CN107043216A - SiO2Modified low temperature sealing glass and its preparation and application method - Google Patents
SiO2Modified low temperature sealing glass and its preparation and application method Download PDFInfo
- Publication number
- CN107043216A CN107043216A CN201710275052.3A CN201710275052A CN107043216A CN 107043216 A CN107043216 A CN 107043216A CN 201710275052 A CN201710275052 A CN 201710275052A CN 107043216 A CN107043216 A CN 107043216A
- Authority
- CN
- China
- Prior art keywords
- glass
- sio
- low temperature
- temperature sealing
- sealing glass
- 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.)
- Pending
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
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Glass Compositions (AREA)
Abstract
The invention discloses a kind of SiO2ZnO, Na in modified low temperature sealing glass and its preparation and application, its raw material composition2O、P2O5、SiO2Mol ratio be 33 ~ 45：15~25：22~40：5~25.The present invention passes through SiO2Introduce SiO4Tetrahedron, utilizes the stable PO of its structural similarity4Tetrahedron, with reinforcing glass network structure, improves its heat endurance, and good stability can still be kept by it is soaked 1000 hours in 80 DEG C of hot water；And SiO2Introducing can promote the densification of glass network structure, reduce oxygen transmission rate.Introduce the ZnO and P of high concentration2O5, the transformetion range of the glass is reduced to 380 435 DEG C；Na2O introducing can reduce the fusion temperature of glass, and improve its sealing property.Gained glass material of the invention is applied to LED fluorescent powder sealing-in, electronic material and other low-temperature sealing fields.
Description
Technical field
The invention belongs to seal glass preparing technical field, and in particular to a kind of SiO2Modified low temperature sealing glass and its
Prepare and application method.
Background technology
Low temperature sealing glass（Sealing temperature<600 DEG C) due to its good heat resistance and chemical stability, high machinery it is strong
Degree, and it is widely used in the various fields such as electric slurry, electrovacuum and microelectric technique, the energy, aerospace, automobile, such as luminous
Diode（LED）Fluorescent material sealing-in in, whether the function admirable of seal, sealing materials directly results in the actual use performance of battery.Envelope
Connect glass and can also be used for mutual sealing-in between glass, ceramics, metal, semiconductor.But, research both at home and abroad at present is generally used
It is the seal, sealing materials containing Pb, this will be polluted to environment.In addition, phosphate glass is because with melting temperature sealing is low, the coefficient of expansion
Adjustable range is wide, price is low, obtain extensive concern the advantages of can substantially reduce environmental pollution.
Patent application（201310259302.6）Disclose a kind of low-temperature lead-free glass dust and preparation method thereof, but the body
Another poisonous material Sb is introduced in system, environmental issue is not solved.And patent application（201210366375.0）It is open
A kind of lead-free glass material and preparation method thereof, it passes through P2O5、K2O、Na2O、ZrO2、TiO2Composition design Deng raw material is kept away
Exempt from environmental pollution, but the softening range of the glass is 500 ~ 600 DEG C, it is difficult to meet low-temperature sealing especially electronics member
The requirement of part low temperature Fast Sintering.The previous work of this seminar is found that B-Bi-Zn system glass can solve the above problems, and Shen
Please patent.However, B-Bi-Zn system glass is because contain transition-metal ions Bi so that glass darkens in sintering process,
So that light transmission rate step-down of the glass in visible light wave range, and B-Bi-Zn system glass is easy to crystallization, is difficult in sealing-in process
Control.Therefore, B-Bi-Zn system glass is limited in terms of optical property by larger.
The content of the invention
It is an object of the invention to provide a kind of SiO2Modified low temperature sealing glass and its preparation and application method, its turn
Temperature ranges as low as 380-435 DEG C, and with good thermal stability and sealing property, it is adaptable to LED fluorescent powder sealing-in, electronics
Material and other low-temperature sealing fields.
