CN1864834A - An addictive-free, long-term stable, high-solid, transparent and conductive nano crystalline water dispersion and method for preparing same - Google Patents
An addictive-free, long-term stable, high-solid, transparent and conductive nano crystalline water dispersion and method for preparing same Download PDFInfo
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- CN1864834A CN1864834A CN 200610043481 CN200610043481A CN1864834A CN 1864834 A CN1864834 A CN 1864834A CN 200610043481 CN200610043481 CN 200610043481 CN 200610043481 A CN200610043481 A CN 200610043481A CN 1864834 A CN1864834 A CN 1864834A
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Abstract
The invention discloses a transparent conduct nanometer dispersion and the method for preparing the same. The method employs simple process of hydrothermal synthesis and final treatment; final treatment employs grinding, ultrasonication, and high-speed centrifugation, and employs no auxiliary agent. The product is characterized by high purity, good transparency and conductivity, stable storage, no aggregation and sedimentation. The invention provides fine raw material for researching structure, synthetic mechanism and water-dispersible mechanism of stalline nanometer material.
Description
Technical field:
The present invention relates to the manufacturing technology field of the brilliant conducting function material of transparent nano, is to use the brilliant aqueous dispersions of transparent conductive nano and preparation method thereof that hydrothermal synthesis method is made the high solid of non-additive long-term stability specifically.
Background technology:
At present, common conductive material such as metal and graphite etc. all are opaque materials, the modern high technology technical field needs the new material of a large amount of not only transparent but also conduction, at present existing antimony oxide and tin ash (ATO) and indium sesquioxide and tin ash (ITO) transparent conductive material, these materials often contain impurity, particle diameter is big, solids content is low, unstable and easily cohesion and sedimentation when depositing, and are difficult for being applied to the technical field of specific (special) requirements; In order to address these problems, people also begin one's study and produce nano level ATO and ITO material, adapting to the technical field of specific (special) requirements, as technical fields such as the antistatic of display system, solar panel and the glass of kinescope, computer display tube, flat panel TV and the computer of CRT, anti-dazzle, radiation proofs; But existing nano level ATO and ITO material, its manufacture method commonly used is: 1, hydroxide co-precipitation---the broken classification of filtration washing---high-temperature roasting---, this method is that disadvantage is that broken classification is very difficult, the rate of recovery is low, the cost height, and need add a large amount of auxiliary agents when making aqueous dispersion, therefore the scope of application also is restricted; 2, hydroxide co-precipitation---the broken classification of filtration washing---hydro-thermal is synthetic---, the advantage of this method is that broken size scale is easier to, shortcoming is mostly at the synthetic eutectic thing auxiliary agent in addition that added of hydro-thermal, do not solve " segregation " problem, problems such as transparency is not high, electric conductivity is bad, bin stability difference often occur.
Summary of the invention:
The objective of the invention is to overcome the deficiency of above-mentioned prior art, and a kind of brilliant aqueous dispersions of transparent conductive nano of high solid of non-additive long-term stability is provided.
Another object of the present invention provides a kind of brilliant aqueous dispersions of transparent conductive nano and preparation method thereof of high solid of non-additive long-term stability.
The present invention solved mainly that existing transparent conductive material contains impurity, particle diameter is big, solids content is low, unstable and easy problems such as cohesion and sedimentation when depositing.
In order to achieve the above object, the present invention is achieved in that the brilliant aqueous dispersions of transparent conductive nano of the high solid of non-additive long-term stability, be that stannic chloride pentahydrate and trichloride antimony are dissolved in the isopropyl alcohol, or stannic chloride pentahydrate and indium trichloride be dissolved in the isopropyl alcohol, again with in the above-mentioned solution impouring boiling water, be neutralized to neutrality with ammoniacal liquor, be incubated 1 hour, after placing cooling, filter with funnel, filtrate is washed with pure water, the sediment that obtains is in container, adding pure water stirs, reinstall in the magnetic agitation high temperature and high pressure kettle, be warming up to 300-400 ℃ after the sealing, pressure remains on 15-22Mpa, heat-insulation pressure keeping 3-5 hour, stop heating and be cooled to room temperature, move to standing demix in the container, another vessel in heating of supernatant liquor impouring is concentrated into thick, lower floor's dope or lower floor's dope and supernatant liquor concentrate put in the sand mill grind half an hour, then disperseed 1 hour with the ultrasonication of ultrasonication dispersion machine, carrying out high speed centrifugation again separates, isolated corase particles can mix sand milling and ultrasonication dispersion again in the synthetic conducting liquid again, and isolated fine particle partly is the brilliant aqueous dispersions of transparent conductive nano of the high solid of non-additive long-term stability.
