CN108996910A - A kind of assembly, mixture, seal glass and preparation method thereof - Google Patents
A kind of assembly, mixture, seal glass and preparation method thereof Download PDFInfo
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- CN108996910A CN108996910A CN201811048465.9A CN201811048465A CN108996910A CN 108996910 A CN108996910 A CN 108996910A CN 201811048465 A CN201811048465 A CN 201811048465A CN 108996910 A CN108996910 A CN 108996910A
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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
-
- 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
-
- 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
- C03C3/16—Silica-free oxide glass compositions containing phosphorus
- C03C3/19—Silica-free oxide glass compositions containing phosphorus containing boron
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- 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
A kind of assembly, mixture, seal glass and preparation method thereof, belong to glass art.Mixture is for making seal glass.The main mixture of mixture is for making seal glass.Mixture includes following components according to parts by weight: 60~80% P2O5, 10~30% BaO, 0.1~3% Al2O3, 0.1~3% B2O3, 1~10% ZnO, 1~10% K2O, 1~10% Sr2O, 0.1~1% oxide.Oxide includes cerium oxide, dysprosia, neodymia.The softening point of seal glass is low, is easy to low-temperature sealing.
Description
Technical field
The present invention relates to glass arts, in particular to a kind of assembly, mixture, seal glass and its production side
Method.
Background technique
Seal glass (Sealing Glass) is can be by metal or alloy, ceramics, other glass (including devitrified glass)
And the middle layer glass that composite material etc. seals up each other.Compared to high molecular material, seal glass is in air-tightness and resistance to
Have the advantages that on hot prominent；Compared to seal, sealing materials such as metal, polymer or ceramics, seal glass have chemical stability,
Heat resistance and stronger mechanical strength, high insulating properties etc..
Seal glass application mainly have the following aspects: 1, be used as encapsulating material, as case package, coating encapsulation,
Passivation film etc..2, pure seal, sealing materials, for the mutual sealing-in between ceramics, metal, glass and other materials.3, it adds
Material improves the performance (silver-colored paddle class) of electronic component as the filler of electronic material.
With the development of economy, social progress, new energy development have become certainty and social consensus.Various equipment are got over
Come more towards save the energy, it is easy to use, save space, safe and efficient, environmentally friendly, safe one-machine-multi-function the features such as direction hair
Exhibition.
The electrode terminal of the shell of traditional lithium battery mostly uses polymer to be sealed.The polymer of sealing can play absolutely
Edge, airtight effect.Polymer belongs to organic material, aging is easy as time goes by or after heated, so as to cause polymer
Decline with the bond strength of electrode metal, in turn results in lithium battery gas leakage.When electrode terminal sealing when something goes wrong, the battery longevity
Life reduces, cannot preferably guarantee safety.Further, due to the decline of bond strength, polymer and electrode metal may
It separates.In this way, electrode terminal is easy ingress of air, and the moisture in air penetrates into electricity from metalwork and polymer junction
Inside pond, water is reacted with inside battery lithium salts reduces battery performance, while integrally also having extremely strong burn into cause safety on battery
Hidden danger battery reliability is low.
Summary of the invention
Based on the deficiencies of the prior art, the present invention provides a kind of assembly, mixture, seal glass and its production sides
Method partly or entirely to improve, even solves problem above.
The present invention is implemented as follows:
In a first aspect, the embodiment of the present invention provides a kind of mixture.
Mixture can be used for making seal glass.
Mixture is mainly made of oxide complex and rare earth oxide, oxide complex include phosphorus pentoxide,
Barium monoxide, aluminum oxide, diboron trioxide, zinc oxide, potassium oxide, strontium dioxide, rare earth oxide include cerium oxide, oxidation
Dysprosium and neodymia；
Mixture includes following components according to parts by weight: 60~80% P2O5, 10~30% BaO, 0.1~3%
Al2O3, 0.1~3% B2O3, 1~10% ZnO, 1~10% K2O, 1~10% Sr2O, 0.1~1% rare earth oxygen
Compound.
