CN106477894B - A kind of low temperature sealing glass and its preparation and application containing Fe - Google Patents
A kind of low temperature sealing glass and its preparation and application containing Fe Download PDFInfo
- Publication number
- CN106477894B CN106477894B CN201610936671.8A CN201610936671A CN106477894B CN 106477894 B CN106477894 B CN 106477894B CN 201610936671 A CN201610936671 A CN 201610936671A CN 106477894 B CN106477894 B CN 106477894B
- Authority
- CN
- China
- Prior art keywords
- glass
- sealing
- low temperature
- temperature sealing
- preparation
- 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.)
- Active
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
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 low temperature sealing glass and its preparation and application containing Fe, raw material group become B2O3、Bi2O3, ZnO and Fe2O3.The present invention passes through Bi2O3With B2O3Coordinative role reduce glass softening temperature, realize low-temperature sealing；By adding Fe2O3The softening temperature of seal glass, and the refractive index of energy stabilized glass, and the internal magnetic Fe of tool generated can not only be further decreased3O4, the automation application efficiency of sealing-in process can be improved.It is simple and easy to get that the present invention prepares raw material, process stabilizing, save the cost, is suitable for photoelectric material and other low-temperature precise encapsulation fields.
Description
Technical field
The invention belongs to low-temperature precise packaged glass fields, and in particular to a kind of low temperature sealing glass and its preparation containing Fe
And application method.
Background technique
Low temperature sealing glass (fusion temperature and sealing temperature < 600 DEG C), due to its good heat resistance and chemical stability,
High mechanical strength is widely used in the various fields such as electric slurry, electrovacuum and microelectric technique, the energy, aerospace, automobile,
Such as in solid oxide fuel cell (SOFC), the performance of seal, sealing materials it is excellent whether directly result in the actual use of battery
Performance；In the application of electronic material, the stability of seal glass also has extreme influence to light decay rate of LED etc..Meanwhile sealing-in
Glass can also be used for the mutual sealing-in between glass, ceramics, metal, semiconductor.For environment caused by the seal, sealing materials containing Pb
Pollution problem, it is contemplated that Bi and Pb because its in the periodic table of elements it is adjacent, there is similar physico-chemical property, bismuthate glass obtains
Obtained extensive concern.For example, the CN201310675606.0 patent that this seminar applies and authorizes, discloses a kind of containing Bi2O3
Crystallization type lead-free low-temperature seal glass and its preparation and application, better meet low-temperature sealing especially electronic component
The requirement of low temperature Fast Sintering.However, this seminar it is nearest the study found that the Bi element in glass is easy in temperature-rise period
Variation of valence (Bi occurs3+To Bi5+Transformation), it is difficult to guarantee the stability of the stability especially refractive index of seal glass.
Summary of the invention
To solve the above-mentioned problems, the present invention provides a kind of containing the low temperature sealing glass of Fe and its side of making and using
Method.The present invention passes through Bi2O3With B2O3Coordinative role reduce glass softening temperature, realize low-temperature sealing；By adding Fe2O3
The softening temperature of seal glass, and the refractive index of energy stabilized glass can not only be further decreased, and internal generation has
Magnetic Fe3O4, the automation application efficiency of sealing-in process can be improved.
The present invention is to be implemented by following technical solution:
A kind of raw material group of the low temperature sealing glass containing Fe becomes B2O3、Bi2O3, ZnO and Fe2O3, molar ratio be 10 ~
50:20 ~ 40:5 ~ 30:0 ~ 30.
A kind of low temperature sealing glass containing Fe, raw material B2O3、Bi2O3, ZnO and Fe2O3Molar ratio be 20 ~ 40:25 ~
35:5 ~ 30:10 ~ 25.
Preparation as described above the low temperature sealing glass containing Fe method the following steps are included:
(1) raw material is uniformly mixed；It is melted by 900-1000 DEG C, soaking time 1-4 hours；To the glass melted
Liquid carries out chilling, obtains glass frit；Then, glass frit is crushed, grinding or ball milling obtain glass powder after sieving；
(2) glass powder and binder, dispersing agent and solvent are mixed into slurry, ball milling disperses in the ball mill；
Tape casting spontaneously dries, is then cut into the idiosome of required shape, glass sealing material is made.
The binder of the step (2) is epoxy resin, methylcellulose, polyvinyl butyral, in polyvinyl alcohol
One or more of mixtures.
The dispersing agent of the step (2) is one or more of fish oil, polyacrylic acid, polyvinyl alcohol, polyacrylamide
Mixture.