To achieve the above object, the present invention is adopted the following technical scheme that：
A kind of SiO2ZnO, Na in modified low temperature sealing glass, its raw material composition2O、P2O5、SiO2Mol ratio be 33 ~ 45：
15~25：22~40：5~25；Preferably, ZnO, Na2O、P2O5、SiO2Mol ratio be 38 ~ 40.5：18~22：27~29.5：10~
15。
The SiO2The preparation method of modified low temperature sealing glass comprises the following steps：
（1）By ZnO, Na2O、P2O5、SiO2It is uniformly mixed according to a ratio, is founded in 880-1100 DEG C and be incubated 1-4h, obtains glass and melt
Liquid；Then gained glass melts are subjected to chilling, obtain glass frit；Glass frit is crushed again, grinding or ball milling, sieving
After obtain glass powder；
（2）Gained glass powder and binding agent, dispersant and solvent are mixed into slurry, ball milling makes it uniformly divide in ball mill
Dissipate, after flow casting molding, natural drying, the idiosome of shape, that is, be made the low temperature sealing glass needed for being cut into.
Step（2）Middle glass powder, binding agent, the consumption percentage of dispersant and solvent are：Glass powder
80 ~ 84%, binding agent 1.5 ~ 2%, dispersant 0.5 ~ 2%, solvent 14 ~ 17%, its percetage by weight sum are 100%；
Wherein, binding agent used is one kind or several in epoxy resin, methylcellulose, polyvinyl butyral resin, polyvinyl alcohol
Kind；
Dispersant used is the one or more in fish oil, polyacrylic acid, polyvinyl alcohol, polyacrylamide；
Solvent for use is the one or more in water, ethanol, isopropanol, n-butanol, toluene, dimethylbenzene, acetone.
The SiO2The application method of modified low temperature sealing glass, is to be placed in the low temperature sealing glass to treat sealing-in portion
Position, 400-500 DEG C is warming up in electric furnace with 1-5 DEG C/min speed, 0.5-1h is incubated, then with 1-5 DEG C/min speed
500-650 DEG C is warming up to, isothermal holding 0.5-1h completes sealing-in.
The remarkable advantage of the present invention is：
（1）The present invention passes through SiO2Introduce SiO4Tetrahedron, with reinforcing glass network structure, so as to improve its heat endurance, drops
Low tendency towards devitrification, good stability can still be kept by gained glass material is soaked 1000 hours in 80 DEG C of hot water；Meanwhile,
SiO2Introducing can promote the densification of glass network structure, reduce oxygen transmission rate；
（2）Present invention introduces the ZnO of high concentration and P2O5, by playing the coordinative role of the two, so that the transformation temperature of the glass
Degree scope is reduced to 380-435 DEG C；
（3）Na in the present invention2O introducing can reduce the glass melting temperature of glass, and can improve its sealing property；
（4）Preparing raw material of the present invention is simple and easy to get, process stabilizing, has reached practical and industrialized condition.
Brief description of the drawings
Fig. 1 is thermal dilatometry of the low temperature sealing glass under the conditions of parallel laboratory test obtained by embodiment 1-4.
Fig. 2 is DSC curve of the low temperature sealing glass under the conditions of parallel laboratory test obtained by embodiment 1-4.
Embodiment
A kind of SiO2ZnO, Na in modified low temperature sealing glass, its raw material composition2O、P2O5、SiO2Mol ratio for 33 ~
45：15~25：22~40：5~25；Preferably, ZnO, Na2O、P2O5、SiO2Mol ratio be 38 ~ 40.5：18~22：27~29.5：
10~15。
The SiO2The preparation method of modified low temperature sealing glass comprises the following steps：
（1）By ZnO, Na2O、P2O5、SiO2It is uniformly mixed according to a ratio, is founded in 880-1100 DEG C and be incubated 1-4h, obtains glass and melt
Liquid；Then gained glass melts are subjected to chilling, obtain glass frit；Glass frit is crushed again, grinding or ball milling, sieving
After obtain glass powder；
（2）Gained glass powder and binding agent, dispersant and solvent are mixed into slurry, ball milling makes it uniformly divide in ball mill
Dissipate, after flow casting molding, natural drying, the idiosome of shape, that is, be made the low temperature sealing glass needed for being cut into.
Step（2）Middle glass powder, binding agent, the consumption percentage of dispersant and solvent are：Glass powder
80 ~ 84%, binding agent 1.5 ~ 2%, dispersant 0.5 ~ 2%, solvent 14 ~ 17%, its percetage by weight sum are 100%；
Wherein, binding agent used is one kind or several in epoxy resin, methylcellulose, polyvinyl butyral resin, polyvinyl alcohol
Kind；
Dispersant used is the one or more in fish oil, polyacrylic acid, polyvinyl alcohol, polyacrylamide；
Solvent for use is the one or more in water, ethanol, isopropanol, n-butanol, toluene, dimethylbenzene, acetone.
