CN101597136A - A kind of lead-free low-melting sealing glass and preparation method thereof - Google Patents
A kind of lead-free low-melting sealing glass and preparation method thereof Download PDFInfo
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- CN101597136A CN101597136A CNA2009101821014A CN200910182101A CN101597136A CN 101597136 A CN101597136 A CN 101597136A CN A2009101821014 A CNA2009101821014 A CN A2009101821014A CN 200910182101 A CN200910182101 A CN 200910182101A CN 101597136 A CN101597136 A CN 101597136A
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Abstract
The invention discloses a kind of lead-free low-melting sealing glass and preparation method thereof, this glass comprises the raw material of following molar percentage: 20～55mol%P
2O
5, 5～30mol%TeO
2, 0～55mol%ZnO and content are no more than the additive component of the total component concentration 30% of glass.Each component of lead-free low-melting sealing glass provided by the invention and set of dispense are not polluted or the lead composition of toxic action than not containing in scientific and reasonable, the component environment and human body had, environmental protection, low toxicity, and the softening temperature of glass and thermal expansivity scope are wide, can be applied to the low temperature encapsulation between different electronic devices and components.And preparation method provided by the invention, simple and direct reasonable, workable, the product qualified rate height can be fit to continuous large-scale industrialized.
Description
Technical field:
The present invention relates to a kind of barium crown sealed glass, be specifically related to a kind of not leadedly and have the low melting point characteristic, can be used for electronic devices and components are carried out the preparation method of glass and this glass of sealing-in.
Background technology:
In electron trade, the glass-sealed mode of normal employing is come between glass assembly, glass workpiece and metal, connection between alloy or pottery seals, the temperature of this sealing-in is wished low as far as possible, injury-free to guarantee to electrical part or electronics implements, in existing most of low temperature seal glass that uses, mainly to contain plumbous oxide, the glass of zinc oxide is main, it is big that these glass have resistance, dielectric loss is little, softening temperature is low, good chemical stability, can satisfy multiple sealing-in requirement preferably, but owing to contain lead element in the component, continuous enhancing with bigger toxicity and people's environmental consciousness, various countries have strengthened unleaded research and the corresponding legistration work of electron trade, green, environmental protection, unleaded trend has become the theme of electronics manufacturing, therefore, for providing unleaded low temperature sealing glass material, electron trade becomes a urgent problem.
At present, the research and development of lead-free low-temperature seal glass mainly concentrates on phosphate system, borate glass system, vanadate system and the bismuthate glass system that contains SnO, ZnO both at home and abroad.
Wherein the sharpest edges of lead-free low-melting phosphate glass are the low sealing temperature that low melting point is brought, but also exist defectives such as thermal expansivity is big, poor chemical stability, complicated process of preparation simultaneously, therefore, often add Al
2O
3, SiO
2, RO oxide compounds such as (R=Zn, Ba, Mg) improves performances such as its chemical stability, thermal expansivity and flowability.P in the lead-free low-melting phosphate glass
2O
5-SnO-ZnO system (be called for short PSZ) research the most extensive, many similar performances of it and flint glass, as 500C viscosity less than 10
3Pa.s, good fluidity in the sealing-in process, crystallization does not too early add the small number of crystal nucleus agent and can effectively control crystallization.Relevant patent report has US5281560, CN1087883, JP2001019473, JP2001139344, JP2003183050 to close US2005255985 etc.But contain a large amount of SnO in the PSZ system glass prescription, found the as easy as rolling off a log SnO of being oxidized to of SnO in the process
2, therefore need under nitrogen and reducing atmosphere, found; The SnO price is more expensive, the cost height, thereby there is certain difficulty in extensive industrialization.
In the borate glass system in recent years with BaO-ZnO-B
2O
3Recently research is many slightly, and after its subject matter was to add the eutectic oxide compound, its sealing temperature and other performance often can not meet the demands simultaneously.The seal glass of vanadate and bismuthate system then mainly is that cost is too high, and sealing temperature is higher, and thermal expansivity is too big, has limited it and has been extensive use of.
