CN100396632C - Preparation method of lead-free sealing glass for metal oxide lightning arrester - Google Patents

Preparation method of lead-free sealing glass for metal oxide lightning arrester Download PDF

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Publication number
CN100396632C
CN100396632C CNB2006100416262A CN200610041626A CN100396632C CN 100396632 C CN100396632 C CN 100396632C CN B2006100416262 A CNB2006100416262 A CN B2006100416262A CN 200610041626 A CN200610041626 A CN 200610041626A CN 100396632 C CN100396632 C CN 100396632C
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glass
analytically pure
zno
melting temperature
ball milling
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CN1807312A (en
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郭宏伟
刘新年
高档妮
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Shaanxi University of Science and Technology
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Shaanxi University of Science and Technology
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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
    • C03C3/16—Silica-free oxide glass compositions containing phosphorus
    • C03C3/21—Silica-free oxide glass compositions containing phosphorus containing titanium, zirconium, vanadium, tungsten or molybdenum

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  • 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 present invention relates to a preparation method of lead-free sealing glass for a metal oxide lightning arrester. Firstly, the following components are proportioned by mass and are uniformly fixed: 20% to 30% of V2O5, 18% to 24% of B2O3, 45% to 55% of ZnO, 0% to 3% of P2O5, 0% to 10% of Bi2O3, 0% to 5% of MO3 and 0% to 5% of BaO; secondly, the batch which is uniformly fixed is added in a corundum crucible or a bisque crucible under 900 DEG C and is smelted, the smelting temperature is from 1000 DEG C to 1100DEG C, and the temperature is preserved for 20 to 40 minutes; thirdly, smelted glass liquid is poured on a clean steel plate to cool off; finally, cooled glass is put in a ball milling pot and is milled, and the milled glass passes through a screen with 300 meshes. The present invention can be firmly and hermetically connected with a metal oxide surge arrester below 530 DEG C, and PbO or alkali metal oxides are not contained in the present invention. The present invention has the advantages of low melting temperature, low hermetical connection temperature, high resistivity, low expansion coefficient and high hermetical connection strength, and can be hermetically connected with a zinc oxide resistance chip.