The SiO2The application method of modified low temperature sealing glass, is to be placed in the low temperature sealing glass to treat sealing-in portion
Position, 400-500 DEG C is warming up in electric furnace with 1-5 DEG C/min speed, 0.5-1h is incubated, then with 1-5 DEG C/min speed
500-650 DEG C is warming up to, isothermal holding 0.5-1h completes sealing-in.
In order that content of the present invention easily facilitates understanding, with reference to embodiment to of the present invention
Technical scheme is described further, but the present invention is not limited only to this.
The component proportion table of low temperature sealing glass in the embodiment 1-4 of table 1（Mole percent, %）
Embodiment 1：
Proportioning according to embodiment 1 in table 1 weighs a certain amount of analysis pure raw material（ZnO、Na2O、P2O5、SiO2）, use planet ball
Grinding machine ball milling is well mixed 24 hours it；Then powder is put into platinum crucible, be placed in chamber type electric resistance furnace, in air atmosphere
Under be heated to 900 DEG C with 3 DEG C/min, be incubated 1h, obtain glass melts；Then take out crucible, by gained glass melts pour into from
Chilling in sub- water, glass frit is obtained through drying；Gained glass frit is ground, 100 mesh sieves is crossed, obtains glass powder.By institute
Glass powder is obtained with polyvinyl alcohol, fish oil, ethanol and toluene by weight 80:2:1:10:7 are mixed into slurry, in ball mill
Ball milling makes its dispersed, and the idiosome of shape, produces low temperature sealing glass needed for being cut into after flow casting molding, natural drying.
The example is to preferably constitute.
Gained low temperature sealing glass is placed in and treats sealing-in position, 400 DEG C are warming up to 2 DEG C/min speed in electric furnace,
And 1h is incubated, 500 DEG C then are warming up to 2 DEG C/min speed, isothermal holding 1h completes sealing-in.
Glass melts after insulation are poured into the stainless steel grinding tool after preheating, Φ=10mm, d=25mm glass circle is obtained
Post, is tested on NETZSCH DIL 402EP thermal dilatometers with the 10 DEG C/min rate of heat addition, obtains glass transition point and softening
Point, its result is shown in Fig. 1,2.Fig. 1,2 show, add 5% SiO2The glass transition point of seal glass be 388 DEG C, softening point is
394 DEG C, linear expansion coefficient is 1.41 × 10-5/K。
Weight-loss ratio after gained low temperature sealing glass is placed 1000 hours in 80 DEG C of hot water is less than 0.001%.In oxygen transmission rate
Its oxygen transmission rate is measured under test condition for 1cm3/m2·d。
Embodiment 2：
Proportioning according to embodiment 2 in table 1 weighs a certain amount of analysis pure raw material（ZnO、Na2O、P2O5、SiO2）, use planet ball
Grinding machine ball milling is well mixed 24 hours it；Then powder is put into platinum crucible, be placed in chamber type electric resistance furnace, in air atmosphere
Under be heated to 950 DEG C with 3 DEG C/min, be incubated 1h, obtain glass melts；Then take out crucible, by gained glass melts pour into from
Chilling in sub- water, glass frit is obtained through drying；Gained glass frit is ground, 100 mesh sieves is crossed, obtains glass powder.By institute
Glass powder is obtained with methylcellulose, polyvinyl alcohol, n-butanol and acetone by weight 82:2:2:8:6 are mixed into slurry, in ball
Ball milling makes its dispersed in grinding machine, and the idiosome of shape, produces low-temperature sealing needed for being cut into after flow casting molding, natural drying
Glass.The example is to preferably constitute.
Gained low temperature sealing glass is placed in and treats sealing-in position, 400 DEG C are warming up to 2 DEG C/min speed in electric furnace,
And 1h is incubated, 500 DEG C then are warming up to 2 DEG C/min speed, isothermal holding 1h completes sealing-in.