The solvent of the step (2) is one of water, ethyl alcohol, isopropanol, n-butanol, toluene, dimethylbenzene, acetone or several
The mixture of kind.
Glass sealing material is placed in sealing-in position, is heated up in electric furnace with the rate of 1-5 DEG C/min, 300-400 DEG C
Then heat preservation 0.5-2 hours is warming up to 450-500 DEG C of sealing-in with the rate of 1-5 DEG C/min and handles 0.5-2 hours, that is, completes envelope
Dress.
Remarkable advantage of the invention is:
(1) pass through Bi2O3With B2O3Coordinative role reduce glass softening temperature, realize low-temperature sealing；
(2) Fe in the glass network of melting chilling preparation2+It is changed into Fe in heating process3+, prevent Bi in glass3+To Bi5+
Transformation, the refractive index of stabilized glass；
(3) Fe ion can not only reduce the softening temperature of seal glass as network ligand, and glass is adjusted
The coefficient of expansion significantly improves the sealing property of seal glass；
(4) part Fe in glass2+It is oxidized to Fe3+, with residual F e2+It constitutes and has magnetic Fe3O4, seal glass is enable to adopt
It is picked and placed with electronic device, to realize the automation of sealing-in process；
(5) the preparation low in raw material price that the present invention selects, process stabilizing have reached practical and industrialized condition.
Detailed description of the invention
Fig. 1 is the thermal dilatometry for adding the low temperature sealing glass of different Fe contents.
Fig. 2 is the DSC curve for adding the low temperature sealing glass of different Fe contents.
Specific embodiment
A kind of raw material group of the low temperature sealing glass containing Fe becomes B2O3、Bi2O3, ZnO and Fe2O3, molar ratio be 10 ~
50:20 ~ 40:5 ~ 30:0 ~ 30.
Preparation as described above the low temperature sealing glass containing Fe method the following steps are included:
(1) raw material is uniformly mixed；It is melted by 900-1000 DEG C, soaking time 1-4 hours；To the glass melted
Liquid carries out chilling, obtains glass frit；Then, glass frit is crushed, grinding or ball milling obtain glass powder after sieving；
(2) glass powder and binder, dispersing agent and solvent are mixed into slurry, ball milling disperses in the ball mill；
Tape casting spontaneously dries, is then cut into the idiosome of required shape, glass sealing material is made.
The binder of the step (2) is epoxy resin, methylcellulose, polyvinyl butyral, in polyvinyl alcohol
One or more of mixtures.
The dispersing agent of the step (2) is one or more of fish oil, polyacrylic acid, polyvinyl alcohol, polyacrylamide
Mixture.
The solvent of the step (2) is one of water, ethyl alcohol, isopropanol, n-butanol, toluene, dimethylbenzene, acetone or several
The mixture of kind.
Glass sealing material is placed in sealing-in position, is heated up in electric furnace with the rate of 1-5 DEG C/min, 300-400 DEG C
Then heat preservation 0.5-2 hours is warming up to 450-500 DEG C of sealing-in with the rate of 1-5 DEG C/min and handles 0.5-2 hours, that is, completes envelope
Dress.
Table 1 is the sealing glass composition table (mole percent) in embodiment 1-5
Embodiment 1
According to the proportion of each component of 1 embodiment 1 of table, analysis pure raw material (B is weighed respectively2O3、Bi2O3、ZnO、Fe2O3),
It was uniformly mixed with planetary ball mill ball milling 24 hours；Then powder is put into platinum crucible, is placed in the air gas of chamber type electric resistance furnace
In atmosphere, 1000 DEG C are heated to 3 DEG C/min, keeps the temperature 1 hour；Then, crucible is taken out, melt is poured into chilling in deionized water,
The dry fragment for obtaining glass melt；Grinding, sieves with 100 mesh sieve, obtains glass powder.By glass powder and polyvinyl alcohol, fish oil, second
Pure and mild toluene (weight ratio is followed successively by 80%, 2%, 1%, 10%, 7%) is mixed into slurry, and ball milling disperses in the ball mill；Curtain coating
Molding spontaneously dries, is then cut into the idiosome of required shape；Idiosome is placed in sealing-in position, with 2 DEG C/min in electric furnace
Rate heating, keep the temperature 1 hour at 400 DEG C, 500 DEG C of sealing-ins be then warming up to the rate of 2 DEG C/min and are handled 2 hours, i.e., it is complete
At encapsulation.The example is to preferably constitute.Melt after heat preservation is poured into the stainless steel grinding tool after preheating, acquisition Φ=10mm, d=
The glass cylinder of 25mm is tested on NETZSCH DIL 402EP thermal dilatometer with the rate of heat addition of 10 DEG C/min, and glass is obtained
Transition point and softening point.Fig. 1,2 show to add the Fe of 10% molar fraction2O3Seal glass glass transition point be 379.8
DEG C, softening point is 418.9 DEG C, and linear expansion coefficient is 1.13 × 10-5/K.The refractive index of the glass is 1.8 ± 0.2, and is not added with
Fe2O3Glass refractive index be 1.8 ± 0.4.
