CN106430979B - A kind of low temperature sealing glass and its preparation and application containing Mn - Google Patents
A kind of low temperature sealing glass and its preparation and application containing Mn Download PDFInfo
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- CN106430979B CN106430979B CN201610935764.9A CN201610935764A CN106430979B CN 106430979 B CN106430979 B CN 106430979B CN 201610935764 A CN201610935764 A CN 201610935764A CN 106430979 B CN106430979 B CN 106430979B
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- 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
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- 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
- C03C3/00—Glass compositions
- C03C3/12—Silica-free oxide glass compositions
- C03C3/14—Silica-free oxide glass compositions containing boron
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Abstract
The invention discloses a kind of low temperature sealing glass and its preparation and application containing Mn, raw material group become B2O3、Bi2O3, ZnO and MnO2.The present invention passes through high concentration Bi2O3With B2O3Coordinative role reduce glass softening temperature, realize low-temperature sealing；By adding MnO2Can not only stabilized glass refractive index, and the softening temperature of seal glass can be further decreased, can also adjust the coefficient of expansion of glass, significantly improve the sealing property of seal glass.It is simple and easy to get that the present invention prepares raw material, and simple process is stablized, save the cost, has reached practical and industrialized condition, which 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 Mn
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 Mn and its side of making and using
Method.Pass through high concentration Bi2O3With B2O3Coordinative role reduce glass softening temperature, realize low-temperature sealing；By adding MnO2
Can not only stabilized glass refractive index, and the softening temperature of seal glass can be further decreased, can also adjust the swollen of glass
Swollen coefficient significantly improves the sealing property of seal glass.
The present invention is to be implemented by following technical solution:
A kind of raw material group of the low temperature sealing glass containing Mn becomes B2O3、Bi2O3, ZnO and MnO2, molar ratio is 10 ~ 50:
20 ~ 40:5 ~ 30:0 ~ 30.
Preparation as described above the low temperature sealing glass containing Mn 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 high concentration Bi2O3With B2O3Coordinative role reduce glass softening temperature, realize low-temperature sealing；
(2) Mn in the glass network of melting chilling preparation3+It is changed into Mn in heating process4+, prevent Bi in glass3+→Bi5+
Transformation, the refractive index of stabilized glass；
(3) Mn ion can not only further decrease the softening temperature of seal glass as network ligand, and adjustable
The coefficient of expansion of glass significantly improves the sealing property of seal glass；
(4) 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 Mn contents.
Fig. 2 is the DSC curve for adding the low temperature sealing glass of different Mn contents.
Specific embodiment
A kind of raw material group of the low temperature sealing glass containing Mn becomes B2O3、Bi2O3, ZnO and MnO2, molar ratio is 10 ~ 50:
20 ~ 40:5 ~ 30:0 ~ 30.
Preparation as described above the low temperature sealing glass containing Mn 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、MnO2), 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, 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, is done
The dry fragment for obtaining glass melt；Grinding, sieves with 100 mesh sieve, obtains glass powder.By glass powder and polyvinyl alcohol, fish oil, ethyl alcohol
It is mixed into slurry with toluene (weight ratio is followed successively by 80%, 2%, 1%, 10%, 7%), ball milling disperses in the ball mill；It is cast into
Type spontaneously dries, is then cut into the idiosome of required shape；Idiosome is placed in sealing-in position, with 2 DEG C/min's in electric furnace
Rate heating keeps the temperature 1 hour at 400 DEG C, is then warming up to 500 DEG C of sealing-ins with the rate of 2 DEG C/min and handles 2 hours, that is, completes
Encapsulation.The example is to preferably constitute.Melt after heat preservation is poured into the stainless steel grinding tool after preheating, Φ=10mm, d=25mm are obtained
Glass cylinder, 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 10% molar fraction MnO2Seal glass glass transition point be 380.2 DEG C, softening
Point is 419.9 DEG C, and linear expansion coefficient is 1.12 × 10-5/K.The refractive index of the glass is 1.82 ± 0.20, and is not added with MnO2's
The refractive index of glass is 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、MnO2), 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, 990 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 methylcellulose, polyvinyl alcohol,
N-butanol and acetone (weight ratio is followed successively by 82%, 2%, 2%, 8%, 6%) are mixed into slurry, and ball milling disperses in the ball mill；Stream
Prolong molding, spontaneously dries, be then cut into the idiosome of required shape；Idiosome is placed in sealing-in position, in electric furnace with 2 DEG C/
The rate of min heats up, and keeps the temperature 1 hour at 380 DEG C, is then warming up to 490 DEG C of sealing-ins processing 1 hour with the rate of 2 DEG C/min, i.e.,
Complete 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 15% molar fraction MnO2Seal glass glass transition point be 361.7 DEG C,
Softening point is 399.3 DEG C, and linear expansion coefficient is 1.23 × 10-5/K.The refractive index of the glass is 1.82 ± 0.15, and is not added with
MnO2Glass refractive index be 1.8 ± 0.4.