Glass melts after insulation are poured into the stainless steel grinding tool after preheating, Φ=10mm, d=25mm glass circle is obtained
Post, is tested on NETZSCH DIL 402EP thermal dilatometers with the 10 DEG C/min rate of heat addition, obtains glass transition point and softening
Point, its result is shown in Fig. 1,2.Fig. 1,2 show, add 10% SiO2The glass transition point of seal glass be 409 DEG C, softening point is
415 DEG C, linear expansion coefficient is 1.39 × 10-5/K。
Weight-loss ratio after gained low temperature sealing glass is placed 1000 hours in 80 DEG C of hot water is less than 0.001%.In oxygen transmission rate
Its oxygen transmission rate is measured under test condition for 0.1cm3/m2·d。
Embodiment 3：
Proportioning according to embodiment 3 in table 1 weighs a certain amount of analysis pure raw material（ZnO、Na2O、P2O5、SiO2）, use planet ball
Grinding machine ball milling is well mixed 24 hours it；Then powder is put into platinum crucible, be placed in chamber type electric resistance furnace, in air atmosphere
Under be heated to 1000 DEG C with 3 DEG C/min, be incubated 1h, obtain glass melts；Then take out crucible, by gained glass melts pour into from
Chilling in sub- water, glass frit is obtained through drying；Gained glass frit is ground, 100 mesh sieves is crossed, obtains glass powder.By institute
Glass powder is obtained with epoxy resin, polyacrylamide, isopropanol and toluene by weight 84:1.5:0.5:9:5 are mixed into slurry,
Ball milling makes its dispersed in ball mill, and the idiosome of shape, produces low temperature needed for being cut into after flow casting molding, natural drying
Seal glass.The example is to preferably constitute.
Gained low temperature sealing glass is placed in and treats sealing-in position, 450 DEG C are warming up to 2 DEG C/min speed in electric furnace,
And 1h is incubated, 550 DEG C then are warming up to 2 DEG C/min speed, isothermal holding 1h completes sealing-in.
Glass melts after insulation are poured into the stainless steel grinding tool after preheating, Φ=10mm, d=25mm glass circle is obtained
Post, is tested on NETZSCH DIL 402EP thermal dilatometers with the 10 DEG C/min rate of heat addition, obtains glass transition point and softening
Point, its result is shown in Fig. 1,2.Fig. 1,2 show, add 15% SiO2The glass transition point of seal glass be 419 DEG C, softening point is
427 DEG C, linear expansion coefficient is 1.35 × 10-5/K。
Weight-loss ratio after gained low temperature sealing glass is placed 1000 hours in 80 DEG C of hot water is less than 0.001%.In oxygen transmission rate
Its oxygen transmission rate is measured under test condition for 0.05cm3/m2·d。
Embodiment 4：
Proportioning according to embodiment 4 in table 1 weighs a certain amount of analysis pure raw material（ZnO、Na2O、P2O5、SiO2）, use planet ball
Grinding machine ball milling is well mixed 24 hours it；Then powder is put into platinum crucible, be placed in chamber type electric resistance furnace, in air atmosphere
Under be heated to 1050 DEG C with 3 DEG C/min, be incubated 1h, obtain glass melts；Then take out crucible, by gained glass melts pour into from
Chilling in sub- water, glass frit is obtained through drying；Gained glass frit is ground, 100 mesh sieves is crossed, obtains glass powder.By institute
Glass powder is obtained with polyvinyl butyral resin, polyacrylic acid, isopropanol and acetone by weight 83:2:1:9:5 are mixed into slurry,
Ball milling makes its dispersed in ball mill, and the idiosome of shape, produces low temperature needed for being cut into after flow casting molding, natural drying
Seal glass.The example is to preferably constitute.
Gained low temperature sealing glass is placed in and treats sealing-in position, 450 DEG C are warming up to 2 DEG C/min speed in electric furnace,
And 1h is incubated, 550 DEG C then are warming up to 2 DEG C/min speed, isothermal holding 1h completes sealing-in.
Glass melts after insulation are poured into the stainless steel grinding tool after preheating, Φ=10mm, d=25mm glass circle is obtained
Post, is tested on NETZSCH DIL 402EP thermal dilatometers with the 10 DEG C/min rate of heat addition, obtains glass transition point and softening
Point, its result is shown in Fig. 1,2.Fig. 1,2 show, add 20% SiO2Seal glass glass transition point be 432 DEG C, softening temperature
For 448 DEG C, linear expansion coefficient is 1.32 × 10-5/K。
Weight-loss ratio after gained low temperature sealing glass is placed 1000 hours in 80 DEG C of hot water is about 0.001%.In oxygen transmission rate
Oxygen transmission rate is measured under test condition for 0.05cm3/m2·d。
The present invention is obtained by above-described embodiment can implement the SiO of sealing-in in low temperature2Modified seal glass.It is significantly imitated
Fruit is embodied a concentrated reflection of, and it has good stability and excellent air-tightness in use environment, it is adaptable to which LED fluorescent powder is sealed
Connect, electronic material and other low-temperature sealing fields.