Embodiment 2
According to the proportion of each component of 1 embodiment 2 of table, analysis pure raw material (B is weighed respectively2O3、Bi2O3、ZnO、Fe2O3),
It was uniformly mixed with planetary ball mill ball milling 24 hours；Then powder is put into platinum crucible, is placed in the air gas of chamber type electric resistance furnace
In atmosphere, 980 DEG C are heated to 3 DEG C/min, keeps the temperature 1 hour；Then, crucible is taken out, melt is poured into chilling in deionized water, is done
The dry fragment for obtaining glass melt；Grinding, sieves with 100 mesh sieve, obtains glass powder.By glass powder and methylcellulose, polyethylene
Alcohol, n-butanol and acetone (weight ratio is followed successively by 82%, 2%, 2%, 8%, 6%) are mixed into slurry, in the ball mill ball milling point
It dissipates；Tape casting spontaneously dries, is then cut into the idiosome of required shape；Idiosome is placed in sealing-in position, in electric furnace with
The rate of 2 DEG C/min heats up, and keeps the temperature 1 hour at 380 DEG C, and it is small to be then warming up to 480 DEG C of sealing-in processing 1 with the rate of 2 DEG C/min
When, that is, complete encapsulation.The example is to preferably constitute.Melt after heat preservation is poured into the stainless steel grinding tool after preheating, acquisition Φ=
The glass cylinder of 10mm, d=25mm are tested on NETZSCH DIL 402EP thermal dilatometer with the rate of heat addition of 10 DEG C/min,
Obtain glass transition point and softening point.Fig. 1,2 show to add the Fe of 15% molar fraction2O3Seal glass glass transition point
It is 362.7 DEG C, softening point is 398.4 DEG C, and linear expansion coefficient is 1.26 × 10-5/K.The refractive index of the glass is 1.8 ± 0.1, and
It is not added with Fe2O3Glass refractive index be 1.8 ± 0.4.
Embodiment 3
According to the proportion of 1 embodiment of table, 3 each component, analysis pure raw material (B is weighed respectively2O3、Bi2O3、ZnO、Fe2O3), it uses
It is uniformly mixed within planetary ball mill ball milling 24 hours；Then powder is put into platinum crucible, is placed in the air atmosphere of chamber type electric resistance furnace
In, 950 DEG C are heated to 3 DEG C/min, keeps the temperature 1 hour；Then, crucible is taken out, melt is poured into chilling in deionized water, it is dry
Obtain the fragment of glass melt；Grinding, sieves with 100 mesh sieve, obtains glass powder.By glass powder and epoxy resin, polyacrylamide,
Isopropanol and toluene (weight ratio is followed successively by 84%, 1.5%, 0.5%, 9%, 5%) are mixed into slurry, in the ball mill ball milling point
It dissipates；Tape casting spontaneously dries, is then cut into the idiosome of required shape；Idiosome is placed in sealing-in position, in electric furnace with
The rate of 2 DEG C/min heats up, and keeps the temperature 1 hour at 360 DEG C, and it is small to be then warming up to 460 DEG C of sealing-in processing 1 with the rate of 2 DEG C/min
When, that is, complete encapsulation.The example is to preferably constitute.Melt after heat preservation is poured into the stainless steel grinding tool after preheating, acquisition Φ=
The glass cylinder of 10mm, d=25mm are tested on NETZSCH DIL 402EP thermal dilatometer with the rate of heat addition of 10 DEG C/min,
Obtain glass transition point and softening point.Fig. 1,2 show to add the Fe of 20% molar fraction2O3Seal glass glass transition point
It is 344.4 DEG C, softening point is 380.8 DEG C, and linear expansion coefficient is 1.33 × 10-5/K.The refractive index of the glass is 1.8 ± 0.05,
And it is not added with Fe2O3Glass refractive index be 1.8 ± 0.4.
