CN101973708B - A kind of phosphorus bismuth system lead-free low-melting-point glass - Google Patents

A kind of phosphorus bismuth system lead-free low-melting-point glass Download PDF

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Publication number
CN101973708B
CN101973708B CN201010511957.4A CN201010511957A CN101973708B CN 101973708 B CN101973708 B CN 101973708B CN 201010511957 A CN201010511957 A CN 201010511957A CN 101973708 B CN101973708 B CN 101973708B
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glass
melting
low
point glass
point
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CN101973708A (en
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罗世永
许文才
张新林
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Beijing Institute of Graphic Communication
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Beijing Institute of Graphic Communication
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Abstract

A kind of phosphorus bismuth system lead-free low-melting-point glass, for making seal glass.Its composition characteristic is oxidized Vanadium Pentoxide in FLAKES and bismuthous oxide bismuth trioxide is major ingredient.Mass percent compositing range is P 2o 510 ~ 80, Bi 2o 310 ~ 60, ZnO? 0 ~ 8, Sb 2o 30 ~ 5, SnO 20 ~ 5, Al 2o 30 ~ 4, Li 2o+Na 2o+K 2o? 0 ~ 10, Ag 2o? 0 ~ 5.The glass transformation temperature that glass sample differential thermal analysis records is between 310 DEG C and 380 DEG C.Can prepare seal glass after regulating thermal expansivity with this low-melting-point glass and low bulk or high mineral filler of expanding, for glass and glass or glass and pottery or the sealing-in between glass and metal, the minimum sintering temperature of seal glass is 400 DEG C.

Description

A kind of phosphorus bismuth system lead-free low-melting-point glass
Technical field
The present invention relates to a kind of phosphorus bismuth system lead-free low-melting-point glass, as seal glass.Seal glass is mainly used in glass and glass or glass and pottery and the sealing-in between glass and metal.Its application art is generally the filler adding adjustment thermal expansivity in low-melting-point glass and forms compound seal glass powder, add organic carrier and be mixed with paste composition, the technique such as application of printed, coating closure is being formed designed shape, then reach the object of sealing-in through high temperature sintering, be mainly used in the level Hermetic Package or the insulation encapsulating that make various vacuum device.
Background technology
The low-melting-point glass great majority being used as bonding phase in electric slurry are at present plumbous borate and lead silicate glass.Because lead is to the harm of environment and human body, various electronic devices and components all require unleaded, therefore, seek lead-free low-melting-point glass and replace and now have great importance with plumbous borate and lead silicate glass.
At present about the report of lead-free low-melting-point glass mainly contains:
US Patent No. 20030047735 reports a kind of lead-free low-melting-point glass for sealing-in between silicon chip and silicon chip in photoelectric commutator, mainly consists of SnO-SiO 2-ZnO-Al 2o 3system, sealing temperature is higher than 700 DEG C.
It is P that Canadian Patent CA2409527 reports a kind of mass percent 2o 530 ~ 50%, Al 2o 315 ~ 30%, Na 2o+Li 2the lead-free and cadmium-free low-melting-point glass of O2 ~ 40%.
It is 30 ~ 80%SnO, 5.5 ~ 20%SiO that US Patent No. 20020019303 reports a kind of molecular fraction 2, 10 ~ 50%P 2o 5silicophosphate low-melting sealing glass.
ASAHITECHNOGLASSCORP company of Japan applies for a patent JP2004059367 and JP 2003-238199, and to report mass percent be 20 ~ 68%SnO, 2 ~ 8%SnO 2, 20 ~ 40%P 2o 5lead-free low-melting-point glass.
MOBAYCHEMICALCORP company of Canada applies for a patent CA1193289 and US4376169 (A1) and reports a kind of mass percent and consist of Na 2o2 ~ 9%, Li 2o2 ~ 7%, B 2o 323 ~ 34%, Al 2o 32 ~ 4%, SiO 230 ~ 45%, F0.75 ~ 4%, P 2o 52-4%, ZnO4 ~ 8%, TiO 2the lead-free low-melting-point glass of 2 ~ 5%.