The brilliant aqueous dispersions of the transparent conductive nano of the high solid of non-additive long-term stability of the present invention, the granularity of its described product is less than 50nm, and solid divides content to reach more than 25%.
The preparation method of the brilliant aqueous dispersions of the transparent conductive nano of the high solid of non-additive long-term stability of the present invention, it comprises following processing step:
A, dissolving; Stannic chloride pentahydrate and trichloride antimony are dissolved in the isopropyl alcohol, or stannic chloride pentahydrate and indium trichloride are dissolved in the isopropyl alcohol;
B, co-precipitation is filtered; In above-mentioned solution impouring boiling water, be neutralized to neutrality with ammoniacal liquor, be incubated 70-90 ℃, temperature retention time 1 hour is placed cooling again, filters with funnel, and filtrate is washed ten times with pure water;
C, the system suspension; The above-mentioned sediment that obtains in container, is added pure water and stirs;
D, the autoclave heating; Above-mentioned suspension is packed in the magnetic agitation high temperature and high pressure kettle, be warming up to 300-400 ℃ after the sealing, pressure remains on 15-22Mpa, heat-insulation pressure keeping 3-5 hour, stops heating and is cooled to room temperature;
E grinds; Product is moved to standing demix in the container, and another vessel in heating of supernatant liquor impouring is concentrated into thick (can concentrate concentrated with repeatedly synthesizing the supernatant liquor that obtains); Lower floor's dope or lower floor's dope and supernatant liquor concentrate put in the sand mill grind half an hour;
F, fragmentation; Above-mentioned product was disperseed 1 hour with the ultrasonication of ultrasonication dispersion machine;
G, the centrifugal product that gets; To separate with high speed centrifugation through the product that ultrasonication disperses to obtain, centrifugal condition is: 8000ram-10000ram, time 10-20 minute, isolated corase particles can mix sand milling and ultrasonication dispersion again in the synthetic conducting liquid again, and isolated fine particle partly is the brilliant aqueous dispersions of transparent conductive nano of the high solid of non-additive long-term stability.
Compared with the prior art brilliant aqueous dispersions of the transparent conductive nano of the high solid of non-additive long-term stability of the present invention and preparation method thereof has outstanding substantive distinguishing features and marked improvement: 1, adopt hydro-thermal synthetic optimum temperature and pressure, improved transparency of products and electric conductivity; 2, adopt simple and direct technological process, avoided the generation of " segregation " phenomenon, make the quality of product high and stable; 3, the ultracentrifugal optimization technology of sand milling---ultrasonication---is adopted in post processing, does not use any auxiliary agent to produce the stable ATO of pure high solid and the aqueous dispersions of ITO, and its particle maximum gauge is less than 50nm, and solids content is more than 25%; 4, because product has the purity height, solid divides high, advantages such as transparency good, excellent conductivity, under the condition of 5-50 ℃ and lucifuge, can steady in a long-termly store, do not condense, not sedimentation, thereby enlarge its range of application.
The specific embodiment:
In order to understand better and to implement, below in conjunction with brilliant aqueous dispersions of transparent conductive nano of the high solid of implementing just to describe in detail the non-additive long-term stability of the present invention and preparation method thereof.