Description

The preparation method of lead-free sealing glass for metal oxide lightning arrester
Technical field:
The present invention relates to a kind of caking agent that is used for pottery and ZnO arrester insulator, particularly a kind of metal vapour thunder arrester preparation method of barium crown sealed glass.
Background technology
The key part of metal oxide arrester is a zinc oxide resistance sheet.Because zinc oxide resistance sheet easily reacts with airborne moisture, thereby its residual voltage value is descended, cause the protection of arrester degradation, can cause the faults such as cracking when serious.In order to guarantee the safe operation of thunder arrester; trouble saving takes place; adopt the low-melting lead-free sealing glass material; seal is carried out in space between the zinc oxide resistance sheet; prevent that malaria from entering; play the effect of protection zinc oxide resistance sheet, thunder arrester work-ing life is improved, reach the purpose of safe and reliable operation.
Japanese NGK insulator (strain) patent USP4796149 has proposed a kind of glass that has good coefficient of thermal expansion to mate with pottery and ZnO ceramic component, can be used for the bonding of pottery and ZnO arrester insulator, and the PbO content of this seal glass is greater than 60 (wt) %.Liu Xinnian etc. have prepared PbO-B 2O 3-SiO 2Metal oxide arrester seal glass, the PbO content of this seal glass be greater than 70 (wt) %, its insulaion resistance height, and sealing temperature is about 500 ℃.In addition, V 2O 5Seal glass comprises V 2O 5-P 2O 5, V 2O 5-TeO 2Can form hermetic seal with device at 400 ℃ Deng, this seal glass, JP flat 2-267137 in Hitachi's has disclosed the V that a class is applicable to the LSI body seal 2O 5-P 2O 5-Sb 2O 3-PbO-TlO seal glass, this seal glass and Al 2O 3Ceramic package through-55～150 ℃ of thermal shocks, does not break for 1000 times repeatedly.
The metal current Oxide Arrester is PbO-B with the seal glass employing 2O 3-SiO 2System's seal glass, wherein the content of PbO is greater than 70 (wt) %; More than related V 2O 5The normal P that adds in the seal glass 2O 5, TeO 2, low-melting material such as PbO adds P 2O 5Can reduce V 2O 5The softening temperature of seal glass, but also reduced V simultaneously 2O 5The chemical stability of seal glass adds TeO 2, the PbO proof can fully reduce V 2O 5The softening temperature of system glass, but TeO 2, PbO has very large pollution to environment, and EU countries, the U.S., the states such as Japan have all promulgated and have clearly forbidden producing and use contains Pb, Cd, Hg, the laws and regulations of the electrical equipment such as Tl and electronic equipment, and proposed to replace and contained Pb, Cd, Hg, the deadline date of the electrical equipment such as Tl and electronic equipment.
Summary of the invention
The objective of the invention is to overcome the shortcoming of above-mentioned existing technology, provide a kind of preparation technology simple, with pottery with the coefficient of expansion of ZnO arrester insulator is consistent and the preparation method of the lead-free sealing glass for metal oxide lightning arrester of leadless environment-friendly.
For achieving the above object, the technical solution used in the present invention is: at first, and by mass percentage with 20～30% V 2O 5, 18～24% B 2O 3, 45～55% ZnO, 0～3% P 2O 5, 0～10% Bi 2O 3, 0～5% MO 3Mix with 0～5% BaO; Secondly, add this raw material that mixes in the corundum crucible under 900 ℃ or the bique crucible and found, glass melting temperature is 1000～1100 ℃, and is incubated 20～40 minutes under glass melting temperature; Again, the glass metal that melts is poured on the clean steel plate cools off; At last, cooled glass is put into the ball grinder ball milling, the glass behind the ball milling is crossed 300 mesh sieves get final product.
V of the present invention 2O 5Introduced B by analytically pure vanadic anhydride 2O 3Introduced by analytically pure boric acid; ZnO is introduced by analytically pure zinc oxide, additive P 2O 5, Bi 2O 3, MO 3, BaO is respectively by analytically pure ammonium dihydrogen phosphate (ADP), bismuth oxide, and molybdenum trioxide, brium carbonate is introduced.
Because the present invention is a raw material with Vanadium Pentoxide in FLAKES, boric acid, zinc oxide, mix the back after 1000～1100 ℃ of fusings ball milling become glass powder, by the test, this seal glass can below 530 ℃ with firm the sealing of metal oxide arrester, and do not contain PbO, the alkali-free metal oxide, temperature of fusion is low, and sealing temperature is low, the resistivity height, the coefficient of expansion is low, can carry out matched seal with zinc oxide resistance sheet, the sealing strength height.
Embodiment
Embodiment 1: at first, and by mass percentage with 25% V 2O 5, 23% B 2O 3, 48% ZnO and 4% MO 3Mix; Secondly, add this batch that mixes in the corundum crucible under 900 ℃ or the bique crucible and found, glass melting temperature is 1050 ℃, and is incubated 25 minutes under glass melting temperature; Again, the glass metal that melts is poured on the clean steel plate cools off; At last, cooled glass is put into the ball grinder ball milling, the glass behind the ball milling is crossed 300 mesh sieves get final product.Wherein, V 2O 5Introduced B by analytically pure vanadic anhydride 2O 3Introduced by analytically pure boric acid; ZnO is introduced by analytically pure zinc oxide, additive MO 3Introduced by analytically pure molybdenum trioxide.