FUTABADENSHIKOGYOKK company of Japan applies for a patent JPJP2004119320, and US2004071925 (A1) and DE10345248 (A1) reports a kind of P for vacuum fluorescent display sealing-in 2o 5-SnO 2system barium crown sealed glass.In addition, NEG open patent 2001-379939, Japan AGC open patent 2001-302279, US Patent No. 20040071925 and Japanese Patent JP2003238199 also report P 2o 5-SnO 2system barium crown sealed glass.
Japanese Patent Laid-Open 9-208259 reports a kind of composition mass percent: P 2o 510 ~ 70%, WO 320 ~ 80%, SiO 2, Li 2o0 ~ 40%, Na 2o0 ~ 40%, Na 2o+Li 2the lead-free low-melting-point glass of O0.1 ~ 40%.
It is Bi that Japanese Patent Laid-Open 2003-34550 reports a kind of mass percent 2o 355 ~ 88%, B 2o 35 ~ 30%, ZnO0 ~ 20%, additional a small amount of SiO 2and Al 2o 3crown glass.Japanese Patent Laid-Open 2000-36220 also reports the bismuth borate low melting glass of proximate composition.
US Patent No. 20040018931 reports a kind of lead-free low-melting-point glass, and its mass percent is SiO 211 ~ 52%, TiO 23.4 ~ 40%, Bi 2o 30 ~ 75%, ZnO0 ~ 40%, wherein Bi 2o 3+ ZnO compositing range is 15 ~ 85%.
Japanese Patent Laid-Open 9-306236 reports the unleaded crystal type low-melting-point glass of electric slurry of a kind of sintering temperature 700-870 DEG C, and it mainly forms mass percent and is: SiO 220 ~ 38%, B 2o 35.5 ~ 13.5%, Al 2o 38 ~ 15.5%, CaO4 ~ 19%, ZnO20 ~ 29%, ZrO 20 ~ 6%, MoO 30.1 ~ 3.8%.
The softening temperature that Japanese Patent Laid-Open 2002-362942 reports a kind of silicon boron zinc system is lower than the low-melting-point glass of 600 DEG C, and its percent mass consists of: SiO 25 ~ 45%, B 2o 310 ~ 60%, ZnO20 ~ 60%, Na 2o+Li 2o+K 2o1 ~ 25%, MgO+CaO+SrO+BaO0 ~ 30%, Bi 2o 30 ~ 15%, Al 2o 3+ ZrO 20 ~ 10%, SnO 2+ CeO 20 ~ 5%, FeO+CoO+NiO+MoO 30 ~ 5%.
US Patent No. 5385871 reports a kind of fluorine-containing borosilicate seal glass, and its softening temperature is 650-725 DEG C.
US Patent No. 5674789 reports a kind of containing molecular fraction La 2the borosilicate glass of O4-22%, its temperature starting to melt is 470-670 DEG C.
It is ZnO20 ~ 40% that US Patent No. 5306674 reports a kind of mass percent, SiO 210 ~ 30%, B 2o 320 ~ 30%, TiO 20 ~ 12%, Na 2o4 ~ 12%, K 2o0 ~ 10%, ZrO 20 ~ 12%, Al 2o 30 ~ 4%, Li 2o0 ~ 5%, the lead-free low-melting-point glass of F0 ~ 5%.
It is K that US Patent No. 5827789 and US6057037 report a kind of mass percent 2o10 ~ 17%, B 2o 310 ~ 25%, TiO 215 ~ 30%, SiO 235 ~ 55%, Al 2o 30 ~ 5%, Bi 2o 3the lead-free low-melting-point glass of 0 ~ 5%, S0 ~ 3%.