Summary of the invention:
Goal of the invention: the objective of the invention is to overcome in the prior art and to have easy oxidation, SnO that cost the is high defective that becomes to grade in poisonous element such as leaded in the seal glass and the phosphate seal glass, a kind of lead-free low-melting sealing glass and preparation method thereof is provided.
Technical scheme: in order to realize above purpose, the present invention by the following technical solutions:
A kind of lead-free low-melting sealing glass, it comprises the raw material of following molar percentage: 20～55mol%P
2O
5, 5～30mol%TeO
2With 0～55mol%ZnO.
As preferred version, can also add 2～20mol%B in the lead-free low-melting sealing glass provided by the invention
2O
3, 0～16mol%Bi
2O
3, 0～12mol%Sb
2O
3, 0～12mol%V
2O
5, 0～12mol%Li
2O, 0～15mol%Na
2O, 0～12mol%K
2O, 0～8mol%MgO, 0～10mol%SrO, 0～12mol%CaO, 0～30mol%BaO, 0～8mol%SnO, 0～4mol%CuO, 0～5mol%Al
2O
3, 0～8mol%La
2O
3, 0～8mol%Fe
2O
3, 0～3mol%SiO
2Or 0～8mol%TiO
2In one or more various ingredients blended additive components.Wherein the additive component total content is no more than the 30mol% of the total component concentration of glass.
Lead-free low-melting sealing glass provided by the invention, also can be according to specific requirement, basic metal in the additive component or alkaline earth metal oxide are replaced with halid one or more combinations of corresponding alkali metal or alkaline-earth metal, wherein, the halid total content of basic metal or alkaline-earth metal is no more than the 5mol% of the total component concentration of glass.
Lead-free low-melting sealing glass provided by the invention, according to the difference of glass ingredient, wherein the softening range of lead-free low-melting sealing glass is 420～470 ℃, the thermal expansivity scope is 65～130 * 10
-7℃.
A kind of preparation method of lead-free low-melting sealing glass may further comprise the steps:
1. take by weighing corresponding raw material by mole per-cent, mix, standby;
2. get step mixture 1. and under 900～1250 ℃, founded 1～3 hour, obtain glass melt;
3. get the glass melt that 2. step obtain and pour into a mould cooling, grind to form glass powder after the cooling promptly.
Lead-free low-melting sealing glass provided by the invention can be applied as between glass assembly, being connected or sealing material between glass workpiece and metal, alloy or pottery.
Beneficial effect: lead-free low-melting sealing glass provided by the invention and glassy phase of the prior art ratio have the following advantages:
1, lead-free low-melting sealing glass provided by the present invention, show through lot of experiments, form each component of glass and proportioning is scientific and reasonable, each component raw material is easy to get, do not contain in the component environment and human body had and pollute or the lead composition of toxic action environmental protection, low toxicity.
2, the softening temperature of lead-free low-melting sealing glass provided by the present invention and thermal expansivity scope are wide, it can be adjusted proportioning between glass ingredient and each component by the temperature of sealing-in product, thermal expansion character etc. according to difference, thereby can satisfy the sealing-in requirement of multiple storeroom, applied range.
3, the preparation method of lead-free low-melting sealing glass provided by the present invention is simple and direct rationally, and workable, the product qualified rate height can be fit to continuous large-scale industrialized.
Embodiment:
According to following embodiment, the present invention may be better understood.Yet, those skilled in the art will readily understand that the described concrete material proportion of embodiment, processing condition and result thereof only are used to illustrate the present invention, and should also can not limit the present invention described in detail in claims.