Embodiment 3
According to the proportion of each component of 1 embodiment 3 of table, analysis pure raw material (B is weighed respectively2O3、Bi2O3、ZnO、MnO2), 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, 960 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 370 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 20% molar fraction MnO2The glass transition point of seal glass be
343.3 DEG C, softening point is 382.1 DEG C, and linear expansion coefficient is 1.30 × 10-5/K.The refractive index of the glass is 1.82 ± 0.08, and
It is not added with MnO2Glass 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、MnO2), 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, 940 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 polyvinyl butyral, poly- third
Olefin(e) 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 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 340 DEG C, and it is small to be then warming up to 450 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 25% molar fraction MnO2The glass transition point of seal glass be
330.9 DEG C, softening temperature is 368.2 DEG C, and linear expansion coefficient is 1.36 × 10-5/K.The refractive index of the glass is 1.82 ± 0.04,
And it is not added with MnO2Glass 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 MnO2The 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 Mn, it is characterised in that: raw material B2O3、Bi2O3, ZnO and MnO2Molar ratio be 20 ~
40:25 ~ 35:5 ~ 30:10 ~ 25.
2. a kind of method for preparing the low temperature sealing glass containing Mn 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, 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；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 Mn, 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 Mn, 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 Mn, 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 Mn 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.
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| CN201610935764.9A CN106430979B (en) | 2016-11-01 | 2016-11-01 | A kind of low temperature sealing glass and its preparation and application containing Mn |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101113075A (en) * | 2007-06-29 | 2008-01-30 | 东华大学 | Barium crown sealed glass and preparation and application thereof |
| CN101113074A (en) * | 2007-06-29 | 2008-01-30 | 东华大学 | Barium crown glass powder for electronic slurry and preparation method thereof |
| CN102010127A (en) * | 2009-09-07 | 2011-04-13 | 上海歌灵新材料科技有限公司 | Lead-free solder glass |
| CN102939271A (en) * | 2010-04-15 | 2013-02-20 | 费罗公司 | Low-melting lead-free bismuth sealing glasses |
| CN103553334A (en) * | 2013-10-23 | 2014-02-05 | 福州大学 | MnO2-containing glass sealing material as well as preparation and use methods thereof |
-
2016
- 2016-11-01 CN CN201610935764.9A patent/CN106430979B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101113075A (en) * | 2007-06-29 | 2008-01-30 | 东华大学 | Barium crown sealed glass and preparation and application thereof |
| CN101113074A (en) * | 2007-06-29 | 2008-01-30 | 东华大学 | Barium crown glass powder for electronic slurry and preparation method thereof |
| CN102010127A (en) * | 2009-09-07 | 2011-04-13 | 上海歌灵新材料科技有限公司 | Lead-free solder glass |
| CN102939271A (en) * | 2010-04-15 | 2013-02-20 | 费罗公司 | Low-melting lead-free bismuth sealing glasses |
| CN103553334A (en) * | 2013-10-23 | 2014-02-05 | 福州大学 | MnO2-containing glass sealing material as well as preparation and use methods thereof |
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