US Patent No. 20040029700 reports a kind of lead-free low-melting-point glass, and its mass percent is SiO 245 ~ 60%, Al 2o 35 ~ 20%, B 2o 35 ~ 20%.
US Patent No. 20030048580 reports a kind of lead-free low-melting-point glass, and its mass percent is SiO 20.5 ~ 14%, B 2o 33 ~ 15%, ZnO4 ~ 22%, Bi 2o 355 ~ 90%, Al 2o 30 ~ 4%, MgO+CaO+SrO0 ~ 15%, Na 2o+Li 2o+K 2o0 ~ 5%.
Shaanxi Tech Univ's number of applying for a patent is 200610041626.2 preparation methods reporting a kind of lead-free sealing glass for metal oxide lightning arrester, and its glass consists of the V of mass percent 20 ~ 30% 2o 5, the B of 18 ~ 24% 2o 3, the ZnO of 45 ~ 55%, the P of 0 ~ 3% 2o 5, the Bi of 0 ~ 10% 2o 3, the MO of 0 ~ 5% 3with 0 ~ 5% BaO.Form mainly V 2o 5-B 2o 3-P 2o 5system.
Donghua University's number of applying for a patent is 200610024793 report a kind of lead-free phosphate sealed glass, it is characterized in that: its component and content are by mole% being calculated as follows: P 2o 520 ~ 50%, ZnO10 ~ 26%, SnO 20 ~ 40%, B 2o 35 ~ 50%, SiO 20 ~ 15%, Al 2o 30 ~ 10%, Na 2o+Li 2o0 ~ 10%, Sb 2o 30 ~ 5%, Fe 2o 30 ~ 2%, MnO 20 ~ 5%, Cr 2o 30 ~ 2% wherein, SiO 2with Al 2o 3content sum be 0 ~ 15%.Consist of P 2o 5-ZnO-SnO 2system.
The Jingdongfang Science and Technology Group Co., Ltd number of applying for a patent CN200310103589.X and CN200310103592.1 reports a kind of seal glass primarily of phosphorus oxide, vanadium oxide and weisspiessglanz composition and preparation method.
The low-melting-point glass reported in periodical literature biases toward the theory of glass structure and aspect of performance, and compositional system is substantially within above-mentioned the scope of the claims.PYShih etc. have studied P 2o 5-Na 2the thermal characteristics of O-CuO system glass and corrosion behavior (JournalofNon-CrystallineSolids224 (1998) 143-152); The RMorena of Corning company of the U.S. have studied SnO-ZnO-P 2o 5system low-melting sealing glass (JournalofNon-CrystallineSolids263 & 264 (2000) 382-387); Duk-NamKim reports a kind of BaO-B 2o 3the lead-free low-melting-point glass (JournalofNon-CrystallineSolids306 (2002) 70-75) of-ZnO system; MFBarba etc. report a kind of with P 2o 5-CaO-SiO 2-K 2o-Na 2o is the seal glass (JournaloftheEuropeanCeramicSociety18 (1998) 1313-1317) of main composition; SBlanchandin etc. have studied TeO 2-Nb 2o 5-Bi 2o 3the glass properties (JournalofAlloysandCompounds347 (2002) 206-212) of system; J-CChampamaud-Mesjard etc. have studied TeO 2-WO 3-Bi 2o 3the glass formation range (AnnChimSciMat23 (1998) 289-292) of system; RaoufEl-Mallawany reviews the visco-elasticity of tellurate glass, phase transformation, debye temperature, thermal properties (MaterialsChemistryandPhysics60 (1999) 103-131); RIordanova etc. have studied V 2o 5-Bi 2o 3-Fe 2o 3system crystal property (JournalofNon-CrystallineSolids204 (1996) 141-150) and V 2o 5-Bi 2o 3-MoO 3the Forming ability of system glass and structure (JournalofNon-CrystallineSolids180 (1994) 58-65); CSRay etc. have studied P 2o 5-Fe 2o 3system glass properties (JournalofNon-CrystallineSolids249 (1999) 1-16); GBPakhomov etc. have studied P 2o 5-Li 2the glass of O system forms (SolidStateIonics119 (1999) 235-244); AEMarino reports a kind of phosphate glass (JournalofNon-CrystallineSolids289 (2001) 37-41) of low transition temperature; JYDing reports a kind of low-melting-point glass (MaterialsChemistryandPhysics82 (2003) 61-67) of a kind of Sn-Ca-P-O-F; RBalaji have studied Li 2o-MO-B 2o 3-V 2o 5the physical properties (PhysicaB348 (2004) 256-271) of glass.