Embodiment 1:
Calculate and choose each raw material, wherein P by 1 design of the example in the table 1
2O
5Introduce with ammonium phosphate, other raw material then is corresponding carbonate, oxide compound and fluorochemical.Raw material weighing is mixed after good, and dry thermal treatment at 260 ℃, grind then, pulverize, place quartz crucible then, quartz crucible is placed in the globars electric furnace then, after 1200 ℃ heating is founded 2 hours down, obtain taking out behind the melten glass body, be cast in immediately then on the chill plate, then cooled glass fragment pulverized, grind, cross 200 mesh sieves and obtain glass powder.
The glass powder of preparation is measured according to the nature parameters that the industry standard SJ/T 10893-6 of China Electronics is correlated with, comprised softening temperature and finished product thermal expansivity etc., corresponding measuring result is as shown in table 1.
Table 1: the glass of different components proportioning and performance measurement result
Embodiment 2
Calculate and choose each raw material, wherein P by 2 designs of the example in the table 1
2O
5Introduce with ammonium phosphate, other raw material then is corresponding carbonate or oxide compound.Raw material weighing is mixed after good, and dry thermal treatment at 250 ℃, grind then, pulverize, place quartz crucible then, quartz crucible is placed in the globars electric furnace then, after 1050 ℃ heating is founded 3 hours down, obtain taking out behind the melten glass body, be cast in immediately then on the chill plate, then cooled glass fragment pulverized, grind, cross 200 mesh sieves and obtain glass powder.
The glass powder of preparation is measured according to the nature parameters that the industry standard SJ/T 10893-6 of China Electronics is correlated with, comprised softening temperature and finished product thermal expansivity etc., corresponding measuring result is as shown in table 1.
Embodiment 3
Calculate and choose each raw material, wherein P by 3 designs of the example in the table 1
2O
5Introduce with ammonium phosphate, other raw material then is corresponding carbonate or oxide compound.Raw material weighing is mixed after good, and dry thermal treatment at 250 ℃, grind then, pulverize, place quartz crucible then, quartz crucible is placed in the globars electric furnace then, after 1100 ℃ heating is founded 3 hours down, obtain taking out behind the melten glass body, be cast in immediately then on the chill plate, then cooled glass fragment pulverized, grind, cross 200 mesh sieves and obtain glass powder.
The glass powder of preparation is measured according to the nature parameters that the industry standard SJ/T 10893-6 of China Electronics is correlated with, comprised softening temperature and finished product thermal expansivity etc., corresponding measuring result is as shown in table 1.
Embodiment 4
Calculate and choose each raw material, wherein P by 4 designs of the example in the table 1
2O
5Introduce with ammonium phosphate, other raw material then is corresponding oxide compound.Raw material weighing is mixed after good, and dry thermal treatment at 260 ℃, grind then, pulverize, place quartz crucible then, quartz crucible is placed in the globars electric furnace then, after 950 ℃ heating is founded 3 hours down, obtain taking out behind the melten glass body, be cast in immediately then on the chill plate, then cooled glass fragment pulverized, grind, cross 200 mesh sieves and obtain glass powder.
The glass powder of preparation is measured according to the nature parameters that the industry standard SJ/T 10893-6 of China Electronics is correlated with, comprised softening temperature and finished product thermal expansivity etc., corresponding measuring result is as shown in table 1.
Embodiment 5
Calculate and choose each raw material, wherein P by 5 designs of the example in the table 1
2O
5Introduce with ammonium phosphate, other raw material then is corresponding oxide compound.Raw material weighing is mixed after good, and dry thermal treatment at 260 ℃, grind then, pulverize, place quartz crucible then, quartz crucible is placed in the globars electric furnace then, after 1230 ℃ heating is founded 3 hours down, obtain taking out behind the melten glass body, be cast in immediately then on the chill plate, then cooled glass fragment pulverized, grind, cross 200 mesh sieves and obtain glass powder.
The glass powder of preparation is measured according to the nature parameters that the industry standard SJ/T 10893-6 of China Electronics is correlated with, comprised softening temperature and finished product thermal expansivity etc., corresponding measuring result is as shown in table 1.