Embodiment 4
According to the proportion of each component of 1 embodiment 4 of table, analysis pure raw material (B is weighed respectively2O3、Bi2O3、ZnO、Fe2O3),
It was uniformly mixed with planetary ball mill ball milling 24 hours；Then powder is put into platinum crucible, is placed in the air gas of chamber type electric resistance furnace
In atmosphere, 920 DEG C are heated to 3 DEG C/min, keeps the temperature 1 hour；Then, crucible is taken out, melt is poured into chilling in deionized water, is done
The dry fragment for obtaining glass melt；Grinding, sieves with 100 mesh sieve, obtains glass powder.By glass powder and polyvinyl butyral, gather
Acrylic acid, isopropanol and acetone (weight ratio is followed successively by 83%, 2%, 1%, 9%, 5%) are mixed into slurry, in the ball mill ball milling
Dispersion；Tape casting spontaneously dries, is then cut into the idiosome of required shape；Idiosome is placed in sealing-in position, in electric furnace
It is heated up with the rate of 2 DEG C/min, keeps the temperature 1 hour at 340 DEG C, 450 DEG C of sealing-in processing 1 are then warming up to the rate of 2 DEG C/min
Hour, that is, complete encapsulation.The example is to preferably constitute.Melt after heat preservation is poured into the stainless steel grinding tool after preheating, acquisition Φ=
The glass cylinder of 10mm, d=25mm are tested on NETZSCH DIL 402EP thermal dilatometer with the rate of heat addition of 10 DEG C/min,
Obtain glass transition point and softening point.Fig. 1,2 show to add the Fe of 25% molar fraction2O3Seal glass glass transition point
It is 330.5 DEG C, softening temperature is 363.5 DEG C, and linear expansion coefficient is 1.37 × 10-5/K.The refractive index of the glass be 1.8 ±
0.05, and it is not added with Fe2O3Glass refractive index be 1.8 ± 0.4.
The present invention is obtained by above-mentioned implementation can be in the glass of low temperature implementation sealing-in.Its significant effect embodies a concentrated reflection of low
In terms of the refractive index of intermediate temperature sealing stabilization, in addition Fe2O3The variations in refractive index fluctuation of glass is lower afterwards.
The foregoing is merely presently preferred embodiments of the present invention, all equivalent changes done according to scope of the present invention patent with
Modification, is all covered by the present invention.
Claims (6)
1. a kind of low temperature sealing glass containing Fe, it is characterised in that: raw material B2O3、Bi2O3, ZnO and Fe2O3Molar ratio be 20 ~
40:25 ~ 35:5 ~ 30:10 ~ 25.
2. a kind of method for preparing the low temperature sealing glass containing Fe as described in claim 1, it is characterised in that: including following step
It is rapid:
(1) raw material is uniformly mixed；It is melted by 900-1000 DEG C, soaking time 1-4 hours；To the glass metal melted, into
Row chilling obtains glass frit；Then, glass frit is crushed, grinds, obtains glass powder after sieving；
(2) glass powder and binder, dispersing agent and solvent are mixed into slurry, ball milling disperses in the ball mill；Curtain coating
Molding spontaneously dries, is then cut into the idiosome of required shape, glass sealing material is made.
3. the preparation method of the low temperature sealing glass according to claim 2 containing Fe, it is characterised in that: the step (2)
Binder be epoxy resin, methylcellulose, polyvinyl butyral, the mixture of one or more of polyvinyl alcohol.
4. the preparation method of the low temperature sealing glass according to claim 2 containing Fe, it is characterised in that: the step (2)
Dispersing agent be one or more of fish oil, polyacrylic acid, polyvinyl alcohol, polyacrylamide mixture.
5. the preparation method of the low temperature sealing glass according to claim 2 containing Fe, it is characterised in that: the step (2)
Solvent be one or more of water, ethyl alcohol, isopropanol, n-butanol, toluene, dimethylbenzene, acetone mixture.