Embodiment 2: at first, and by mass percentage with 25% V 2O 5, 18% B 2O 3, 48% ZnO, 3% P 2O 5, 2% Bi 2O 3, 3% MO 3Mix with 1% BaO; Secondly, add this batch that mixes in the corundum crucible under 900 ℃ or the bique crucible and found, glass melting temperature is 1100 ℃, and is incubated 30 minutes under glass melting temperature; Again, the glass metal that melts is poured on the clean steel plate cools off; At last, cooled glass is put into the ball grinder ball milling, the glass behind the ball milling is crossed 300 mesh sieves get final product.Wherein, V 2O 5Introduced B by analytically pure vanadic anhydride 2O 3Introduced by analytically pure boric acid; ZnO is introduced by analytically pure zinc oxide, additive P 2O 5, Bi 2O 3, MO 3, BaO is respectively by analytically pure ammonium dihydrogen phosphate (ADP), bismuth oxide, and molybdenum trioxide, brium carbonate is introduced.
Embodiment 3: at first, and by mass percentage with 28.5% V 2O 5, 24% B 2O 3Mix with 47.5% ZnO; Secondly, add this batch that mixes in the corundum crucible under 900 ℃ or the bique crucible and found, glass melting temperature is 1000 ℃, and is incubated 20 minutes under glass melting temperature; Again, the glass metal that melts is poured on the clean steel plate cools off; At last, cooled glass is put into the ball grinder ball milling, the glass behind the ball milling is crossed 300 mesh sieves get final product.Wherein, V 2O 5Introduced B by analytically pure vanadic anhydride 2O 3Introduced by analytically pure boric acid; ZnO is introduced by analytically pure zinc oxide.
Embodiment 4: at first, and by mass percentage with 30% V 2O 5, 18% B 2O 3, 45% ZnO, 1% P 2O 5, 3% Bi 2O 3, 1% MO 3Mix with 2% BaO; Secondly, add this batch that mixes in the corundum crucible under 900 ℃ or the bique crucible and found, glass melting temperature is 1020 ℃, and is incubated 40 minutes under glass melting temperature; Again, the glass metal that melts is poured on the clean steel plate cools off; At last, cooled glass is put into the ball grinder ball milling, the glass behind the ball milling is crossed 300 mesh sieves get final product.Wherein, V 2O 5Introduced B by analytically pure vanadic anhydride 2O 3Introduced by analytically pure boric acid; ZnO is introduced by analytically pure zinc oxide, additive P 2O 5, Bi 2O 3, MO 3, BaO is respectively by analytically pure ammonium dihydrogen phosphate (ADP), bismuth oxide, and molybdenum trioxide, brium carbonate is introduced.
Embodiment 5: at first, and by mass percentage with 20% V 2O 5, 22% B 2O 3, 55% ZnO and 3% BaO mix; Secondly, add this batch that mixes in the corundum crucible under 900 ℃ or the bique crucible and found, glass melting temperature is 1080 ℃, and is incubated 28 minutes under glass melting temperature; Again, the glass metal that melts is poured on the clean steel plate cools off; At last, cooled glass is put into the ball grinder ball milling, the glass behind the ball milling is crossed 300 mesh sieves get final product.Wherein, V 2O 5Introduced B by analytically pure vanadic anhydride 2O 3Introduced by analytically pure boric acid; ZnO is introduced by analytically pure zinc oxide, and additive BaO is introduced by analytically pure brium carbonate respectively.
Embodiment 6: at first, and by mass percentage with 20% V 2O 5, 20% B 2O 3, 50% ZnO, 10% Bi 2O 3, mix; Secondly, add this batch that mixes in the corundum crucible under 900 ℃ or the bique crucible and found, glass melting temperature is 1030 ℃, and is incubated 35 minutes under glass melting temperature; Again, the glass metal that melts is poured on the clean steel plate cools off; At last, cooled glass is put into the ball grinder ball milling, the glass behind the ball milling is crossed 300 mesh sieves get final product.Wherein, V 2O 5Introduced B by analytically pure vanadic anhydride 2O 3Introduced by analytically pure boric acid; ZnO is introduced by analytically pure zinc oxide, additive Bi 2O 3Introduced by analytically pure bismuth oxide.
Embodiment 7: at first, and by mass percentage with 22% V 2O 5, 19% B 2O 3, 52% ZnO, 1% P 2O 5, 5% MO 3Mix with 1% BaO; Secondly, add this batch that mixes in the corundum crucible under 900 ℃ or the bique crucible and found, glass melting temperature is 1060 ℃, and is incubated 30 minutes under glass melting temperature; Again, the glass metal that melts is poured on the clean steel plate cools off; At last, cooled glass is put into the ball grinder ball milling, the glass behind the ball milling is crossed 300 mesh sieves get final product.Wherein, V 2O 5Introduced B by analytically pure vanadic anhydride 2O 3Introduced by analytically pure boric acid; ZnO is introduced by analytically pure zinc oxide, additive P 2O 5, MO 3, BaO is respectively by analytically pure ammonium dihydrogen phosphate (ADP), molybdenum trioxide, and brium carbonate is introduced.
Embodiment 8: at first, and by mass percentage with 23% V 2O 5, 21% B 2O 3, 46% ZnO, 5% Bi 2O 3Mix with 5% BaO; Secondly, add this batch that mixes in the corundum crucible under 900 ℃ or the bique crucible and found, glass melting temperature is 1050 ℃, and is incubated 30 minutes under glass melting temperature; Again, the glass metal that melts is poured on the clean steel plate cools off; At last, cooled glass is put into the ball grinder ball milling, the glass behind the ball milling is crossed 300 mesh sieves get final product.Wherein, V 2O 5Introduced B by analytically pure vanadic anhydride 2O 3Introduced by analytically pure boric acid; ZnO is introduced by analytically pure zinc oxide, additive Bi 2O 3Introduced by analytically pure bismuth oxide and brium carbonate respectively with BaO.
In use sealing glass powder of the present invention is mixed with organic binder bond (acetate butyl), adopt the method that sprays to be coated in the periphery of ZnO arrester insulator, refill ceramic package, get final product carrying out sealing-in below 530 ℃, in addition, test shows that the room temperature resistivity of measuring seal glass under 1000v is all greater than 10 14Ω m.

