene filter film through arc discharge method | |
| CN103276404A (en) | Preparation method of gas diffusion electrode | |
| CN202814909U (en) | Inter-electrode distance adjustable electrolytic bath | |
| CN113666367B (en) | Electrolytic tank for preparing graphite intercalation and preparation method of graphite intercalation | |
| CN113430558B (en) | Dual-function self-supporting electrode with heterostructure as well as preparation method and application thereof | |
| CN115874216A (en) | Platinum-based amorphous alloy porous catalyst for chlorine evolution reaction and preparation method thereof | |
| CN105513802A (en) | Manufacturing method of composite dielectric film-containing low-voltage formed foil | |
| CN108640165A (en) | A kind of metal oxide nanostructure composite material and preparation method | |
| CN2851281Y (en) | Electrode plate used for production of succinic acid | |
| CN201660470U (en) | Alkalescence negative potential brine electrolysis preparing device and electrolytic water dispenser | |
| CN1320171C (en) | Lead dioxide electrode and preparing method thereof | |
| RU153346U1 (en) | ELECTROLYTIC PLANT FOR PRODUCING A GAS MIXTURE OF HYDROGEN AND OXYGEN | |
| CN113249740A (en) | Method for preparing graphene by electrochemical continuous and synchronous stripping and reduction | |
| CN106676563B (en) | A kind of ultrasonic electrolysis preparation method of carboxylated carbon nanosheet | |
| CN210765535U (en) | Bipolar electrolytic tank for electrolyzing tetramethyl ammonium hydroxide | |
| CN105405683B (en) | A kind of active charcoal super capacitor high pressure resistant aqueous electrolyte and preparation method thereof | |
| CN110284168A (en) | A kind of electric depositing solution formula preparing foam nickel-molybdenum alloy | |
| KR20150004720A (en) | Electrode material for fuel cell and manufacturing method thereof | |
| CN112626568A (en) | Method for preparing copper powder by recovering copper from etching solution and electrolyzing | |
| CN202936495U (en) | Counter current-resistant titanium anode plate | |
| CN108251864A (en) | A kind of Zinc electrolysis additive and its application method |
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: 20120321 Termination date: 20141214 |
|
| EXPY | Termination of patent right or utility model |