In other one or more examples, mixture includes following components according to parts by weight:
65~75% P2O5, 13~28% BaO, 0.4~2.7% Al2O3, 0.1~2.9% B2O3, 1.6~
9.4% ZnO, 1.4~9.2% K2O, 1.7~9.6% Sr2O, 0.2~0.9% rare earth oxide.
Preferably, 67~75% P2O5, 14~24.4% BaO, 0.4~2.4% Al2O3, 0.2~2.2%
B2O3, 1.8~8.6% ZnO, 2~8% K2O, 3~9% Sr2O, 0.3~0.8% rare earth oxide；
It is highly preferred that 69~75% P2O5, 15~18.6% BaO, 0.5~1.8% Al2O3, 0.4~1.2%
B2O3, 4~8% ZnO, 3.1~7% K2O, 3.9~5% Sr2O, 0.4~0.7% rare earth oxide；
It is further preferred that 69~72% P2O5, 15~18% BaO, 0.5~1% Al2O3, 0.2~0.5%
B2O3, 5~8% ZnO, 4~6% K2O, 4~5% Sr2O, 0.5~0.6% rare earth oxide.
In other one or more examples, mixture is powdered.
In second aspect, the embodiment of the invention provides a kind of seal glasses.
Seal glass is made by above-mentioned mixture.
In other one or more examples, powder that seal glass is 1~5 μm of partial size.
Preferably 1.4~4.6 μm.
More preferably 2.5~4.0 μm.
Further preferably 3.2~3.6 μm.
In other one or more examples, the fusion temperature of seal glass is 1200~1400 DEG C.
Preferably 1220~1380 DEG C.
More preferably 1260~1320 DEG C.
Further preferably 1290~1300 DEG C.
In the third aspect, the embodiment of the invention provides a kind of production methods of seal glass.Production method includes to mixed
It closes material and carries out melting.
In other one or more examples, the method for melting mixture include: by mixed material heating to 1200~
1400 DEG C of conditions, and constant temperature 1~2 hour under the conditions of 1200~1400 DEG C.
In other one or more examples, production method further includes the cooling and grinding carried out after melting.
In fourth aspect, the embodiment of the invention provides a kind of assemblys.
Assembly includes first element, second element, and first element and second element pass through seal glass above-mentioned
Fusion seal.
The utility model has the advantages that
Seal glass provided in an embodiment of the present invention has fusion temperature/fusing point low (350~400 DEG C), the coefficient of expansion high
(13×10-6/ DEG C~15 × 10-6/ DEG C), lead-free feature.Further, seal glass, can in the use process of sealing-in
To reduce the content of gas significantly.For generally, the seal glass stability is good, softening point is low, the coefficient of expansion is high is applicable in
In aluminium, aluminium alloy, copper, copper alloy low melting point high expansion lithium battery composite terminal post metal sealing, it is also applied for other eutectics simultaneously
Point high expansion metal device sealing-in.
In addition, the performance that also there is seal glass resistant to hydrogen fluoric acid to corrode, so as to be applied to some batteries (in battery
Some substances can generate hydrofluoric acid), thereby may be ensured that in battery that accumulation of energy material performance is constant, extends battery life, mentions
High battery security.
The compound pole of battery (such as lithium ion battery) is encapsulated using the seal glass in example of the present invention.Glass-encapsulated
Terminal can be through high temperature sintering and realize.By high temperature sintering, glass combines together with metal, and intensity is that polymer is several
Ten times, pressure resistance reach 25 kilograms or more, air-tightness reaches 1~10-8 or more, guarantees 10 years or more battery air tightness guarantees battery
Leakproof pond liquid, battery by under the conditions of external impacts, guarantee battery security.
Specific embodiment
Embodiment of the present invention is described in detail below in conjunction with embodiment, but those skilled in the art will
Understand, the following example is merely to illustrate the present invention, and is not construed as limiting the scope of the invention.It is not specified in embodiment specific
Condition person carries out according to conventional conditions or manufacturer's recommended conditions.Reagents or instruments used without specified manufacturer is
The conventional products that can be obtained by commercially available purchase.
In actual application, seal glass typically as solder come using.Seal glass is used to through welding
Mode connects the component of various similar and different ingredients.For example, by seal glass connect two kinds of metals, or connection glass and
Metal, or two kinds of metals of connection.
Under some special application scenarios, user often it is expected to carry out sealing-in under vacuum conditions, has to be formed
The device of certain vacuum degree, equipment.For example, feedthrough component, battery cover board in flat panel TV in the prior art, sensor, pressure
Contracting machine hermetic terminal.
Under other special application scenarios, for by sealing-in object, user may want to seal glass with anti-corruption
The performance of erosion.For example, hydrofluoric acid may be generated for some batteries.Therefore, operation is being packaged using seal glass
When, the corrosive nature that seal glass resists hydrofluoric acid is desired to have.
For cannot or usually should not also be welded to it by high-temperature process by sealing-in object in the selection for considering solder
Jointing temp carries out corresponding selection appropriate.
In addition, determining product (such as electronics device after sealing-in due to the compaction rate of the connection between the object by sealing-in
Part) performance superiority and inferiority, therefore, in the seal glass for being selected as solder, it is often necessary to consider its compaction rate.Further
Ground, the selection of solder also need to consider that closure has enough intensity, fastness, have stronger both thermally and chemically stable
Property.
Based on different sealing-in products, solder can mainly be controlled in terms of following four.
Softening point: in the operating temperature section of sealing-in product, the softening point of solder suitably (or even as far as possible) is reduced,
It can guarantee to soften the wetting effect that the solder of (fusing) has had, and can be damaged to avoid by sealing-in object by high temperature.
Thermal expansion coefficient: in some sealing structures, the thermal expansion coefficient of seal glass be required it is lower, with reduce in answer
Power.In such an application, the thermal expansion coefficient of seal glass can usually be required less than 5%.In other applications, sealing-in
The thermal expansion coefficient of glass be required it is higher, with reduce two connected components between there is the problem of mismatch, with reduce hair
Raw isolation/division/gap, and then avoid the leakage of fluid.
Electrical insulating property: sealing device is generally used for electronic product, and the effect of seal glass a part has been insulating effect, institute
There must be high insulation and high voltage withstanding with seal glass.
Stability: including technology stability and chemical stability, furthermore seal glass should also have preferable wetability and
Mobility, water-resistance.
It is excessively high using temperature for existing seal glass (solder) in example of the present invention, and be easy (especially for needing
In the field for carrying out vacuum seal) bubble is led to the problem of, propose a kind of new seal glass.
In practice, inventors have found that under vacuum conditions in use, the part bubble inside seal glass can be gathered into
It is long, to form big bubble and generate the trend of precipitation.And during Bubble, seal glass surface simultaneously again into
Row curing reaction, and then cause inside glass to generate big bubble cannot to be precipitated.Phenomenon has higher welding in solder in this way
Show more obvious when temperature.
As a result, under elevated temperature in vacuo, the gas that air pocket existing for seal glass inside, glass composition volatilize is all
It will lead to the air-tightness decline of sealing-in product, while also causing the intensity decline of seal glass, to also easily cause sealing-in
Cracking glasses fall off, and make the quality degradation of sealing-in product.
Based on the above cognition, a kind of new seal glass is inventors herein proposed.Its main component that can be used as solder.It changes
Yan Zhi contains most seal glass in solder, and can also use some other ingredients as needed.Alternatively, one
In a little application examples, seal glass constitutes the whole components of solder.
The seal glass provided in example has fusing point, and low (softening temperature is relatively low, fusing point substantially 350~400
DEG C) the advantages of, and thermal expansion coefficient is high.Also, the ingredient in seal glass is not easy to generation gas and was therefore welding
It is not easy to form bubble in journey.It is especially outstanding to be, it is not use containing lead composition initiatively, therefore it is used in the seal glass
Safer, environmental issue is greatly reduced.
A kind of assembly, mixture, seal glass below for the embodiment of the present invention and preparation method thereof carry out specific
Illustrate:
The exemplary major part of the present invention is mainly to contain P2O5, BaO glass substance based on.Invent also further base
In proposing use-case --- the seal glass of this kind of glass substance.Although this kind of glass application field provided in invention not by
Limitation, but it is particularly valuable that the substitute (sealing-in in example of the present invention of the leaded seal glass of height as seal glass
One of main feature of glass is it without lead.).
Inventor firmly believes:
Since halide especially fluoride can be such that glass is easier to by thermal softening, and therefore reduce the envelope of seal glass
Jointing temp, and when operating under vacuum, the seal glass containing halide is easy heated and releases gas, and with aforementioned phase
With reason and generate bubble, influence sealing-in effect (such as intensity decline, air-tightness reduce).Therefore, it is mentioned in example of the present invention
What is supplied is used to make in the raw material (mixture) of seal glass, what chloride was not expect to be present usually.
The introducing of alkali metal oxide can promote the process of the crystallization process of seal glass to a certain extent.In addition,
The presence of alkali metal oxide can make seal glass be easier to heated and soften, and can also increase to a certain extent and treat
The wellability of sealing-in object (more due to dispersing, spreading in sealing-in subject surface).And on the other hand, alkali metal oxide
Presence can to a certain degree increase seal glass the coefficient of expansion (thermal expansion coefficient).Therefore, by alkali metal oxide
Content need to be carried out regulation appropriate, can make the mixture for making seal glass that there is better service performance.Originally show
In example, introducing in alkali metal oxide has potassium oxide (K2O)
The content of phosphorus pentoxide cannot be excessive, can not be very little.On the one hand, content is too low can cause sealing-in unstable
It is fixed；Content is too high, and being easy to cause the resist chemical performance of seal glass to reduce, (seal glass is difficult to crystallize, and glass is presented
State).Excessively easily soften in addition, the too high levels of phosphorus pentoxide will lead to seal glass, this is for needing under the high temperature conditions
It works or to need the product for carrying out reheating sealing-in that can generate significant unfavorable.I.e. sealing part is because of the heated or sealing-in that works
In the process secondary heated and soften, the rough sledding such as be subjected to displacement/misplace so as to cause the different components in sealing-in product.
Based on the above, mainly including oxygen for the mixture for being used to make seal glass provided by example of the present invention
Compound complex, and rare earth element is also particularly introduced in the form of simple substance.That is, mixture is mainly by oxide complex
It is constituted with the oxide form (rare earth oxide) of rare earth element.
Wherein, oxide complex include phosphorus pentoxide, barium monoxide, aluminum oxide, diboron trioxide, zinc oxide,
Potassium oxide, strontium dioxide；Rare earth oxide includes cerium oxide, dysprosia and neodymia.
The content of each component in mixture is defined as follows comprising following components according to parts by weight: 60~
80% P2O5, 10~30% BaO, 0.1~3% Al2O3, 0.1~3% B2O3, 1~10% ZnO, 1~10%
K2O, 1~10% Sr2O, 0.1~1% rare earth oxide.
In some other example, mixture includes following components according to parts by weight: 65~75% P2O5, 13~
28% BaO, 0.4~2.7% Al2O3, 0.1~2.9% B2O3, 1.6~9.4% ZnO, 1.4~9.2% K2O、
1.7~9.6% Sr2O, 0.2~0.9% rare earth oxide；
Or, 67~72% P2O5, 14~24.4% BaO, 0.6~2.4% Al2O3, 0.1~2.6% B2O3、
1.8~8.6% ZnO, 2~8% K2O, 3~9% Sr2O, 0.3~0.8% rare earth oxide；
Or, 69~70% P2O5, 15~18.6% BaO, 0.7~2.2% Al2O3, 1~2.2% B2O3, 3~
6% ZnO, 3.1~7% K2O, 3.9~5% Sr2O, 0.4~0.7% rare earth oxide；
Or, 66~70% P2O5, 15~18% BaO, 1~2% Al2O3, 1.5~2% B2O3, 4~5%
ZnO, 4~6% K2O, 4~5% Sr2O, 0.5~0.6% rare earth oxide.
Convenience based on subsequent production considers, and the contact between various composition, interaction for convenience, mixing
Material is provided and is used with powdered state.Therefore, it is used to carry out sealing-in between two components in seal glass
When, it can be implemented as follows: it is two components are opposite and be arranged close to, so that powdered seal glass is wrapped in two
Between component, seal glass is heated with ring-shaped heater.
Based on above-mentioned mixture, as a kind of use-case of mixture, one kind also proposed in embodiment by mixture system
Seal glass made of work.Based on the convenience used, seal glass can be the mode of appearance such as powdered, rodlike, strip
It provides and is welded by using.In the use-case as powdered seal glass, seal glass can be 1~5 μm of partial size
Powder, preferably 1.4~4.6 μm, more preferably 2.5~4.0 μm, further preferably 3.2~3.6 μm.
The investigation condition that a kind of use as seal glass is welded, the fusion temperature of the seal glass is 1200~
1400 DEG C, preferably 1220~1380 DEG C, more preferably 1260~1320 DEG C, further preferably 1290~1300 DEG C.
The production method of seal glass can choose for carry out melting, i.e., by melting make the various composition in mixture it
Between contact with each other, act on and form glass substance.For example, by mixed material heating to 1200~1400 DEG C of conditions, and 1200~
Constant temperature 1~2 hour under the conditions of 1400 DEG C.Further, the cooling carried out after melting obtains solid seal glass, then basis
It is ground, to be crushed to required partial size.
Based on the above seal glass, a kind of assembly is additionally provided in example.The assembly includes first element, second yuan
Part, and first element and second element pass through seal glass fusion seal.
In a kind of optional example, a kind of assembly with metal and glass is provided.Assembly mainly includes sequence
Metal, seal glass and the glass of arrangement.Metal and glass need the surface connected and pass through polishing, polishing, cleaning, drying
Equal operations are processed for exposing smooth, clean surface.It puts the surface to be connected of metal and glass is relatively close,
Then it carries out powdered seal glass accumulation to make seal glass be molten into fluid/molten state by heating therebetween,
Keep glass and metal relatively close to contacting, makes the two contraposition to seal glass cooled and solidified.Then, pass through the modes pair such as polishing
The defects of extra seal glass is removed, and reduces crackle, the hole of seal glass.
As an example, the ingredient and performance of the seal glass being listed briefly are enumerated in following table 1 and table 2.
1 sealing glass composition of table (wherein content is weight percentage)
Table 2 lists the performance of the seal glass in each example.
It could be aware that by the above Tables 1 and 2, the comprehensive performance of seal glass provided in an embodiment of the present invention is more excellent,
Softening temperature and sealing temperature are lower for existing seal glass, therefore, can under lower operation temperature into
Row sealing-in processing.In addition, the performance of the acid-resisting corrosion of the seal glass in invention example is higher than existing product also significantly.
Meanwhile the coefficient of expansion for inventing the seal glass of offer is relatively higher, is conducive to it in the sealing-in field for being easy to produce mismatch
Using.
Although illustrate and describing the present invention with specific embodiment, it will be appreciated that without departing substantially from of the invention
Many other change and modification can be made in the case where spirit and scope.It is, therefore, intended that in the following claims
Including belonging to all such changes and modifications in the scope of the invention.
Claims (10)
1. a kind of mixture, for making seal glass, which is characterized in that the mixture is mainly by oxide complex and dilute
Native oxide is constituted, and the oxide complex includes phosphorus pentoxide, barium monoxide, aluminum oxide, diboron trioxide, oxidation
Zinc, potassium oxide, strontium oxide strontia, the rare earth oxide include cerium oxide, dysprosia and neodymia；
The mixture includes following components according to parts by weight: 60~80% P2O5, 10~30% BaO, 0.1~3%
Al2O3, 0.1~3% B2O3, 1~10% ZnO, 1~10% K2O, 1~10% Sr2O, 0.1~1% rare earth oxygen
Compound.