Claims (9)

1. the preparation method of lead-free sealing glass for metal oxide lightning arrester is characterized in that:
1) at first, by mass percentage with 20～30% V 2O 5, 18～24% B 2O 3, 45～55% ZnO, 0～3% P 2O 5, 0～10% Bi 2O 3, 0～5% MO 3Mix said V with 0～5% BaO 2O 5Introduced B by analytically pure vanadic anhydride 2O 3Introduced by analytically pure boric acid; ZnO is introduced by analytically pure zinc oxide, additive P 2O 5, Bi 2O 3, MO 3, BaO is respectively by analytically pure ammonium dihydrogen phosphate (ADP), bismuth oxide, and molybdenum trioxide, brium carbonate is introduced;
2) secondly, add this admixtion that mixes in corundum crucible under 900 ℃ or the bique crucible and found, glass melting temperature is 1000～1100 ℃, and is incubated 20～40 minutes under glass melting temperature;
3) once more, the glass metal that melts is poured on the clean steel plate cools off;
4) last, cooled glass is put into the ball grinder ball milling, the glass behind the ball milling is crossed 300 mesh sieves get final product.
2. the preparation method of lead-free sealing glass for metal oxide lightning arrester according to claim 1 is characterized in that: at first, and by mass percentage with 25% V 2O 5, 23% B 2O 3, 48% ZnO and 4% MO 3Mix; Secondly, add this batch that mixes in the corundum crucible under 900 ℃ or the bique crucible and found, glass melting temperature is 1050 ℃, and is incubated 25 minutes under glass melting temperature; Again, the glass metal that melts is poured on the clean steel plate cools off; At last, cooled glass is put into the ball grinder ball milling, the glass behind the ball milling is crossed 300 mesh sieves get final product, wherein, V 2O 5Introduced B by analytically pure vanadic anhydride 2O 3Introduced by analytically pure boric acid; ZnO is introduced by analytically pure zinc oxide, additive MO 3Introduced by analytically pure molybdenum trioxide.
3. the preparation method of lead-free sealing glass for metal oxide lightning arrester according to claim 1 is characterized in that: at first, and by mass percentage with 25% V 2O 5, 18% B 2O 3, 48% ZnO, 3% P 2O 5, 2% Bi 2O 3, 3% MO 3Mix with 1% BaO; Secondly, add this batch that mixes in the corundum crucible under 900 ℃ or the bique crucible and found, glass melting temperature is 1100 ℃, and is incubated 30 minutes under glass melting temperature; Again, the glass metal that melts is poured on the clean steel plate cools off; At last, cooled glass is put into the ball grinder ball milling, the glass behind the ball milling is crossed 300 mesh sieves get final product, wherein, V 2O 5Introduced B by analytically pure vanadic anhydride 2O 3Introduced by analytically pure boric acid; ZnO is introduced by analytically pure zinc oxide, additive P 2O 5, Bi 2O 3, MO 3, BaO is respectively by analytically pure ammonium dihydrogen phosphate (ADP), bismuth oxide, and molybdenum trioxide, brium carbonate is introduced.
4. the preparation method of lead-free sealing glass for metal oxide lightning arrester according to claim 1 is characterized in that: at first, and by mass percentage with 28.5% V 2O 5, 24% B 2O 3Mix with 47.5% ZnO; Secondly, add this batch that mixes in the corundum crucible under 900 ℃ or the bique crucible and found, glass melting temperature is 1000 ℃, and is incubated 20 minutes under glass melting temperature; Again, the glass metal that melts is poured on the clean steel plate cools off; At last, cooled glass is put into the ball grinder ball milling, the glass behind the ball milling is crossed 300 mesh sieves get final product, wherein, V 2O 5Introduced B by analytically pure vanadic anhydride 2O 3Introduced by analytically pure boric acid; ZnO is introduced by analytically pure zinc oxide.
5. the preparation method of lead-free sealing glass for metal oxide lightning arrester according to claim 1 is characterized in that: at first, and by mass percentage with 30% V 2O 5, 18% B 2O 3, 45% ZnO, 1% P 2O 5, 3% Bi 2O 3, 1% MO 3Mix with 2% BaO; Secondly, add this batch that mixes in the corundum crucible under 900 ℃ or the bique crucible and found, glass melting temperature is 1020 ℃, and is incubated 40 minutes under glass melting temperature; Again, the glass metal that melts is poured on the clean steel plate cools off; At last, cooled glass is put into the ball grinder ball milling, the glass behind the ball milling is crossed 300 mesh sieves get final product, wherein, V 2O 5Introduced B by analytically pure vanadic anhydride 2O 3Introduced by analytically pure boric acid; ZnO is introduced by analytically pure zinc oxide, additive P 2O 5, Bi 2O 3, MO 3, BaO is respectively by analytically pure ammonium dihydrogen phosphate (ADP), bismuth oxide, and molybdenum trioxide, brium carbonate is introduced.