The foregoing is only presently preferred embodiments of the present invention, all equivalent changes done according to scope of the present invention patent with
Modification, should all belong to the covering scope of the present invention.
Claims (7)
1. a kind of SiO2Modified low temperature sealing glass, it is characterised in that：ZnO, Na in raw material composition2O、P2O5、SiO2Mole
Than for 33 ~ 45：15~25：22~40：5~25.
2. SiO according to claim 12Modified low temperature sealing glass, it is characterised in that：ZnO、Na2O、P2O5、SiO2's
Mol ratio is 38 ~ 40.5：18~22：27~29.5：10~15.
3. one kind prepares SiO as claimed in claim 12The method of modified low temperature sealing glass, it is characterised in that：Including with
Lower step：
（1）By ZnO, Na2O、P2O5、SiO2It is uniformly mixed according to a ratio, is founded in 880-1100 DEG C and be incubated 1-4h, obtains glass and melt
Liquid；Then gained glass melts are subjected to chilling, obtain glass frit；Glass frit is crushed again, grinding or ball milling, sieving
After obtain glass powder；
（2）Gained glass powder and binding agent, dispersant and solvent are mixed into slurry, ball milling makes its dispersed, through curtain coating
After shaping, natural drying, the idiosome of shape, that is, be made the low temperature sealing glass needed for being cut into.
4. SiO according to claim 32The preparation method of modified low temperature sealing glass, it is characterised in that：Step（2）In
Binding agent used is the one or more in epoxy resin, methylcellulose, polyvinyl butyral resin, polyvinyl alcohol.
5. SiO according to claim 32The preparation method of modified low temperature sealing glass, it is characterised in that：Step（2）In
Dispersant used is the one or more in fish oil, polyacrylic acid, polyvinyl alcohol, polyacrylamide.
6. SiO according to claim 32The preparation method of modified low temperature sealing glass, it is characterised in that：Step（2）In
Solvent for use is the one or more in water, ethanol, isopropanol, n-butanol, toluene, dimethylbenzene, acetone.
7. a kind of SiO as claimed in claim 12The application method of modified low temperature sealing glass, it is characterised in that：Will be described
Low temperature sealing glass, which is placed in, treats sealing-in position, and 400-500 DEG C is warming up to 1-5 DEG C/min speed in electric furnace, is incubated 0.5-
1h, is then warming up to 500-650 DEG C, isothermal holding 0.5-1h completes sealing-in with 1-5 DEG C/min speed.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710275052.3A CN107043216A (en) | 2017-04-25 | 2017-04-25 | SiO2Modified low temperature sealing glass and its preparation and application method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710275052.3A CN107043216A (en) | 2017-04-25 | 2017-04-25 | SiO2Modified low temperature sealing glass and its preparation and application method |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN107043216A true CN107043216A (en) | 2017-08-15 |
Family
ID=59545778
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710275052.3A Pending CN107043216A (en) | 2017-04-25 | 2017-04-25 | SiO2Modified low temperature sealing glass and its preparation and application method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107043216A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108483919A (en) * | 2018-05-09 | 2018-09-04 | 哈尔滨工业大学 | A kind of preparation method of glass adhesive tape |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1696071A (en) * | 2004-05-11 | 2005-11-16 | 日本电气硝子株式会社 | Sealing glass |
| CN101007706A (en) * | 2007-01-19 | 2007-08-01 | 东华大学 | Lead-free phosphate sealed glass for electrothermal tube and its preparation method |
| CN101157518A (en) * | 2007-09-14 | 2008-04-09 | 东华大学 | Sealing glass member for electrothermal tube and preparation method thereof |
| CN101367615A (en) * | 2008-09-28 | 2009-02-18 | 陈培 | Sealing glass with additive nano-aluminum oxide and method of manufacturing the same |
| CN101863622A (en) * | 2009-04-15 | 2010-10-20 | 李胜春 | Nanooxide-doped red solder glass and preparation method thereof |
| CN106495489A (en) * | 2016-11-01 | 2017-03-15 | 福州大学 | One kind contains P2O5LED low temperature sealing glass |
-
2017
