CN106477893B - A kind of preparation method of barium crown sealed glass - Google Patents
A kind of preparation method of barium crown sealed glass Download PDFInfo
- Publication number
- CN106477893B CN106477893B CN201610883508.XA CN201610883508A CN106477893B CN 106477893 B CN106477893 B CN 106477893B CN 201610883508 A CN201610883508 A CN 201610883508A CN 106477893 B CN106477893 B CN 106477893B
- Authority
- CN
- China
- Prior art keywords
- glass
- added
- stirred
- dry
- temperature
- 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
Classifications
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
- C03C8/24—Fusion seal compositions being frit compositions having non-frit additions, i.e. for use as seals between dissimilar materials, e.g. glass and metal; Glass solders
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C1/00—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels
- C03C1/02—Pretreated ingredients
- C03C1/026—Pelletisation or prereacting of powdered raw materials
Abstract
The present invention relates to a kind of preparation methods of barium crown sealed glass, belong to glass making techniques field.The present invention first mixes ethyl orthosilicate with dehydrated alcohol, and deionized water is added dropwise, add the mixed liquor of boric acid and dehydrated alcohol, agitating and heating, obtain vitreosol liquid, and its pH is adjusted with hydrochloric acid, through drying, obtain dry gel powder, then by itself and magnesia, strontium oxide strontia, the metal oxides such as barium monoxide carry out ball milling, obtain mixed material, finally carried out high-temperature calcination, obtain glass metal, through water quenching, dried and screened, obtain barium crown sealed glass, barium crown sealed glass kind prepared by the present invention does not contain heavy metal lead, environmental and human health impacts will not be had an impact, and there is high voltage performance, the requirement in high-pressure electronic field can be met.
Description
Technical field
The present invention relates to a kind of preparation methods of barium crown sealed glass, belong to glass making techniques field.
Background technique
Seal glass is a kind of advanced welding material, has convenient fusion temperature and sealing temperature, good resistance to
Hot and chemical stability, high mechanical strength, be widely used in electrovacuum and microelectric technique, laser and infrared technique,
The various fields such as high-energy physics, the energy, aerospace, automobile.Realize the mutual sealing-in between glass, ceramics, metal, semiconductor.It answers
Product has cathode-ray tube display, vacuum fluorescent display, plasma scope, vacuum glass, solar energy heating
Pipe, laser, magnetic material magnetic head and magnetic material film etc..
Seal glass be it is a kind of be commonly used in sealing of metal, nonmetallic or ceramic material, currently, electronic field use
The platinum group seal glass arrived can be by metal, nonmetallic or crunch seal together, but this eka-platinium group seal glass is high pressure resistant
Property it is poor, be not able to satisfy the demand in high-pressure electronic field, moreover, wherein contain heavy metal lead, human health and environment can be generated
It influences.
Summary of the invention
The technical problems to be solved by the invention: contain heavy metal lead for existing seal glass kind, to human health
And environmental effects, and the problem of high voltage performance difference, the present invention first mixes ethyl orthosilicate with dehydrated alcohol, and drips
Add deionized water, add the mixed liquor of boric acid and dehydrated alcohol, agitating and heating obtains vitreosol liquid, and adjusted with hydrochloric acid
Its pH obtains dry gel powder through drying, and the metal oxides such as itself and magnesia, strontium oxide strontia, barium monoxide are then carried out ball milling,
Mixed material is obtained, high-temperature calcination is finally carried out, obtains glass metal, through water quenching, dried and screened, obtains no leaded joint glass
Glass, barium crown sealed glass kind prepared by the present invention do not contain heavy metal lead, will not have an impact to environmental and human health impacts, and have
There is high voltage performance, the requirement in high-pressure electronic field can be met.
In order to solve the above technical problems, the technical solution adopted by the present invention is that:
(1) measure 50~60mL ethyl orthosilicate be added in three-necked flask, into three-necked flask be added dropwise 50~60mL without
Water-ethanol, control are dripped off in 15~20min, are stirred after dropwise addition, and continue dropwise addition 70~90mL deionized water, control rate of addition
For 1~3 drop/s, continue 70~90min of stirring after completion of dropwise addition；
(2) 3~5g boric acid is weighed to be added in 60~80mL dehydrated alcohol, be stirred after 20~30min be added to it is above-mentioned
In three-necked flask, 100~120mL mass fraction, 20% hydrochloric acid is added after being stirred 20~30min, is put into water-bath, 40
It is stirred to react 1~2h at a temperature of~60 DEG C, 30~50mL deionized water is added after reaction, is formed after being stirred transparent molten
It is 0.8~1.0 that glue, which is 2mol/L hydrochloric acid adjusting vitreosol liquid pH with concentration, and 6~8h is stirred after adjusting, is stood after stirring
50~60h obtains gel, is put into baking oven, dry 10~12h under the conditions of 80~90 DEG C, and smashes it through 80~100 meshes
Obtain dry gel powder；
(3) 2~4g magnesia, 1~3g strontium oxide strontia, 0.3~0.6g barium monoxide, the oxidation of 0.1~0.3g tri- two are weighed respectively
1~2h of ball milling in ball mill is added in aluminium, 15~18g zinc oxide, 20~30g zirconium dioxide and the above-mentioned dry gel powder of 60~80g,
Obtain mixed material；
(4) said mixture material is placed in graphite crucible, is put into silicon molybdenum high temperature furnace, first with l0~15 DEG C/min speed
Rate is warming up to 200~250 DEG C, keeps the temperature 30~50min, then be warming up to 1200~1300 DEG C with the rate of 5~10 DEG C/min, heat preservation
Glass metal is obtained after 1~2h of processing, glass metal is poured into distilled water, water quenching obtains glass disintegrating slag, and glass disintegrating slag is put into baking
In case, dry 8~10h, grinds after dry at a temperature of 100~120 DEG C, crosses 100~120 meshes, no leaded joint can be obtained
Glass.
Barium crown sealed glass softening temperature prepared by the present invention is 350~390 DEG C, and sealing temperature is 450~500 DEG C, line
The coefficient of expansion is 90 × 10-7~150 × 10-7/ DEG C, at 1000V, resistivity is greater than 2 × 1014Ω·m。
The present invention is compared with other methods, and advantageous effects are:
(1) barium crown sealed glass prepared by the present invention does not contain heavy metal lead, nontoxic, will not be strong to the body of environment and people
Health has an impact；
(2) barium crown sealed glass prepared by the present invention has high voltage performance, and at 1000V, resistivity is greater than 2 × 1014
Ω m can meet the requirement in high-pressure electronic field.
Specific embodiment
First measure 50~60mL ethyl orthosilicate be added in three-necked flask, into three-necked flask be added dropwise 50~60mL without
Water-ethanol, control are dripped off in 15~20min, are stirred after dropwise addition, and continue dropwise addition 70~90mL deionized water, control rate of addition
For 1~3 drop/s, continue 70~90min of stirring after completion of dropwise addition；3~5g boric acid is weighed again to be added in 60~80mL dehydrated alcohol,
It is added in above-mentioned three-necked flask after being stirred 20~30min, 100~120mL mass is added after being stirred 20~30min
20% hydrochloric acid of score, is put into water-bath, is stirred to react 1~2h at a temperature of 40~60 DEG C, and 30~50mL is added after reaction
Deionized water forms vitreosol liquid after being stirred, with concentration be 2mol/L hydrochloric acid adjust vitreosol liquid pH be 0.8~
1.0,6~8h is stirred after adjusting, 50~60h is stood after stirring, gel is obtained, is put into baking oven, is done under the conditions of 80~90 DEG C
Dry 10~12h, and smash it through 80~100 meshes and obtain dry gel powder；Then 2~4g magnesia, 1~3g oxidation are weighed respectively
Strontium, 0.3~0.6g barium monoxide, 0.1~0.3g aluminum oxide, 15~18g zinc oxide, 20~30g zirconium dioxide and 60~80g
Above-mentioned dry gel powder is added 1~2h of ball milling in ball mill, obtains mixed material；Said mixture material is finally placed in graphite crucible
In, it is put into silicon molybdenum high temperature furnace, is first warming up to 200~250 DEG C with l0~15 DEG C/min rate, keep the temperature 30~50min, then with
The rate of 5~10 DEG C/min is warming up to 1200~1300 DEG C, obtains glass metal after 1~2h of isothermal holding, and glass metal is poured into steaming
In distilled water, water quenching obtains glass disintegrating slag, and glass disintegrating slag is put into baking oven, and dry 8~10h, does at a temperature of 100~120 DEG C
Grinding after dry, crosses 100~120 meshes, barium crown sealed glass can be obtained.