In above-mentioned patent and periodical literature, what glass system report was more mainly contains P 2o 5-SnO 2system, P 2o 5-V 2o 5the borosilicate system of system and high bi content.And according to the difference applied, the glass ingredient of same composition system is also different.
Summary of the invention
The present invention by glass composition with phosphorus oxide and bismuth oxide for main component, add ZnO0 ~ 8, Sb 2o 30 ~ 5, SnO 20 ~ 5, Al 2o 30 ~ 4, Li 2o+Na 2o+K 2o0 ~ 10, Ag 2oxide compound composition conventional in the low-melting-point glass such as grade of O0 ~ 5 obtains has eutectic performance, has again the low-melting-point glass of better mechanical strength and chemical stability simultaneously.Over-all properties good glass quality percentage ratio compositing range is: P 2o 510 ~ 80, Bi 2o 310 ~ 60, ZnO0 ~ 8, Sb 2o 30 ~ 5, SnO 20 ~ 5, Al 2o 30 ~ 4, Li 2o+Na 2o+K 2o0 ~ 10, Ag 2o0 ~ 5.
Low-melting-point glass is prepared with traditional fusion preparation method.P in glass 2o 5use NH 4h 2pO 4or (NH 4) 2hPO 4introduce, various raw material uses the oxide compound of corresponding technical grade or carbonate powder to introduce, and by various raw material according to after the formula accurate-metering of design, mixes.At 180-240 DEG C of insulation 60-90 minute in quartz, aluminum oxide or platinum crucible, be then warmed up to 900-1150 DEG C of insulation fusing in 30 ~ 60 minutes.The cast of the glass metal of melting is pressed into thin slice or is poured into shrend in clean water and becomes particulate state.According to different application requiring, by sheet glass or particulate abrasive for subsequent use to certain fineness.
Gained sample differential thermal analyzer will be founded and measure glass transformation temperature.Different according to composition, the glass transformation temperature that glass transformation temperature records between glass sample differential thermal analysis is between 310 DEG C and 380 DEG C.Glass sample reheats a certain temperature between 400 ~ 500 DEG C can soften flowing, namely there will not be obvious crystallization during glass remelting.
One of the application of the unleaded phosphorus bismuth low-melting-point glass that the present invention proposes adds after low bulk or the high filler expanded regulate thermal expansivity to be used as seal glass, for glass and glass or glass and ceramic and between glass and metal sealing-in.The thermal expansivity of low-melting-point glass body is different according to glass composition, and its room temperature to 300 DEG C mean thermal expansion coefficients is 70 × 10 -7/ DEG C to 100 × 10 -7/ DEG C between, for sealing-in or when making coating on body material, the thermal expansivity of seal glass needs a little less than by the thermal expansivity of closure or body material usually.Therefore, the low-melting-point glass that the present invention proposes, when being used as seal glass, needs the filler adding low bulk or high expansion to regulate thermal expansivity and a small amount of mineral dye to regulate the color of sintered compact.The filler low bulk that can add can be ZrSiO 4, ZnSiO 4with β eucryptite etc., the high bulking filler that can add can be aluminium powder, copper powder, the high copper base alloy powder expanded etc.