Embodiment 1,120g stannic chloride pentahydrate and 14.3g trichloride antimony are dissolved in the 600ml isopropyl alcohol, in above-mentioned solution impouring 1200ml boiling water, be neutralized to neutrality with ammoniacal liquor, put on the low-temperature furnace and be incubated 70-90 ℃, 1 hour time, after placing cooling then, filter with the Buchner funnel of completing fine and close filter paper, then with pure water washing ten times, the sediment that obtains is transferred in the suitable vessel, add pure water to 800ml, stir, again above-mentioned suspension is packed in the magnetic agitation high temperature and high pressure kettle of 2L, be warming up to 300-400 ℃ after the sealing, pressure remains on 15-22Mpa, heat-insulation pressure keeping 3-5 hour, stop heating and be cooled to room temperature, product is transferred to standing demix in the container, another vessel in heating of supernatant liquor impouring is concentrated into thick, also can be with repeatedly the synthetic supernatant liquor that obtains is concentrated concentrated, lower floor's dope also can be merged the supernatant liquor concentrate, put in the sand mill and grind half an hour, disperseed 1 hour with the ultrasonication of ultrasonic disruption dispersion machine again, to use high speed centrifugation 800-1000ram centrifugation 10-20 minute through the product that ultrasonication disperses to obtain, isolated corase particles can mix sand milling and ultrasonication dispersion again in the synthetic conduction liquid again, and isolated fine particle partly is the brilliant aqueous dispersions of transparent conductive nano of the high solid of non-additive long-term stability of the present invention.
Embodiment 2,600g stannic chloride pentahydrate and 71.5g trichloride antimony are dissolved in the 3000ml isopropyl alcohol, in above-mentioned solution impouring 6000ml boiling water, be neutralized to neutrality with ammoniacal liquor, put on the low-temperature furnace and be incubated 70-90 ℃, 1 hour time, after placing cooling then, filter with the Buchner funnel of completing fine and close filter paper, then with pure water washing ten times, the sediment that obtains is transferred in the suitable vessel, add pure water to 4000ml, stir, again above-mentioned suspension is packed in the magnetic agitation high temperature and high pressure kettle of 10L, be warming up to 300-400 ℃ after the sealing, pressure remains on 15-22Mpa, heat-insulation pressure keeping 3-5 hour, stop heating and be cooled to room temperature, product is transferred to standing demix in the container, another vessel in heating of supernatant liquor impouring is concentrated into thick, also can be with repeatedly the synthetic supernatant liquor that obtains is concentrated concentrated, lower floor's dope also can be merged the supernatant liquor concentrate, put in the sand mill and grind half an hour, disperseed 1 hour with the ultrasonication of ultrasonic disruption dispersion machine again, to use high speed centrifugation 800-1000ram centrifugation 10-20 minute through the product that ultrasonication disperses to obtain, isolated corase particles can mix sand milling and ultrasonication dispersion again in the synthetic conduction liquid again, and isolated fine particle partly is the brilliant aqueous dispersions of transparent conductive nano of the high solid of non-additive long-term stability of the present invention.
Embodiment 3,7g stannic chloride pentahydrate and 91g indium trichloride are dissolved in the 600ml isopropyl alcohol, in above-mentioned solution impouring 1200ml boiling water, be neutralized to neutrality with ammoniacal liquor, put on the low-temperature furnace and be incubated 70-90 ℃, 1 hour time, after placing cooling then, filter with the Buchner funnel of completing fine and close filter paper, then with pure water washing ten times, the sediment that obtains is transferred in the suitable vessel, add pure water to 800ml, stir, again above-mentioned suspension is packed in the magnetic agitation high temperature and high pressure kettle of 2L, be warming up to 300-400 ℃ after the sealing, pressure remains on 15-22Mpa, heat-insulation pressure keeping 3-5 hour, stop heating and be cooled to room temperature, product is transferred to standing demix in the container, another vessel in heating of supernatant liquor impouring is concentrated into thick, also can be with repeatedly the synthetic supernatant liquor that obtains is concentrated concentrated, lower floor's dope also can be merged the supernatant liquor concentrate, put in the sand mill and grind half an hour, disperseed 1 hour with the ultrasonication of ultrasonic disruption dispersion machine again, to use high speed centrifugation 800-1000ram centrifugation 10-20 minute through the product that ultrasonication disperses to obtain, isolated corase particles can mix sand milling and ultrasonication dispersion again in the synthetic conduction liquid again, and isolated fine particle partly is the brilliant aqueous dispersions of transparent conductive nano of the high solid of non-additive long-term stability of the present invention.
Embodiment 4,35g stannic chloride pentahydrate and 455g indium trichloride are dissolved in the 300ml isopropyl alcohol, in above-mentioned solution impouring 6000ml boiling water, be neutralized to neutrality with ammoniacal liquor, put on the low-temperature furnace and be incubated 70-90 ℃, 1 hour time, after placing cooling then, filter with the Buchner funnel of completing fine and close filter paper, then with pure water washing ten times, the sediment that obtains is transferred in the suitable vessel, add pure water to 4000ml, stir, again above-mentioned suspension is packed in the magnetic agitation high temperature and high pressure kettle of 10L, be warming up to 300-400 ℃ after the sealing, pressure remains on 15-22Mpa, heat-insulation pressure keeping 3-5 hour, stop heating and be cooled to room temperature, product is transferred to standing demix in the container, another vessel in heating of supernatant liquor impouring is concentrated into thick, also can be with repeatedly the synthetic supernatant liquor that obtains is concentrated concentrated, lower floor's dope also can be merged the supernatant liquor concentrate, put in the sand mill and grind half an hour, disperseed 1 hour with the ultrasonication of ultrasonic disruption dispersion machine again, to use high speed centrifugation 800-1000ram centrifugation 10-20 minute through the product that ultrasonication disperses to obtain, isolated corase particles can mix sand milling and ultrasonication dispersion again in the synthetic conduction liquid again, and isolated fine particle partly is the brilliant aqueous dispersions of transparent conductive nano of the high solid of non-additive long-term stability of the present invention.
Claims (4)
1, the brilliant aqueous dispersions of the transparent conductive nano of the high solid of non-additive long-term stability, be that stannic chloride pentahydrate and trichloride antimony are dissolved in the isopropyl alcohol, or stannic chloride pentahydrate and indium trichloride be dissolved in the isopropyl alcohol, again with in the above-mentioned solution impouring boiling water, be neutralized to neutrality with ammoniacal liquor, be incubated 1 hour, after placing cooling, filter with funnel, filtrate is washed with pure water, the sediment that obtains is in container, adding pure water stirs, reinstall in the magnetic agitation high temperature and high pressure kettle, be warming up to 300-400 ℃ after the sealing, pressure remains on 15-22Mpa, heat-insulation pressure keeping 3-5 hour, stop heating and be cooled to room temperature, move to standing demix in the container, another vessel in heating of supernatant liquor impouring is concentrated into thick, lower floor's dope or lower floor's dope and supernatant liquor concentrate put in the sand mill grind half an hour, then disperseed 1 hour, carry out high speed centrifugation again and separate with the ultrasonication of ultrasonication dispersion machine, isolated corase particles can mix sand milling and ultrasonication dispersion again in the synthetic conducting liquid again, and isolated fine particle partly is the brilliant aqueous dispersions of transparent conductive nano of the high solid of non-additive long-term stability.
2, the brilliant aqueous dispersions of the transparent conductive nano of the high solid of non-additive long-term stability according to claim 1, the granularity that it is characterized in that described product is less than 50nm, and solid divides content to reach more than 25%.
3, the preparation method of the brilliant aqueous dispersions of the transparent conductive nano of the high solid of the described non-additive long-term stability of claim 1, it comprises following processing step:
A, dissolving; Stannic chloride pentahydrate and trichloride antimony are dissolved in the isopropyl alcohol, or stannic chloride pentahydrate and indium trichloride are dissolved in the isopropyl alcohol;
B, co-precipitation and filtration; In above-mentioned solution impouring boiling water, be neutralized to neutrality with ammoniacal liquor, be incubated 70-90 ℃, temperature retention time 1 hour is placed cooling again, filters with funnel, and filtrate is washed ten times with pure water;
C, the system suspension; The above-mentioned sediment that obtains in container, is added pure water and stirs;
D, the autoclave heating; Above-mentioned suspension is packed in the magnetic agitation high temperature and high pressure kettle, be warming up to 300-400 ℃ after the sealing, pressure remains on 15-22Mpa, heat-insulation pressure keeping 3-5 hour, stops heating and is cooled to room temperature;
E grinds; Product is moved to standing demix in the container, and another vessel in heating of supernatant liquor impouring is concentrated into thick; Lower floor's dope or lower floor's dope and supernatant liquor concentrate put in the sand mill grind half an hour;
F, fragmentation; Above-mentioned product was disperseed 1 hour with the ultrasonication of ultrasonication dispersion machine;
G, the centrifugal product that gets; To separate with high speed centrifugation through the product that ultrasonication disperses to obtain, isolated corase particles can mix sand milling and ultrasonication dispersion again in the synthetic conducting liquid again, and isolated fine particle partly is the brilliant aqueous dispersions of transparent conductive nano of the high solid of non-additive long-term stability.
4, the preparation method of the brilliant aqueous dispersions of the transparent conductive nano of the high solid of non-additive long-term stability according to claim 3, it is characterized in that centrifugal condition is in described centrifugal the product step: 8000ram-10000ram, time 10-20 minute.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102679954A (en) * | 2012-05-31 | 2012-09-19 | 张文知 | Five-electrode four-direction electronic level meter of nanometer conducting liquid switch |
| CN102709099A (en) * | 2012-05-30 | 2012-10-03 | 张文知 | Nano conductive liquid switch |
| CN102760510A (en) * | 2011-04-26 | 2012-10-31 | 张文知 | ATO (Antimonial Tin Oxide) nanocrystal aqueous dispersion liquid and preparation method thereof |
| CN102760509A (en) * | 2011-04-26 | 2012-10-31 | 张文知 | ITO (Indium Tin Oxide) nanocrystal aqueous dispersion liquid and preparation method thereof |
| US20130153406A1 (en) * | 2011-12-14 | 2013-06-20 | Electronics And Telecommunications Research Institute | Methods of manufacturing metal oxide nanoparticles |
| CN102760510B (en) * | 2011-04-26 | 2016-12-14 | 南京大学淮安高新技术研究院 | ATO nano crystalline water dispersion and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP4488623B2 (en) * | 1998-09-06 | 2010-06-23 | ライプニッツ−インスティトゥート フィア ノイエ マテリアーリエン ゲマインニュッツィゲ ゲゼルシャフト ミット ベシュレンクタ ハフトゥンク | Suspension and powder preparation method based on indium tin oxide and use thereof |
| JP2004123403A (en) * | 2002-09-30 | 2004-04-22 | Fuji Photo Film Co Ltd | Method for manufacturing crystalline ito dispersion |
| KR100608318B1 (en) * | 2003-07-03 | 2006-08-04 | 전자부품연구원 | Method of manufacturing ITO nano powder |
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- 2006-04-04 CN CNB200610043481XA patent/CN100427192C/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102760510A (en) * | 2011-04-26 | 2012-10-31 | 张文知 | ATO (Antimonial Tin Oxide) nanocrystal aqueous dispersion liquid and preparation method thereof |
| CN102760509A (en) * | 2011-04-26 | 2012-10-31 | 张文知 | ITO (Indium Tin Oxide) nanocrystal aqueous dispersion liquid and preparation method thereof |
| CN102760510B (en) * | 2011-04-26 | 2016-12-14 | 南京大学淮安高新技术研究院 | ATO nano crystalline water dispersion and preparation method thereof |
| US20130153406A1 (en) * | 2011-12-14 | 2013-06-20 | Electronics And Telecommunications Research Institute | Methods of manufacturing metal oxide nanoparticles |
| CN102709099A (en) * | 2012-05-30 | 2012-10-03 | 张文知 | Nano conductive liquid switch |
| CN102679954A (en) * | 2012-05-31 | 2012-09-19 | 张文知 | Five-electrode four-direction electronic level meter of nanometer conducting liquid switch |
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| CN100427192C (en) | 2008-10-22 |
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