CN104150778B - A kind of leadless and low-melting point sealing glass - Google Patents
A kind of leadless and low-melting point sealing glass Download PDFInfo
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- CN104150778B CN104150778B CN201410389494.7A CN201410389494A CN104150778B CN 104150778 B CN104150778 B CN 104150778B CN 201410389494 A CN201410389494 A CN 201410389494A CN 104150778 B CN104150778 B CN 104150778B
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Abstract
The invention belongs to special glass manufacturing technology field, it is proposed to a kind of leadless and low-melting point sealing glass, be mainly used in the sealing-in of chemical industry, electronic material.The component of described seal glass and percentage by weight be: Zn O16～24%, B2O34.2～8%, SrO 5～12%, Bi2O38～15%, P2O530.85～61%, GeO20.29～0.8%, V2O53.5～25%.In seal glass of the present invention, the poisonous and harmful substances such as not leaded, cadmium, thallium, has the relatively low coefficient of expansion, it is desirable to can reach transition temperature 416 DEG C, and softening temperature 455 DEG C, at 20～300 DEG C of averages coefficient of linear expansion 78.5 × 10-7/ DEG C, chemical stability is good, and what be suitable between glass, pottery, metal and quasiconductor is inter-adhesive；Auxiliary agent or filler can be done in coating, electric slurry or resin, be particularly well-suited to the sealing-in of electronic devices and components.
Description
Technical field
The invention belongs to special glass manufacturing technology field, it is proposed to a kind of leadless and low-melting point sealing glass, be mainly used in the sealing-in of chemical industry, electronic material.
Background technology
Low-melting point sealing glass refers to that fusing point is substantially less than the seal glass of simple glass, and it is applied in vacuum technique and electronic technology as a kind of solder, and domestic at present main in low-melting point sealing glass field that adopt is PbO-B2O3-SiO2, PbO-ZnO-B2O3Deng lead bearing glass system, lead bearing glass has that dielectric loss is little, softening temperature is low, good chemical stability, but is as the progressively attention to environmental protection, the plumbous murder by poisoning to the mankind and the pollution to environment, more and more causes the attention of each side.Poisonous and harmful element lead in China's Ministry of Information Industry's clear stipulaties glass dust, hydrargyrum, Cr VI, PBBs, PBDEs maximum allowable content be 0.1%, requiring to implement lead-free process, in all electronic products, the content of poisonous and harmful element to be up to state standards.The Related product sold on European market from 1 day July in 2006 is necessary for lead-free product, faces the unleaded policy of China and the restriction of International Environmental Protection policy, it is necessary to develop new low-melting point lead-less glasses powder.
Summary of the invention
It is an object of the invention to propose leadless and low-melting point sealing glass and the preparation method of a kind of environmental protection, meet the requirement of different sealing-in object.The present invention is applicable to glass, pottery, sealing-in between quasiconductor and glass, pottery and metal；The present invention meets the requirement of the nonhazardous element of national regulation.
The present invention adopts the following technical scheme that for completing above-mentioned purpose
A kind of leadless and low-melting point sealing glass, the glass component of described seal glass and mass percent be: ZnO16～24%, B2O34.2～8%, SrO5～12%, Bi2O38～15%, P2O530.85～61%, GeO20.29～0.8%, V2O53.5～25%.The knee pointy temperature Tg of described leadless and low-melting point sealing glass is 416～498 DEG C, and softening point temperature Ts is 455～530 DEG C, and coefficient of expansion α is 74.1～83.6 × 10-7/℃。
Can not be too high and require chemical stability this contradiction good in order to solve glass sealing temperature；Described seal glass, it is necessary to having good chemical stability, relatively low sealing temperature, for avoiding upper and lower base plate to burst because thermal stress is excessive, the coefficient of expansion of the low melting point of design must match with the thermal coefficient of expansion of substrate.
A kind of leadless and low-melting point sealing glass, the mass percent of the preferred glass component of described seal glass is: ZnO19.2%, B2O35.5%, SrO8.15%, Bi2O311%, P2O530.85%, GeO20.3%, V2O525%。
Seal glass thermalexpansioncoefficientα after optimization20～300 DEG CIt is 78.5 × 10-7, knee pointy temperature 416 DEG C, softening point temperature 455 DEG C, meet the industrial requirement to seal glass.
Oxide raw material in described leadless and low-melting point sealing glass: ZnO is introduced by analytically pure zinc oxide；B2O3Introduced by analytically pure boric acid；SrO is introduced by analytically pure strontium carbonate；Bi2O3Introduced by analytically pure bismuth oxide；P2O5Introduced by analytically pure phosphorus pentoxide；GeO2Introduced by analytically pure germanium oxide；V2O5Introduced by analytically pure ammonium metavanadate.
Described leadless and low-melting point sealing glass, introduces Bi ensureing that Network former is suitable when enough2O3, Bi2O3The softening point to reducing glass that adds have certain effect, when its content is less than 8%, it is impossible to fully reduce the softening point of glass, when its content is more than 15%, the heat stability of glass is deteriorated, and the coefficient of expansion raises.Therefore Bi in the present invention2O3Content is decided to be 8～15%.
The present invention has been simultaneously introduced GeO2, GeO2A part enters network with Network former, makes glass transition temperature all slightly raise, and chemical stability improves；A part exists with network outer body, plays weakening role of network and makes the coefficient of expansion raise.When chemical stability is more or less the same, Germania content is when 0.29～0.8%, and softening point is relatively low, therefore GeO2Content is decided to be 0.29～0.8%.