The invention has the beneficial effects as follows: propose a kind of lead-free low-melting-point glass being main component with phosphorus oxide and bismuth oxide newly.Not containing the lead, cadmium, the chromium element that human body and environment are had to harm in composition, the leaded low-melting-point glass that current seal glass used uses can be substituted.The sintering temperature of application product is low, and the glass transformation temperature of prepared low-melting-point glass is between 310 DEG C and 380 DEG C.During as seal glass, adding filler and the ZrSiO of low bulk 4, ZnSiO 4after eucryptite, DEG C mean thermal expansion coefficients adjustment of the room temperature to 300 of seal glass is low to moderate about 45 × 10 -7/ DEG C time, the minimum sintering temperature of application product can be 400 DEG C.
Accompanying drawing explanation
Without accompanying drawing.
Embodiment
By following specific embodiment, the invention will be further described.
Embodiment 1
Glass consists of: P 2o 565%, Bi 2o 315%, ZnO4%, Sb 2o 31%, SnO 25%, Na 2o3%, K 2o3%, Ag 2o4%.After levigate to commercially available PHOSPHORIC ACID TECH.GRADE ammonium dihydrogen, bismuthous oxide bismuth trioxide, zinc oxide, antimonous oxide, tindioxide, sodium carbonate and salt of wormwood, after formula accurate-metering, mix.First 210 DEG C of insulations 60 minutes in alumina crucible, ammonium di-hydrogen phosphate is fully decomposed, then 950 DEG C of insulations fusing in 50 minutes in alumina crucible, is then pressed into thin slice by the cast of the glass metal of melting.After being ground by sheet glass, by 200 mesh sieves, add the filler ZrSiO regulating thermal expansivity 4it is 8 × 10 that powder is adjusted to thermal expansivity -7/ DEG C, may be used for the hermetic seal between ordinary plate glass.
The glass transformation temperature of differential thermal analysis gained glass is 342 DEG C, and sealing temperature is 450 DEG C.
By low-melting-point glass, black inorganic pigment and ZrSiO 4mix by 64: 2: 34 mass ratioes and be prepared seal glass powder.When seal glass is incubated at 450 DEG C, flowing property is good, and the mean thermal expansion coefficients of sintered compact room temperature to 300 DEG C is 78 × 10 -7/ DEG C.Powder being dispersed in mass percent is be prepared as paste composition in the ethyl cellulose ethyl acetate solution of 3%, be coated on ordinary plate glass by the method for needle tubing spraying, drying in 10 minutes is incubated at 160 DEG C, then in 430 DEG C of insulations presintering in 10 minutes, again with another sheet glass substrate under fixture effect, be heated to 450 DEG C of insulations and within 10 minutes, complete the sealing-in of glass and glass.Sealing-in place smooth appearance, has good sealing strength.
Embodiment 2
Glass consists of: P 2o 525%, Bi 2o 365%, ZnO3%, Sb 2o 31%, SnO 23%, Li 2o1%, Na 2o1%, K 2o1%.After levigate to commercially available PHOSPHORIC ACID TECH.GRADE ammonium dihydrogen, bismuthous oxide bismuth trioxide, zinc oxide, antimonous oxide, tindioxide, Quilonum Retard, sodium carbonate and salt of wormwood, after formula accurate-metering, mix.First 210 DEG C of insulations 60 minutes in alumina crucible, ammonium di-hydrogen phosphate is fully decomposed, then 1100 DEG C of insulations fusing in 40 minutes in alumina crucible, is then pressed into thin slice by the cast of the glass metal of melting.After sheet glass is ground, by 200 mesh sieves.
The glass transformation temperature of differential thermal analysis gained glass is 327 DEG C.