6. the preparation method of lead-free sealing glass for metal oxide lightning arrester according to claim 1 is characterized in that: at first, and by mass percentage with 20% V 2O 5, 22% B 2O 3, 55% ZnO and 3% BaO mix; Secondly, add this batch that mixes in the corundum crucible under 900 ℃ or the bique crucible and found, glass melting temperature is 1080 ℃, and is incubated 28 minutes under glass melting temperature; Again, the glass metal that melts is poured on the clean steel plate cools off; At last, cooled glass is put into the ball grinder ball milling, the glass behind the ball milling is crossed 300 mesh sieves get final product, wherein, V 2O 5Introduced B by analytically pure vanadic anhydride 2O 3Introduced by analytically pure boric acid; ZnO is introduced by analytically pure zinc oxide, and additive BaO is introduced by analytically pure brium carbonate.
7. the preparation method of lead-free sealing glass for metal oxide lightning arrester according to claim 1 is characterized in that: at first, and by mass percentage with 20% V 2O 5, 20% B 2O 3, 50% ZnO, 10% Bi 2O 3, mix; Secondly, add this batch that mixes in the corundum crucible under 900 ℃ or the bique crucible and found, glass melting temperature is 1030 ℃, and is incubated 35 minutes under glass melting temperature; Again, the glass metal that melts is poured on the clean steel plate cools off; At last, cooled glass is put into the ball grinder ball milling, the glass behind the ball milling is crossed 300 mesh sieves get final product, wherein, V 2O 5Introduced B by analytically pure vanadic anhydride 2O 3Introduced by analytically pure boric acid; ZnO is introduced by analytically pure zinc oxide, additive Bi 2O 3Introduced by analytically pure bismuth oxide.
8. the preparation method of lead-free sealing glass for metal oxide lightning arrester according to claim 1 is characterized in that: at first, and by mass percentage with 22% V 2O 5, 19% B 2O 3, 52% ZnO, 1% P 2O 5, 5% MO 3Mix with 1% BaO; Secondly, add this batch that mixes in the corundum crucible under 900 ℃ or the bique crucible and found, glass melting temperature is 1060 ℃, and is incubated 30 minutes under glass melting temperature; Again, the glass metal that melts is poured on the clean steel plate cools off; At last, cooled glass is put into the ball grinder ball milling, the glass behind the ball milling is crossed 300 mesh sieves get final product, wherein, V 2O 5Introduced B by analytically pure vanadic anhydride 2O 3Introduced by analytically pure boric acid; ZnO is introduced by analytically pure zinc oxide, additive P 2O 5, MO 3, BaO is respectively by analytically pure ammonium dihydrogen phosphate (ADP), molybdenum trioxide, and brium carbonate is introduced.
9. the preparation method of lead-free sealing glass for metal oxide lightning arrester according to claim 1 is characterized in that: at first, and by mass percentage with 23% V 2O 5, 21% B 2O 3, 46% ZnO, 5% Bi 2O 3Mix with 5% BaO; Secondly, add this batch that mixes in the corundum crucible under 900 ℃ or the bique crucible and found, glass melting temperature is 1050 ℃, and is incubated 30 minutes under glass melting temperature; Again, the glass metal that melts is poured on the clean steel plate cools off; At last, cooled glass is put into the ball grinder ball milling, the glass behind the ball milling is crossed 300 mesh sieves get final product, wherein, V 2O 5Introduced B by analytically pure vanadic anhydride 2O 3Introduced by analytically pure boric acid; ZnO is introduced by analytically pure zinc oxide, additive Bi 2O 3Introduced by analytically pure bismuth oxide and brium carbonate respectively with BaO.
CNB2006100416262A 2006-01-10 2006-01-10 Preparation method of lead-free sealing glass for metal oxide lightning arrester Expired - Fee Related CN100396632C (en)