Use a part of V2O5Replace P2O5, it is the key point in the present invention, P2O5Although the softening point of glass can be reduced, but chemical stability extreme difference, simultaneously along with P2O5Increase, the coefficient of expansion also has the trend of increase, and vanadium ion is with [VO6] octahedral form enters into the network structure of glass, vanadium is easily polarized, is also easily shielded by oxygen anion, so the coefficient of expansion of glass reduces further, and V2O5Introducing can play reduce glass expansion coefficient effect, its softening temperature is then first raise, and then progressively declines, and works as V2O5Time content is more than 30%, vanadate glass is crystallize very easily, causes that the mobility of glass reduces, it is impossible to complete sealing-in, therefore V2O5Content is decided to be 3.5～25%.
The advantage of leadless and low-melting point sealing glass material of the present invention is in that: the feature of environmental protection is good, the poisonous and harmful substance such as not leaded, cadmium, thallium；Glass melting temperature is low, at 900 DEG C i.e. melting；Chemical stability is good, and thermal coefficient of expansion is adjustable within the specific limits, it is adaptable to the sealing-in of electronic devices and components.The seal glass knee pointy temperature Tg that glass component of the present invention and mass percent are founded out is 416～498 DEG C, and softening point temperature Ts is 455～530 DEG C, and coefficient of expansion α is 74.1～83.6 × 10-7/ DEG C within the scope of adjustable.Low softening point temperature and the low coefficient of expansion are also advantages of the present invention and environment does not constitute pollution.
Detailed description of the invention
In conjunction with specific embodiments the present invention is illustrated: (component content in embodiment is all by percentage to the quality):
Embodiment:
According to this glass composition, adopting phosphorus pentoxide, boric acid, strontium carbonate, bismuth oxide, zinc oxide, germanium oxide, ammonium metavanadate is raw material, and the percentage composition according to each component of seal glass calculates the quality of raw material, weigh raw material mix homogeneously, make batch.Melting at 900 DEG C of temperature, be incubated one hour, pulverize after the vitreous humour cast molding melted or shrend, glass powder granule crosses 200 mesh sieves, can obtain glass for sealing powder.It is embodied as formula and test result please be shown in Table 1.
Table 1: seal glass formula and test result
From table, in the present invention, the knee pointy temperature Tg of seal glass is 416～498 DEG C, and softening point temperature Ts is 455～530 DEG C, and coefficient of expansion α is 74.1～83.6 × 10-7/ DEG C within the scope of adjustable.
Claims (1)
1. a leadless and low-melting point sealing glass, is characterized in that the glass component of described seal glass and mass percent are: ZnO19.2%, B2O35.5%, SrO8.15%, Bi2O311%, P2O530.85%, GeO20.3%, V2O525%；The thermalexpansioncoefficientα of described leadless and low-melting point sealing glass20～300 DEG CIt is 78.5 × 10-7/ DEG C, knee pointy temperature 416 DEG C, softening point temperature 455 DEG C.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201410389494.7A CN104150778B (en) | 2014-08-11 | 2014-08-11 | A kind of leadless and low-melting point sealing glass |
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| CN201410389494.7A CN104150778B (en) | 2014-08-11 | 2014-08-11 | A kind of leadless and low-melting point sealing glass |
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| CN104150778A CN104150778A (en) | 2014-11-19 |
| CN104150778B true CN104150778B (en) | 2016-07-06 |
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Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| 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 |
| CN111689691B (en) * | 2020-05-27 | 2022-11-08 | 上海大学 | Lead-free low-melting-point glass solder, and preparation method and application thereof |
| CN114230187B (en) * | 2022-01-19 | 2023-07-14 | 西安石油大学 | Low-temperature lead-free electronic glass powder for photoelectric sealing |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102046549B (en) * | 2008-08-06 | 2014-05-28 | 日本电气硝子株式会社 | Sealing glass |
| CN101863620A (en) * | 2009-04-20 | 2010-10-20 | 郑庆云 | Phosphate low-melting-point glass for decoration and preparation method thereof |
| CN101624263B (en) * | 2009-08-05 | 2011-09-14 | 贵研铂业股份有限公司 | Low-melting-point neutral nuisanceless glass for electronic paste and preparation method thereof |
| CN101708956A (en) * | 2009-11-06 | 2010-05-19 | 郑庆云 | Low melting-point glass powder for field of computers and preparation method thereof |
| CN102190442A (en) * | 2010-03-12 | 2011-09-21 | 郑庆云 | Low-melting-point glass powder for vacuum glass sealing, and preparation method thereof |
| JP2013157161A (en) * | 2012-01-30 | 2013-08-15 | Hitachi Chemical Co Ltd | Electronic component, manufacturing method of the same and seal material paste used therefor |
| KR20150050575A (en) * | 2012-08-30 | 2015-05-08 | 코닝 인코포레이티드 | Antimony-free glass, antimony-free frit and a glass package that is hermetically sealed with the frit |
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Address after: 571924 Fuyin Road, Laocheng Economic Development Zone, Chengmai County, Hainan Province Patentee after: Xinyi Glass (Hainan) Co.,Ltd. Address before: 571924 South First Ring Road, old town economic development zone, Chengmai County, Hainan Patentee before: HAINAN AVIC SPECIAL GLASS MATERIALS Co.,Ltd. |