Low-melting-point glass, β eucryptite and black inorganic pigment are mixed by 68: 32: 2 mass ratioes and is prepared seal glass powder.Seal glass is functional 400 DEG C of current downflow, and the mean thermal expansion coefficients of sintered compact room temperature to 300 DEG C is 92 × 10 -7/ DEG C.Powder being dispersed in mass percent is be prepared as paste composition in the terpineol solution of ethyl cellulose of 4%, drying in 10 minutes is incubated at 170 DEG C, then in 380 DEG C of insulations presintering in 10 minutes, under fixture effect, the sealing-in that 400 DEG C of insulations complete ordinary plate glass and glass exhaust tube for 10 minutes is heated to.Sealing-in place smooth appearance, has good sealing strength.
It should be noted that, above embodiment, only for technical scheme of the present invention, it will be understood by those skilled in the art that and carries out various variation and equivalence replacement to technical scheme of the present invention, and do not deviate from principle and the scope of technical solution of the present invention, among the scope that all should be encompassed in the claims in the present invention.

Claims (2)

1. a phosphorus bismuth system lead-free low-melting-point glass, for making seal glass, its composition characteristic is for major ingredient with Vanadium Pentoxide in FLAKES and bismuthous oxide bismuth trioxide; Mass percent compositing range is: P 2o 510 ~ 80, Bi 2o 310 ~ 60, ZnO0 ~ 8, Sb 2o 31 ~ 5, SnO 23 ~ 5, Al 2o 30 ~ 4, Li 2o+Na 2o+K 2o0 ~ 10, Ag 2o0 ~ 5; P in glass 2o 5use NH 4h 2pO 4or (NH 4) 2hPO 4introduce, various raw material uses the oxide compound of corresponding technical grade or carbonate powder to introduce, and by various raw material according to after the formula accurate-metering of design, mixes; 180 ~ 240 DEG C of insulations 60 ~ 90 minutes in quartz, aluminum oxide or platinum crucible, be then warmed up to 900 ~ 1150 DEG C of insulations fusing in 30 ~ 60 minutes; The cast of the glass metal of melting is pressed into thin slice or is poured into shrend in clean water and becomes particulate state; According to different application requiring, by sheet glass or particulate abrasive for subsequent use to certain fineness; The glass transformation temperature that glass sample differential thermal analysis records is between 310 DEG C and 380 DEG C, and glass sample reheats a certain temperature between 400 ~ 500 DEG C can soften flowing.
2. lead-free low-melting-point glass according to claim 1, it is characterized in that: add low bulk or the high mineral filler adjustment thermal expansivity expanded in this low-melting-point glass after, can seal glass be used as, for glass and glass or glass and pottery or the sealing-in between glass and metal, bonding effect has been softened in low-melting-point glass melting when sintering, and the minimum sintering temperature of seal glass is 400 DEG C.
CN201010511957.4A 2010-10-20 2010-10-20 A kind of phosphorus bismuth system lead-free low-melting-point glass Expired - Fee Related CN101973708B (en)

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CN102898026B (en) * 2012-08-22 2014-12-24 广州市儒兴科技开发有限公司 Lead-free inorganic adhesive used in silver paste on crystalline silicon solar cell back, and preparation method thereof
CN102875020B (en) * 2012-09-27 2016-03-09 广东风华高新科技股份有限公司 Lead-free glass material and preparation method thereof
CN107459257A (en) * 2016-06-03 2017-12-12 南京豪祺新材料有限公司 A kind of sealing-in Unlead low-smelting point glass and preparation method thereof
CN106495489B (en) * 2016-11-01 2019-03-12 福州大学 One kind containing P2O5LED low temperature sealing glass
CN108164150B (en) * 2016-12-07 2022-04-29 辽宁省轻工科学研究院有限公司 Preparation method and application of aluminum alloy sealing glass powder with high resistivity and high expansion coefficient
CN108164144A (en) * 2016-12-07 2018-06-15 辽宁法库陶瓷工程技术研究中心 A kind of low temperature high expansion coefficient titanium alloy seal glass and its preparation method and application

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CN101633560A (en) * 2008-07-23 2010-01-27 中国科学院过程工程研究所 Lead-free low-melting-point 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

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