Embodiment 6
Calculate and choose each raw material, wherein P by 6 designs of the example in the table 2
2O
5Introduce with ammonium phosphate, other raw material then is corresponding oxide compound.Raw material weighing is mixed after good, and dry thermal treatment at 260 ℃, grind then, pulverize, place quartz crucible then, quartz crucible is placed in the globars electric furnace then, after 1150 ℃ heating is founded 2 hours down, obtain taking out behind the melten glass body, be cast in immediately then on the chill plate, then cooled glass fragment pulverized, grind, cross 200 mesh sieves and obtain glass powder.
The glass powder of preparation is measured according to the nature parameters that the industry standard SJ/T 10893-6 of China Electronics is correlated with, comprised softening temperature and finished product thermal expansivity etc., corresponding measuring result is as shown in table 2.
Table 2: the glass of different components proportioning and performance measurement result
Each raw material is calculated and chosen to scheme according to embodiment in the table 27 to 10 design, prepares the lead-free low-melting sealing glass of different components proportioning according to the method for embodiment 6, and it is as shown in table 2 that each organizes the performance test results of glass.
Show that by above specific embodiment result lead-free low-melting sealing glass provided by the invention has the good comprehensive performance, by adjusting the proportioning of component and component, bigger variation has taken place in each character of forming glass, the constant interval of softening temperature is 420～470 ℃, and thermal expansivity is 65～130 * 10
-7℃.Therefore, lead-free low-melting sealing glass provided by the invention can be applied to the low temperature encapsulation between different electronic devices and components.
Claims (7)
1, a kind of lead-free low-melting sealing glass is characterized in that: it comprises the raw material of following molar percentage: 20～55mol%P
2O
5, 5～30mol%TeO
2, 0～55mol%ZnO.
2, lead-free low-melting sealing glass according to claim 1 is characterized in that: also contain 2～20mol%B in the described lead-free low-melting sealing glass
2O
3, 0～16mol%Bi
2O
3, 0～12mol%Sb
2O
3, 0～12mol%V
2O
5, 0～12mol%Li
2O, 0～15mol%Na
2O, 0～12mol%K
2O, 0～8mol%MgO, 0～10mol%SrO, 0～12mol%CaO, 0～30mol%BaO, 0～8mol%SnO, 0～4mol%CuO, 0～5mol%Al
2O
3, 0～8mol%La
2O
3, 0～8mol%Fe
2O
3, 0～3mol%SiO
2Or 0～8mol%TiO
2In one or more various ingredients blended additive components.
3, lead-free low-melting sealing glass according to claim 2 is characterized in that: described additive component total content is no more than the 30mol% of the total component concentration of glass.
4, lead-free low-melting sealing glass according to claim 2, it is characterized in that: basic metal in the described additive component or alkaline earth metal oxide can be halid one or more the combination of corresponding alkali metal or alkaline-earth metal, wherein, the total content of the halogenide of basic metal or alkaline-earth metal composition is no more than the 5mol% of the total component concentration of glass.
According to each described lead-free low-melting sealing glass of claim 1 to 4, it is characterized in that 5, the softening temperature of described lead-free low-melting sealing glass is 420～470 ℃.
6, according to each described lead-free low-melting sealing glass of claim 1 to 4, it is characterized in that: the thermal expansivity of described lead-free low-melting sealing glass is 65～130 * 10
-7/ ℃.