6. a kind of application method of the low temperature sealing glass containing Fe as described in claim 1, it is characterised in that: by glass sealing
Material is placed in sealing-in position, is heated up in electric furnace with the rate of 1-5 DEG C/min, 300-400 DEG C heat preservation 0.5-2 hours, then
450-500 DEG C of sealing-in is warming up to the rate of 1-5 DEG C/min to handle 0.5-2 hours, that is, completes encapsulation.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610936671.8A CN106477894B (en) | 2016-11-01 | 2016-11-01 | A kind of low temperature sealing glass and its preparation and application containing Fe |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610936671.8A CN106477894B (en) | 2016-11-01 | 2016-11-01 | A kind of low temperature sealing glass and its preparation and application containing Fe |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106477894A CN106477894A (en) | 2017-03-08 |
| CN106477894B true CN106477894B (en) | 2019-03-12 |
Family
ID=58272833
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610936671.8A Active CN106477894B (en) | 2016-11-01 | 2016-11-01 | A kind of low temperature sealing glass and its preparation and application containing Fe |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106477894B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107759091B (en) * | 2017-10-11 | 2020-08-11 | 福州大学 | Iron oxide-cobaltous oxide externally-doped sealing glass and preparation and use methods thereof |
| CN112456803A (en) * | 2020-11-05 | 2021-03-09 | 东南大学 | Preparation method of high-performance sealing glass for kovar alloy |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5491118A (en) * | 1994-12-20 | 1996-02-13 | E. I. Du Pont De Nemours And Company | Cadmium-free and lead-free thick film paste composition |
| CN101723589B (en) * | 2008-10-29 | 2013-04-17 | 珠海彩珠实业有限公司 | Lead-free glass powder with low melting point for sealing PDP and preparation method thereof |
| WO2012023413A1 (en) * | 2010-08-17 | 2012-02-23 | 日本電気硝子株式会社 | Glass for use in forming electrodes, and electrode-forming material using same |
| CN103319097A (en) * | 2013-06-26 | 2013-09-25 | 上海志感电子科技有限公司 | Low temperature lead-free glass dust and preparation method thereof |
| KR102200849B1 (en) * | 2013-10-21 | 2021-01-11 | 니폰 덴키 가라스 가부시키가이샤 | Sealing material |
| CN103739201B (en) * | 2013-12-16 | 2015-10-14 | 福州大学 | A kind of intermediate temperature SOFC sealing glass ceramic and preparation and application thereof |
-
2016
- 2016-11-01 CN CN201610936671.8A patent/CN106477894B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN106477894A (en) | 2017-03-08 |
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 | |
| CN106587641B (en) | Glass powder with low melting point and its laser lighting glass ceramics of manufacture | |
| CN103739201B (en) | A kind of intermediate temperature SOFC sealing glass ceramic and preparation and application thereof | |
| CN106495487B (en) | A kind of low temperature sealing glass and its preparation and application containing Ce | |
| CN106477894B (en) | A kind of low temperature sealing glass and its preparation and application containing Fe | |
| CN106495490B (en) | One kind containing SiO2LED low temperature sealing glass | |
| CN106495492B (en) | A kind of low temperature sealing glass and its preparation and application containing Sn | |
| CN106430979B (en) | A kind of low temperature sealing glass and its preparation and application containing Mn | |
| CN105481253B (en) | A kind of preparation method of compound low temperature sealing glass solder soldering paste | |
| CN106495489B (en) | One kind containing P2O5LED low temperature sealing glass | |
| CN107117959A (en) | A kind of high-curie temperature PTC thermal sensitive ceramic materials and preparation method thereof | |
| CN101734730A (en) | Inter-metallic compound material with near-zero thermal expansion character and anti-perovskite structure | |
| CN107043215A (en) | A kind of low temperature sealing glass of lanthana modification and its preparation and application method | |
| CN107971937A (en) | A kind of vitrified CBN wheel bonding agent for harmonic reducer of robot | |
| CN103540806A (en) | Novel composite material Al-Y2W3O12 and preparation method thereof | |
| CN102351403B (en) | Method for preparing ultrafine glass powder used for solar battery slurry | |
| CN110335694A (en) | A kind of Rapid microwave treatment method of radioactive pollution soil | |
| CN109305811A (en) | A kind of microwave-assisted zinc oxide ceramics sintering method | |
| CN106495491B (en) | One kind containing Al2O3LED low temperature sealing glass | |
| CN106946461B (en) | A kind of CeO2Modified low temperature sealing glass and its preparation and application method | |
| CN107043216A (en) | SiO2Modified low temperature sealing glass and its preparation and application method | |
| CN106927680A (en) | ZrO2Modified 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 | |
| CN109320263A (en) | Sintering aid and quartz-ceramics and its preparation and application method | |
| CN107651852A (en) | The seal glass and its preparation and application mixed outside a kind of cobalt sesquioxide nickel oxide |
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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |