CN102432173A - Phosphate sealing glass with ultra-low expansion softening temperature and preparation method thereof - Google Patents
Phosphate sealing glass with ultra-low expansion softening temperature and preparation method thereof Download PDFInfo
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- CN102432173A CN102432173A CN2011102577819A CN201110257781A CN102432173A CN 102432173 A CN102432173 A CN 102432173A CN 2011102577819 A CN2011102577819 A CN 2011102577819A CN 201110257781 A CN201110257781 A CN 201110257781A CN 102432173 A CN102432173 A CN 102432173A
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Abstract
The invention relates to phosphate sealing glass with ultra-low expansion softening temperature and a preparation method thereof, which belong to the technical field of special glass. The existing phosphate sealing glass has too high expansion softening temperature, so the molten sealing temperature is too high. The preparation method of the existing phosphate sealing glass has too high melting temperature, and in addition, the sectional temperature rise is also needed, so the preparation time is long, and the melting process is complicated. The phosphate sealing glass comprises the following glass ingredients in percentage by mass: 13 to 40 weight percent of P2O5, 40 to 70 weight percent of SnO, 0 to 5 weight percent of ZnO, 0 to 10 weight percent of WO3, 0 to 10 weight percent of Bi2O3, 0 to 5 weight percent of Sm2O3 and 0 to 3 weight percent of Sb2O3. The preparation method of the phosphate sealing glass sequentially comprises the following work procedures of proportioning, melting and annealing, SnO is introduced in the proportioning work procedure through SnCl2, the temperature is raised to the melting temperature from the room temperature in one step in the melting work procedure, the melting temperature is 320 to 450 DEG C, and the melting lasts 10 to 50 minutes at the melting temperature. The damage to sealed elements caused by high temperature can be effectively avoided when the glass sealing is adopted.
Description
Technical field
The present invention relates to a kind of phosphate seal glass with super-low expansion softening temperature and preparation method thereof, this seal glass is used for the sealing-in of electron device etc. as a kind of welding material, belongs to the special glass technical field.
Background technology
Seal glass is also claimed solder glass; It is a kind of welding material; The welded encapsulation that is used for opto-electronic device, microelectronic device, electron tube, solar energy heat collection pipe etc. requires to have lower expansion softening temperature, higher sealing strength, adjustable linear expansivity, good chemical stability and electrical insulating property, simultaneously; As a kind of Chemicals, the ideal production technique should have characteristics such as advantages of nontoxic raw materials, raw material type are few.
Phosphate seal glass is a kind of seal glass commonly used.
U.S. Pat 2002019303 proposes a kind of SnO-P
2O
5The seal glass of-ZnO system; The expansion softening temperature is positioned at 430～500 ℃ of intervals, causes melting temperature sealing higher, is kept for some time under such high temperature by the device of sealing-in; Therefore its serviceability and work-ing life can reduce, even can in the sealing-in process, damage device.
Application number is that an one Chinese patent application of 200610024793.6 discloses a kind of powdery seal glass, and its basal component and molar percentage thereof are: P
2O
520～50%, ZnO 10～26%, SnO 20～40%, B
2O
35～50, SiO
20～15%, Al
2O
30～10%, Na
2O+Li
2O 0～10%, Sb
2O
30～5%, Fe
2O
30～2%, MnO
20～5%, Cr
2O
30～2%.The introducing of alkali metal makes the migration because of alkalimetal ion in practical application of this glass influence by the serviceability of the semiconducter device of sealing-in.Its expansion softening temperature interval is 440～500 ℃.Prepare this seal glass, the raw material type that relates to is too many, causes complex process.
Application number is that an one Chinese patent application of 201010190237.2 has proposed a kind of Unlead low-smelting point electronic display sealing glass and preparation method thereof.This glass basal component and mass percent thereof are: ZnO 10～45%, P
2O
510～45%%, V
2O
55～35%%, B
2O
31～10%%, Al
2O
31～10%%, Fe
2O
31～10%%.Deleterious V
2O
5Content is bigger, in the process of founding, also is prone to bubble, and contaminate environment and raw material availability are lower.In addition, the expansion softening temperature interval of this glass is 300～360 ℃, and is still higher.
Said two Chinese patents all contain more ZnO aspect component, also contain B
2O
3Though, improved the one-tenth glass properties,, improved the expansion softening temperature of glass; All contain Al
2O
3, can improve into glass property, improve chemicalstability, can also be through changing Al
2O
3Proportioning, regulate the linear expansivity of product glass, still, also caused the raising of expansion softening temperature; All contain Fe
2O
3Though, improved the flowability of product glass in the process that is used for sealing-in,, the introducing of this component also cause the expanding raising of softening temperature.
In view of this; There is a common deficiency in existing phosphate seal glass; That softening temperature that expands exactly is too high, causes melting temperature sealing higher, is not suitable for because of needed the sealing process of sealing-in at a lower temperature by the characteristics of closure material or structure aspects; As being coated with fluorescent material, be semiconducter device etc. by closure by closure.
Its deficiency of preparation method of existing phosphate seal glass is that glass melting temperature is high, up to 1000～1200 ℃, but also needs temperature-gradient method, causes preparation time long, and melting technology is complicated.
Summary of the invention
The objective of the invention is guaranteeing that phosphate seal glass has under the prerequisite of higher sealing strength, adjustable linear expansivity, good chemical stability and electrical insulating property to have lower expansion softening temperature, kind still less and nontoxic preparation raw material; Aspect the preparation method of phosphate seal glass, reduce glass melting temperature, shorten melting time, simplify melting technology, for this reason, we have invented a kind of phosphate seal glass with super-low expansion softening temperature and preparation method thereof.
The present invention's the phosphate seal glass with super-low expansion softening temperature has P in its proportioning
2O
5Component is characterized in that, glass ingredient and quality percentage composition thereof are: P
2O
513～40, SnO 40～70, ZnO 0～5, WO
30～10, Bi
2O
30～10, Sm
2O
30～5, Sb
2O
30～3, said data unit is wt%.
The present invention's the phosphate seal glass preparing method's with super-low expansion softening temperature operation is followed successively by batching, founds, anneals, it is characterized in that, at burden process with SnCl
2Introduce SnO; Be warmed up to glass melting temperature at melting process from one step of room temperature, glass melting temperature is 320～450 ℃, under glass melting temperature, founds 10～50 minutes.
Its technique effect of the present invention is:
About having the phosphate seal glass of super-low expansion softening temperature, the P in the component
2O
5Be glass-former, help to improve the chemicalstability of glass simultaneously, work as P
2O
5The quality percentage composition less than 13% o'clock, its glass forming ability weakens, and works as P
2O
5The quality percentage composition greater than 40% o'clock, the chemicalstability of glass significantly reduces.SnO in the component can obviously reduce the expansion softening temperature of glass, and makes glass have good chemical stability, and its optimum quality percentage composition in glass is 40～70%.The content of ZnO in the component is relevant with the linear expansivity of glass, and along with the introducing of ZnO and the increase of introducing amount, the linear expansivity of glass decreases; But; When the introducing amount is too much, can improve the expansion softening temperature of glass again, the preferred mass percentage composition is 0～5%.WO in the component
3Not only can reduce the expansion softening temperature of glass, and the adhesive power of ability reinforcing glass when being used for sealing-in, improving sealing strength, its best in quality percentage composition is 0～10%.Bi in the component
2O
3Good glass forming ability is arranged, and its adding can be repaired the network structure of phosphate glass, improves the chemicalstability of glass, and can not cause the raising of the expansion softening temperature of glass, and its best in quality percentage composition is 0～10%.Sm in the component
2O
3Can improve the sealing strength of glass.Sb in the component
2O
3Can oxidizing atmosphere be provided in the process of founding, prevent Sn
2+, Bi
3+In the process of founding, be reduced.
About the preparation method of phosphate seal glass with super-low expansion softening temperature, SnO is with SnCl
2Introduce, not only reduced glass melting temperature, and, Cl wherein
1-Still a kind of finings quickens the discharge of the bubble in the glass metal in the process of founding, and has certain effect aspect the shortening melting time.This method is warmed up to glass melting temperature at melting process from one step of room temperature, and glass melting temperature is merely 320～450 ℃, and melting time is merely 10～50 minutes, compares prior art, and melting technology is simplified to some extent, and glass melting temperature significantly reduces, and melting time obviously shortens.
In addition, maximum seven kinds of its component of the phosphate seal glass with super-low expansion softening temperature of the present invention, minimum have only two kinds; And, do not contain poisonous component, therefore; Prepare the also therefore minimizing of raw material type that this glass adopts, simplified preparation technology, avoid pollution environment.
The present invention's the phosphate seal glass with super-low expansion softening temperature is because of the difference of glass ingredient and quality percentage composition thereof, and its expansion softening temperature is compared prior art and significantly reduced 120～180 ℃ of scopes; Linear expansivity is 90～170 * 10
-7Adjustable in the/℃ scope.This glass can either effectively be avoided being damaged by closure Yin Gaowen as a kind of seal glass, again can be different with thermal expansion respectively by the closure thermal expansion matching.
Embodiment
Mode with instance further specifies the present invention below.
Burden process:
The glass ingredient proportioning of confirming by last table takes by weighing raw material, and wherein SnO is by SnCl
22H
2O introduces, and other component is directly introduced with the form of oxide compound, and mixed grinding is even, gets compound.
Melting process:
With the said compound corundum crucible of packing into, put into the globars electric furnace again and heat, be warmed up to glass melting temperature from one step of room temperature, heating mode is that nature heats up, and does not just stipulate temperature rise rate, glass melting temperature and melting time see the following form,
| Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | |
| Glass melting temperature (℃) | 350 | 360 | 370 | 385 | 400 |
| Melting time (min) | 15 | 25 | 25 | 25 | 35 |
Obtain glass melt.
Annealing operation:
Said glass melt is cast on the iron plate of preheating and obtains block glass, and to put into the furnace chamber temperature immediately be that 200 ℃ retort furnace is annealed, be incubated to stop insulation after 1 hour, naturally cool to room temperature with stove.
Obtain frit glass if desired, then directly pour said glass melt in water shrend, obtain glass particle, oven dry back ball milling sieves.
Claims (5)
1. the phosphate seal glass with super-low expansion softening temperature has P in its proportioning
2O
5Component is characterized in that, glass ingredient and quality percentage composition thereof are: P
2O
513～40, SnO 40～70, ZnO 0～5, WO
30～10, Bi
2O
30～10, Sm
2O
30～5, Sb
2O
30～3, said data unit is wt%.
2. the phosphate seal glass with super-low expansion softening temperature according to claim 1 is characterized in that, glass ingredient and quality percentage composition preferred version thereof are: P
2O
528～32, SnO 52～69, ZnO 0～3, WO
30～3, Bi
2O
30～3, Sm
2O
30～3, Sb
2O
30～1, said data unit is wt%.
3. phosphate seal glass preparation method with super-low expansion softening temperature, its operation is followed successively by batching, founds, anneals, it is characterized in that, at burden process with SnCl
2Introduce SnO; Be warmed up to glass melting temperature at melting process from one step of room temperature, glass melting temperature is 320～450 ℃, under glass melting temperature, founds 10～50 minutes.
4. the phosphate seal glass preparation method with super-low expansion softening temperature according to claim 3 is characterized in that, the melting process heating mode is that nature heats up.
5. the phosphate seal glass preparation method with super-low expansion softening temperature according to claim 3 is characterized in that, glass melting temperature and melting time preferred version are: 350～400 ℃ of glass melting temperatures, melting time 15～35 minutes.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011102577819A CN102432173A (en) | 2011-09-02 | 2011-09-02 | Phosphate sealing glass with ultra-low expansion softening temperature and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011102577819A CN102432173A (en) | 2011-09-02 | 2011-09-02 | Phosphate sealing glass with ultra-low expansion softening temperature and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102432173A true CN102432173A (en) | 2012-05-02 |
Family
ID=45980572
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2011102577819A Pending CN102432173A (en) | 2011-09-02 | 2011-09-02 | Phosphate sealing glass with ultra-low expansion softening temperature and preparation method thereof |
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| Country | Link |
|---|---|
| CN (1) | CN102432173A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103951189A (en) * | 2014-04-09 | 2014-07-30 | 京东方科技集团股份有限公司 | Lead-free sealing glass powder and preparation method thereof |
| CN110156326A (en) * | 2018-02-11 | 2019-08-23 | 天津理工大学 | Fluorescent glass ceramics based on glass powder with low melting point and preparation method thereof |
| CN110423007A (en) * | 2019-07-15 | 2019-11-08 | 长春理工大学 | The unleaded high stability low temperature sealing glass of alkali-free |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5281560A (en) * | 1993-06-21 | 1994-01-25 | Corning Incorporated | Non-lead sealing glasses |
-
2011
- 2011-09-02 CN CN2011102577819A patent/CN102432173A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5281560A (en) * | 1993-06-21 | 1994-01-25 | Corning Incorporated | Non-lead sealing glasses |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103951189A (en) * | 2014-04-09 | 2014-07-30 | 京东方科技集团股份有限公司 | Lead-free sealing glass powder and preparation method thereof |
| CN103951189B (en) * | 2014-04-09 | 2016-03-30 | 京东方科技集团股份有限公司 | A kind of barium crown sealed glass powder and preparation method thereof |
| CN110156326A (en) * | 2018-02-11 | 2019-08-23 | 天津理工大学 | Fluorescent glass ceramics based on glass powder with low melting point and preparation method thereof |
| CN110156326B (en) * | 2018-02-11 | 2021-11-26 | 天津理工大学 | Fluorescent glass ceramic based on low-melting-point glass powder and preparation method thereof |
| CN110423007A (en) * | 2019-07-15 | 2019-11-08 | 长春理工大学 | The unleaded high stability low temperature sealing glass of alkali-free |
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Application publication date: 20120502 |