Example 1
60mL ethyl orthosilicate is measured first to be added in three-necked flask, and 60mL dehydrated alcohol is added dropwise into three-necked flask,
Control is dripped off in 20min, is stirred after dropwise addition, and continues that 90mL deionized water is added dropwise, and control rate of addition is 3 drops/s, and knot is added dropwise
Continue to stir 90min after beam；5g boric acid is weighed again to be added in 80mL dehydrated alcohol, is added to above-mentioned three after being stirred 30min
In mouth flask, 20% hydrochloric acid of 120mL mass fraction is added after being stirred 30min, is put into water-bath, is stirred at a temperature of 60 DEG C
Reaction 2h is mixed, 50mL deionized water is added after reaction, vitreosol liquid is formed after being stirred, is 2mol/L salt with concentration
It is 1.0 that acid, which adjusts vitreosol liquid pH, and 8h is stirred after adjusting, 60h is stood after stirring, obtains gel, be put into baking oven, at 90 DEG C
Under the conditions of dry 12h, and smash it through 100 meshes and obtain dry gel powder；Then 4g magnesia, 3g strontium oxide strontia, 0.6g are weighed respectively
Ball milling in ball mill is added in barium monoxide, 0.3g aluminum oxide, 18g zinc oxide, 30g zirconium dioxide and the above-mentioned dry gel powder of 80g
2h obtains mixed material；Finally said mixture material is placed in graphite crucible, is put into silicon molybdenum high temperature furnace, first with 15 DEG C/min
Rate be warming up to 250 DEG C, keep the temperature 50min, then be warming up to 1300 DEG C with the rate of 10 DEG C/min, obtain glass after isothermal holding 2h
Glass liquid, glass metal is poured into distilled water, and water quenching obtains glass disintegrating slag, and glass disintegrating slag is put into baking oven, at a temperature of 120 DEG C
Dry 10h, grinds after dry, crosses 120 meshes, barium crown sealed glass can be obtained.
Barium crown sealed glass softening temperature prepared by the present invention is 390 DEG C, and sealing temperature is 500 DEG C, and linear expansion coefficient is
150×10-7/ DEG C, at 1000V, resistivity is 3 × 1014Ω·m。
Example 2
50mL ethyl orthosilicate is measured first to be added in three-necked flask, and 50mL dehydrated alcohol is added dropwise into three-necked flask,
Control is dripped off in 15min, is stirred after dropwise addition, and continues that 70mL deionized water is added dropwise, and control rate of addition is 1 drop/s, and knot is added dropwise
Continue to stir 70min after beam；3g boric acid is weighed again to be added in 60mL dehydrated alcohol, is added to above-mentioned three after being stirred 20min
In mouth flask, 20% hydrochloric acid of 100mL mass fraction is added after being stirred 20min, is put into water-bath, is stirred at a temperature of 40 DEG C
Reaction 1h is mixed, 30mL deionized water is added after reaction, vitreosol liquid is formed after being stirred, is 2mol/L salt with concentration
It is 0.8 that acid, which adjusts vitreosol liquid pH, and 6h is stirred after adjusting, 50h is stood after stirring, obtains gel, be put into baking oven, at 80 DEG C
Under the conditions of dry 10h, and smash it through 80 meshes and obtain dry gel powder；Then 2g magnesia, 1g strontium oxide strontia, 0.3g oxygen are weighed respectively
Change barium, 0.1g aluminum oxide, 15g zinc oxide, 20g zirconium dioxide and the above-mentioned dry gel powder of 60g, ball milling in ball mill is added
1h obtains mixed material；Finally said mixture material is placed in graphite crucible, is put into silicon molybdenum high temperature furnace, first with l0 DEG C/min
Rate be warming up to 200 DEG C, keep the temperature 30min, then be warming up to 1200 DEG C with the rate of 5 DEG C/min, obtain glass after isothermal holding 1h
Glass liquid, glass metal is poured into distilled water, and water quenching obtains glass disintegrating slag, and glass disintegrating slag is put into baking oven, at a temperature of 100 DEG C
Dry 8h, grinds after dry, sieves with 100 mesh sieve, barium crown sealed glass can be obtained.