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Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101164939B (en) * 2006-10-19 2010-08-18 北京印刷学院 Leadless barium borate low melting glass and application thereof
CN101265023B (en) * 2007-03-15 2010-05-26 北京印刷学院 Vanadium-silver low melting glass and conductive slurry containing the glass
CN101503292B (en) * 2009-03-07 2011-09-14 抚顺电瓷制造有限公司 Formula of direct current zinc oxide resistance chip
CN102757182B (en) * 2012-08-06 2014-12-10 西安创联宏晟电子有限公司 Low-temperature low expansion coefficient high-rigidity lead-free electronic glass powder and preparation method thereof
CN110372215A (en) * 2019-08-07 2019-10-25 北京北旭电子材料有限公司 A kind of sealing glass material and preparation method thereof, connection component

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4796149A (en) * 1986-11-27 1989-01-03 Ngk Insulators, Ltd. Lightning arrestor insulator
WO2004074198A1 (en) * 2003-02-19 2004-09-02 Yamato Electronic Co., Ltd. Lead-free glass material for use in sealing and, sealed article and method for sealing using the same
WO2005000755A1 (en) * 2003-06-27 2005-01-06 Yamato Electronic Co., Ltd. Lead-free glass material for use in sealing and, sealed article and method for sealing using the same
CN1616366A (en) * 2003-11-11 2005-05-18 京东方科技集团股份有限公司 Lead-free sealing glass powder and producing method

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4796149A (en) * 1986-11-27 1989-01-03 Ngk Insulators, Ltd. Lightning arrestor insulator
WO2004074198A1 (en) * 2003-02-19 2004-09-02 Yamato Electronic Co., Ltd. Lead-free glass material for use in sealing and, sealed article and method for sealing using the same
WO2005000755A1 (en) * 2003-06-27 2005-01-06 Yamato Electronic Co., Ltd. Lead-free glass material for use in sealing and, sealed article and method for sealing using the same
CN1616366A (en) * 2003-11-11 2005-05-18 京东方科技集团股份有限公司 Lead-free sealing glass powder and producing method

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