7, a kind of preparation method of lead-free low-melting sealing glass is characterized in that, may further comprise the steps:
1. take by weighing corresponding raw material by mole per-cent, mix, standby;
2. get step 1. compound under 900～1250 ℃, founded 1～3 hour;
3. get the glass melt that 2. step obtain and pour into a mould cooling, grind to form glass powder after the cooling promptly.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2009101821014A CN101597136A (en) | 2009-07-23 | 2009-07-23 | A kind of lead-free low-melting sealing glass and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2009101821014A CN101597136A (en) | 2009-07-23 | 2009-07-23 | A kind of lead-free low-melting sealing glass and preparation method thereof |
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| CN101597136A true CN101597136A (en) | 2009-12-09 |
Family
ID=41418764
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|---|---|---|---|
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| CN103342451A (en) * | 2013-06-20 | 2013-10-09 | 山东康友光电科技股份有限公司 | Manufacturing method for lead-free sealing glass with transitional expansion coefficient |
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| CN104193180A (en) * | 2014-08-22 | 2014-12-10 | 洛阳兰迪玻璃机器股份有限公司 | Low-melting point glass powder |
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| CN107140839A (en) * | 2017-06-05 | 2017-09-08 | 西安工程大学 | A kind of lead-free glass powder with low melting point and preparation method thereof |
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| CN108996910A (en) * | 2018-09-07 | 2018-12-14 | 苏州融睿电子科技有限公司 | A kind of assembly, mixture, seal glass and preparation method thereof |
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| CN103402941B (en) * | 2011-02-18 | 2019-03-01 | 肖特公开股份有限公司 | Glass, especially glass solder or melten glass |
| CN103402941A (en) * | 2011-02-18 | 2013-11-20 | 肖特公开股份有限公司 | Glass, in particular glass solder or fusible glass |
| US20130330600A1 (en) * | 2011-02-18 | 2013-12-12 | Schott Ag | Glass, in particular solder glass or fusible glass |
| US20130330604A1 (en) * | 2011-02-18 | 2013-12-12 | Schott Ag | Feed-through and method for integrating the feed-through in a housing by ultrasonic welding |
| US20180169785A1 (en) * | 2011-02-18 | 2018-06-21 | Shott Ag | Glass, in particular solder glass or fusible glass |
| US20180178312A1 (en) * | 2011-02-18 | 2018-06-28 | Schott Ag | Feed-through component |
| CN102898024A (en) * | 2012-09-27 | 2013-01-30 | 广东风华高新科技股份有限公司 | Tellurium-containing glass material and preparation method and application thereof |
| CN103342451A (en) * | 2013-06-20 | 2013-10-09 | 山东康友光电科技股份有限公司 | Manufacturing method for lead-free sealing glass with transitional expansion coefficient |
| CN103342451B (en) * | 2013-06-20 | 2015-03-25 | 山东康友光电科技股份有限公司 | Manufacturing method for lead-free sealing glass with transitional expansion coefficient |
| CN104193180A (en) * | 2014-08-22 | 2014-12-10 | 洛阳兰迪玻璃机器股份有限公司 | Low-melting point glass powder |
| CN107043215A (en) * | 2017-04-25 | 2017-08-15 | 福州大学 | A kind of low temperature sealing glass of lanthana modification and its preparation and application method |
| CN107140839A (en) * | 2017-06-05 | 2017-09-08 | 西安工程大学 | A kind of lead-free glass powder with low melting point and preparation method thereof |
| CN108328912A (en) * | 2018-04-08 | 2018-07-27 | 武汉理工大学 | A kind of anode linkage method and device for vacuum glass sealing-in |
| CN108328912B (en) * | 2018-04-08 | 2020-01-31 | 武汉理工大学 | anodic bonding method and device for vacuum glass sealing |
| CN108996910A (en) * | 2018-09-07 | 2018-12-14 | 苏州融睿电子科技有限公司 | A kind of assembly, mixture, seal glass and preparation method thereof |
| CN111540501A (en) * | 2020-05-04 | 2020-08-14 | 上海匡宇科技股份有限公司 | Glass powder and solar cell anode conductive silver paste prepared from same |
| CN114180843A (en) * | 2021-12-28 | 2022-03-15 | 海南大学 | Sealing glass and preparation method thereof |
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Open date: 20091209 |