2. mixture according to claim 1, which is characterized in that the mixture includes according to parts by weight with the following group
Point:
65~75% P2O5, 13~28% BaO, 0.4~2.7% Al2O3, 0.3~2% B2O3, 1.6~9.4%
ZnO, 1.4~9.2% K2O, 1.7~9.6% Sr2O, 0.2~0.9% rare earth oxide；
Or, 67~72% P2O5, 14~24.4% BaO, 0.6~2.4% Al2O3, 0.9~2.6% B2O3, 1.8~
8.6% ZnO, 2~8% K2O, 3~9% Sr2O, 0.3~0.8% rare earth oxide；
Or, 69~70% P2O5, 15~18.6% BaO, 0.7~2.2% Al2O3, 1~2.2% B2O3, 3~6%
ZnO, 3.1~7% K2O, 3.9~5% Sr2O, 0.4~0.7% rare earth oxide；
Or, 66~70% P2O5, 15~18% BaO, 1~2% Al2O3, 1.5~2% B2O3, 4~5% ZnO, 4
~6% K2O, 4~5% Sr2O, 0.5~0.6% rare earth oxide.
3. mixture according to claim 1 or 2, which is characterized in that the mixture is powdered.
4. a kind of seal glass, which is characterized in that the mixture as described in any one of claims 1 to 3 is made.
5. seal glass according to claim 4, which is characterized in that the powder that the seal glass is 1~5 μm of partial size,
Preferably 1.4~4.6 μm, more preferably 2.5~4.0 μm, further preferably 3.2~3.6 μm.
6. seal glass according to claim 4, which is characterized in that the fusion temperature of the seal glass be 1200~
1400 DEG C, preferably 1220~1380 DEG C, more preferably 1260~1320 DEG C, further preferably 1290~1300 DEG C.
7. a kind of production method of the seal glass as described in any one of claim 4~6, which is characterized in that described
Mixture carries out melting.
8. the production method of seal glass according to claim 7, which is characterized in that the method packet of mixture described in melting
It includes: by the mixed material heating to 1200~1400 DEG C of conditions, and constant temperature 1~2 hour under the conditions of 1200~1400 DEG C.
9. the production method of seal glass according to claim 8, which is characterized in that the production method further includes molten
The cooling and grinding carried out after refining.
10. a kind of assembly, which is characterized in that the assembly includes first element, second element, the first element and institute
It states second element and passes through the seal glass fusion seal as described in any one of claim 4~6.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN201811048465.9A CN108996910A (en) | 2018-09-07 | 2018-09-07 | A kind of assembly, mixture, seal glass and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201811048465.9A CN108996910A (en) | 2018-09-07 | 2018-09-07 | A kind of assembly, mixture, seal glass and preparation method thereof |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001180972A (en) * | 1999-12-27 | 2001-07-03 | Asahi Glass Co Ltd | Lead free glass with low melting point |
| CN101597136A (en) * | 2009-07-23 | 2009-12-09 | 苏州恒仓红外光学材料研发中心有限责任公司 | A kind of lead-free low-melting sealing glass and preparation method thereof |
| CN101863620A (en) * | 2009-04-20 | 2010-10-20 | 郑庆云 | Phosphate low-melting-point glass for decoration and preparation method thereof |
| CN108423998A (en) * | 2018-05-31 | 2018-08-21 | 北京北旭电子材料有限公司 | Glass powder composition, glass sealing material and preparation method thereof and battery |
-
2018
- 2018-09-07 CN CN201811048465.9A patent/CN108996910A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001180972A (en) * | 1999-12-27 | 2001-07-03 | Asahi Glass Co Ltd | Lead free glass with low melting point |
| CN101863620A (en) * | 2009-04-20 | 2010-10-20 | 郑庆云 | Phosphate low-melting-point glass for decoration and preparation method thereof |
| CN101597136A (en) * | 2009-07-23 | 2009-12-09 | 苏州恒仓红外光学材料研发中心有限责任公司 | A kind of lead-free low-melting sealing glass and preparation method thereof |
| CN108423998A (en) * | 2018-05-31 | 2018-08-21 | 北京北旭电子材料有限公司 | Glass powder composition, glass sealing material and preparation method thereof and battery |
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Application publication date: 20181214 |
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