- 2017-04-25 CN CN201710275052.3A patent/CN107043216A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1696071A (en) * | 2004-05-11 | 2005-11-16 | 日本电气硝子株式会社 | Sealing glass |
| CN101007706A (en) * | 2007-01-19 | 2007-08-01 | 东华大学 | Lead-free phosphate sealed glass for electrothermal tube and its preparation method |
| CN101157518A (en) * | 2007-09-14 | 2008-04-09 | 东华大学 | Sealing glass member for electrothermal tube and preparation method thereof |
| CN101367615A (en) * | 2008-09-28 | 2009-02-18 | 陈培 | Sealing glass with additive nano-aluminum oxide and method of manufacturing the same |
| CN101863622A (en) * | 2009-04-15 | 2010-10-20 | 李胜春 | Nanooxide-doped red solder glass and preparation method thereof |
| CN106495489A (en) * | 2016-11-01 | 2017-03-15 | 福州大学 | One kind contains P2O5LED low temperature sealing glass |
Non-Patent Citations (2)
| Title |
|---|
| 王伟等: "《玻璃生产工艺技术》", 31 December 2013, 武汉理工大学出版社 * |
| 田良英等: "《新编玻璃工艺学》", 30 June 2009, 中国轻工业出版社 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108483919A (en) * | 2018-05-09 | 2018-09-04 | 哈尔滨工业大学 | A kind of preparation method of glass adhesive tape |
| CN108483919B (en) * | 2018-05-09 | 2020-12-18 | 哈尔滨工业大学 | Preparation method of glass adhesive tape |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103626398B (en) | A kind of crystallization type lead-free low-temperature seal glass and preparation thereof and using method | |
| CN104556967B (en) | The development of silicon dioxide aerogel powder/vitrified bond composite heat-insulated material | |
| CN103030278B (en) | Glass sealing material, as well as preparation and using methods thereof | |
| CN103641314B (en) | A kind of sealing glass ceramic containing ZnO and preparation and application thereof | |
| CN103739201B (en) | A kind of intermediate temperature SOFC sealing glass ceramic and preparation and application thereof | |
| CN105670377A (en) | Microcrystal glass powder containing moderate-high temperature glass printing ink and preparation method thereof | |
| CN106495490B (en) | One kind containing SiO2LED low temperature sealing glass | |
| CN106495487B (en) | A kind of low temperature sealing glass and its preparation and application containing Ce | |
| CN105481253B (en) | A kind of preparation method of compound low temperature sealing glass solder soldering paste | |
| CN107043215A (en) | A kind of low temperature sealing glass of lanthana modification and its preparation and application method | |
| CN107043216A (en) | SiO2Modified low temperature sealing glass and its preparation and application method | |
| CN107971937A (en) | A kind of vitrified CBN wheel bonding agent for harmonic reducer of robot | |
| CN106495489B (en) | One kind containing P2O5LED low temperature sealing glass | |
| CN106927680A (en) | ZrO2Modified low temperature sealing glass and its preparation and application method | |
| CN106495492B (en) | A kind of low temperature sealing glass and its preparation and application containing Sn | |
| CN108328929A (en) | A kind of high-temperature high-insulation glass and preparation method thereof for electric heating pipe port sealing-in | |
| CN106477894B (en) | A kind of low temperature sealing glass and its preparation and application containing Fe | |
| CN102351403B (en) | Method for preparing ultrafine glass powder used for solar battery slurry | |
| CN106430979B (en) | A kind of low temperature sealing glass and its preparation and application containing Mn | |
| CN106946461B (en) | A kind of CeO2Modified low temperature sealing glass and its preparation and application method | |
| CN107082567A (en) | A kind of alumina modified low temperature sealing glass and its preparation and application method | |
| CN104844196B (en) | Thermal sensitive ceramic material with Curie temperature | |
| CN106495491B (en) | One kind containing Al2O3LED low temperature sealing glass | |
| CN101774765A (en) | Frit of fuse substrate in monolithic structure and manufacture method thereof | |
| CN106336118B (en) | A kind of preparation method of waterproof fused quartz ceramic product |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20170815 |
|
| RJ01 | Rejection of invention patent application after publication |