Barium crown sealed glass softening temperature prepared by the present invention is 350 DEG C, and sealing temperature is 450 DEG C, and linear expansion coefficient is
90×10-7/ DEG C, at 1000V, resistivity is 2.5 × 1014Ω·m。
Example 3
55mL ethyl orthosilicate is measured first to be added in three-necked flask, and 55mL dehydrated alcohol is added dropwise into three-necked flask,
Control is dripped off in 17min, is stirred after dropwise addition, and continues that 80mL deionized water is added dropwise, and control rate of addition is 2 drops/s, and knot is added dropwise
Continue to stir 75min after beam；4g boric acid is weighed again to be added in 70mL dehydrated alcohol, is added to above-mentioned three after being stirred 25min
In mouth flask, 20% hydrochloric acid of 110mL mass fraction is added after being stirred 25min, is put into water-bath, stirs at 50 °C
Reaction 2h is mixed, 40mL deionized water is added after reaction, vitreosol liquid is formed after being stirred, is 2mol/L salt with concentration
It is 0.9 that acid, which adjusts vitreosol liquid pH, and 7h is stirred after adjusting, 55h is stood after stirring, obtains gel, be put into baking oven, at 85 DEG C
Under the conditions of dry 11h, and smash it through 90 meshes and obtain dry gel powder；Then 3g magnesia, 2g strontium oxide strontia, 0.5g oxygen are weighed respectively
Change barium, 0.2g aluminum oxide, 17g zinc oxide, 25g zirconium dioxide and the above-mentioned dry gel powder of 70g, ball milling in ball mill is added
1h obtains mixed material；Finally said mixture material is placed in graphite crucible, is put into silicon molybdenum high temperature furnace, first with l2 DEG C/min
Rate be warming up to 220 DEG C, keep the temperature 40min, then be warming up to 1250 DEG C with the rate of 7 DEG C/min, obtain glass after isothermal holding 1h
Glass liquid, glass metal is poured into distilled water, and water quenching obtains glass disintegrating slag, and glass disintegrating slag is put into baking oven, at a temperature of 110 DEG C
Dry 9h, grinds after dry, crosses 110 meshes, barium crown sealed glass can be obtained.
Barium crown sealed glass softening temperature prepared by the present invention is 370 DEG C, and sealing temperature is 470 DEG C, and linear expansion coefficient is
100×10-7/ DEG C, at 1000V, resistivity is 2.5 × 1014Ω·m。
Claims (1)
1. a kind of preparation method of barium crown sealed glass, it is characterised in that specific preparation step are as follows:
(1) it measures 50~60mL ethyl orthosilicate to be added in three-necked flask, the anhydrous second of 50~60mL is added dropwise into three-necked flask
Alcohol, control are dripped off in 15~20min, are stirred after dropwise addition, and continue dropwise addition 70~90mL deionized water, and control rate of addition is 1
~3 drops/s continue 70~90min of stirring after completion of dropwise addition；
(2) it weighs 3~5g boric acid to be added in 60~80mL dehydrated alcohol, is added to above-mentioned three mouthfuls after being stirred 20~30min
In flask, 100~120mL mass fraction, 20% hydrochloric acid is added after being stirred 20~30min, is put into water-bath, 40~60
It is stirred to react 1~2h at a temperature of DEG C, 30~50mL deionized water is added after reaction, forms vitreosol after being stirred
It is 0.8~1.0 that liquid, which is 2mol/L hydrochloric acid adjusting vitreosol liquid pH with concentration, and 6~8h is stirred after adjusting, stands 50 after stirring
~60h, obtains gel, is put into baking oven, dry 10~12h under the conditions of 80~90 DEG C, and smashes it through 80~100 meshes and obtain
Dry gel powder；
(3) 2~4g magnesia, 1~3g strontium oxide strontia, 0.3~0.6g barium monoxide, 0.1~0.3g aluminum oxide, 15 are weighed respectively
~18g zinc oxide, 20~30g zirconium dioxide and the above-mentioned dry gel powder of 60~80g are added 1~2h of ball milling in ball mill, must mix
Material；
(4) said mixture material is placed in graphite crucible, is put into silicon molybdenum high temperature furnace, first with l0~15 DEG C/min rate liter
Temperature keeps the temperature 30~50min to 200~250 DEG C, then is warming up to 1200~1300 DEG C with the rate of 5~10 DEG C/min, isothermal holding
Glass metal is obtained after 1~2h, and glass metal is poured into distilled water, water quenching obtains glass disintegrating slag, glass disintegrating slag is put into baking oven,
Dry 8~10h, grinds after dry at a temperature of 100~120 DEG C, crosses 100~120 meshes, barium crown sealed glass can be obtained.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610883508.XA CN106477893B (en) | 2016-10-11 | 2016-10-11 | A kind of preparation method of barium crown sealed glass |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610883508.XA CN106477893B (en) | 2016-10-11 | 2016-10-11 | A kind of preparation method of barium crown sealed glass |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106477893A CN106477893A (en) | 2017-03-08 |
| CN106477893B true CN106477893B (en) | 2019-04-05 |
Family
ID=58269521
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610883508.XA Expired - Fee Related CN106477893B (en) | 2016-10-11 | 2016-10-11 | A kind of preparation method of barium crown sealed glass |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106477893B (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007132754A1 (en) * | 2006-05-15 | 2007-11-22 | Nippon Electric Glass Co., Ltd. | Bismuth-based sealing material and bismuth-base paste material |
| CN102120693A (en) * | 2010-01-11 | 2011-07-13 | 上海歌灵新材料科技有限公司 | Lead-free sealing glass and preparation method thereof |
| WO2014049117A1 (en) * | 2012-09-28 | 2014-04-03 | Danmarks Tekniske Universitet | Glass composition for the use as a sealant |
| CN105859144A (en) * | 2016-03-29 | 2016-08-17 | 西安赛尔电子材料科技有限公司 | Sealing glass powder for electric connectors, preparation method for sealing glass powder and sealing process of sealing glass powder |
-
2016
- 2016-10-11 CN CN201610883508.XA patent/CN106477893B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007132754A1 (en) * | 2006-05-15 | 2007-11-22 | Nippon Electric Glass Co., Ltd. | Bismuth-based sealing material and bismuth-base paste material |
| CN102120693A (en) * | 2010-01-11 | 2011-07-13 | 上海歌灵新材料科技有限公司 | Lead-free sealing glass and preparation method thereof |
| WO2014049117A1 (en) * | 2012-09-28 | 2014-04-03 | Danmarks Tekniske Universitet | Glass composition for the use as a sealant |
| CN105859144A (en) * | 2016-03-29 | 2016-08-17 | 西安赛尔电子材料科技有限公司 | Sealing glass powder for electric connectors, preparation method for sealing glass powder and sealing process of sealing glass powder |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106477893A (en) | 2017-03-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100526244C (en) | Glass scintillator for thermal neutron detection and its preparation method | |
| CN107285770B (en) | A kind of purity is high zirconic acid lanthanum gadolinium powder of uniform morphology and crystalline ceramics preparation method | |
| CN104556230B (en) | Molybdenum disulfide nano laurustinus structural semiconductor material and preparation method thereof | |
| CN104018295B (en) | A kind of Infrared-Visible multi-Functional Camouflage composite cellulosic membrane and preparation method thereof | |
| CN109054452A (en) | Copper-chromium black pigment and preparation method thereof | |
| CN104926304A (en) | Gadolinium oxide ceramics and method for manufacturing same | |
| CN109835927A (en) | A kind of high temperature resistant, Gao Shushui fused magnesium oxide powder and preparation method thereof | |
| CN105174723A (en) | Method for preparing micro-crystal glass by means of desulfurized fly ash | |
| CN106477893B (en) | A kind of preparation method of barium crown sealed glass | |
| CN106316134B (en) | A kind of diopside and feldspar principal crystalline phase devitrified glass and preparation method thereof | |
| CN105481253B (en) | A kind of preparation method of compound low temperature sealing glass solder soldering paste | |
| CN102219513A (en) | Method for preparing near-zero thermal expansion composite material | |
| CN105693246B (en) | A kind of preparation method of yttrium oxide transparent ceramic | |
| CN106495487B (en) | A kind of low temperature sealing glass and its preparation and application containing Ce | |
| CN105272252A (en) | Fluorite-type Eu-doped Y2Ce2O7 nano ceramic pigment and preparation method | |
| CN110698070B (en) | Preparation method of magnesium-aluminum-silicon microcrystalline glass for LTCC (Low temperature Co-fired ceramic) packaging material | |
| CN105602564B (en) | A kind of enhanced rare-earth oxide sulfate up-conversion luminescent material of Zn and preparation method | |
| CN106086520A (en) | Zircaloy smelting technology | |
| CN102716701A (en) | Method for preparing nickel-doped bismuth silicon oxide microspheres by ultrasonic spray | |
| CN105948135A (en) | Monodisperse porous magnetic submicrosphere and preparation method thereof | |
| CN110451810A (en) | A kind of CuO doping Bi2SiO5The preparation method of polycrystalline glass | |
| CN106495489B (en) | One kind containing P2O5LED low temperature sealing glass | |
| CN103408224A (en) | Low-temperature electric melting formula for transparent glass, process method thereof and transparent glass prepared through low-temperature electric melting formula and process method | |
| CN103951220B (en) | Rare earth ion doped BaBr2Devitrified glass and preparation method thereof | |
| CN108892979A (en) | One kind is for environment friendly heat resistant refractory coating and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| TA01 | Transfer of patent application right | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20190313 Address after: 528478 No. 86 Shunxing North Road, Henglan Town, Zhongshan City, Guangdong Province Applicant after: ZHONGSHAN CHUNGUANG GLASS CO.,LTD. Address before: 213164 No. 151, Yanjiang West Road, Wei village, Chun Jiang Town, Xinbei District, Changzhou, Jiangsu Applicant before: CHANGZHOU DINGRI ENVIRONMENTAL PROTECTION TECHNOLOGY Co.,Ltd. |
|
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20190405 Termination date: 20211011 |