CN101058478A - Electronic slurry lead-free low melting point glass and preparing method - Google Patents

Electronic slurry lead-free low melting point glass and preparing method Download PDF

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Publication number
CN101058478A
CN101058478A CNA2007100389325A CN200710038932A CN101058478A CN 101058478 A CN101058478 A CN 101058478A CN A2007100389325 A CNA2007100389325 A CN A2007100389325A CN 200710038932 A CN200710038932 A CN 200710038932A CN 101058478 A CN101058478 A CN 101058478A
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point glass
free low
lead
melting point
molar percentage
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李胜春
陈培
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Donghua University
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Donghua University
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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
    • C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
    • 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
    • C03C3/04—Glass compositions containing silica
    • C03C3/062—Glass compositions containing silica with less than 40% silica by weight
    • 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
    • C03C3/04—Glass compositions containing silica
    • C03C3/062—Glass compositions containing silica with less than 40% silica by weight
    • C03C3/064—Glass compositions containing silica with less than 40% silica by weight containing boron
    • C03C3/066—Glass compositions containing silica with less than 40% silica by weight containing boron containing zinc
    • 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
    • C03C3/17—Silica-free oxide glass compositions containing phosphorus containing aluminium or beryllium
    • 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
    • C03C3/19—Silica-free oxide glass compositions containing phosphorus containing boron

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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 invention discloses a non-lead low-fusing point glass of electronic slurry, which comprises the following parts: (1) necessary component: 30-55mol% P2O5, 20-55mol% ZnO, 2-10mol% Al2O3, 3-15mol% K2O, 0-1mol%Li2O, (2) adding component: 0-25mol% B2O3, 0-10mol% SiO2, 0-3mol%Fe2O3, 0-8mol%CuO, (3) stable component: not more than 30% two or more oxidizer compounds, wherein allocation of different components is adjusted to obtain the non-lead low-fusing point glass with bulking coefficient at 64-140X10-7/deg. c and the sealing temperature at 430-600 deg. c.

Description

A kind of electronic slurry lead-free low melting point glass and preparation method
Technical field
The invention belongs to electric slurry glass and preparation field, particularly relate to a kind of electronic slurry lead-free low melting point glass and preparation method.
Background technology
Existing electric slurry is with containing a large amount of heavy metal leads in the low-melting-point glass, lead is one of human 6 kinds of metals that use the earliest, it is bigger to human health risk, can gather in vivo and cause lead poisoning, saturnine effect is quite slow and toxicity is hidden, is not easy to be perceiveed before toxicity presents.Lead is a kind of cumulative toxicant, and it is easy to by gastrointestinal absorption, and wherein a part is destroyed blood and made the red blood corpuscle decomposition, and part is diffused into whole body organ and tissue by blood, goes forward side by side into bone.And the lead compound that is deposited in internal organs and the marrow is extremely slow by the speed of discharging in the body, forms chronic poisoning gradually.
Along with the enhancing of various countries' environmental consciousness, a lot of countries begin to pay close attention to a series of Lead contamination problems that leaded seal glass causes, and have launched respectively relevant policies or have taked related measure.For example American National electronics manufacturing association has finished the exploitation of unleaded preparation electron device, and each main Electronic Products Corporation of Japan has provided the timetable of using lead-free.European Union's electrical equipment and electronics offal treatment method (Waste Electrical and Electronic Equipment.WEEE) propose, and will ban use of in 2008 to contain Pb, Cd, the material of heavy metals such as Hg.National governments actively support to be engaged in environmental protection important function for of research and development, mainly are that waste reclaims, environmental protection equipment is tax-free, increase the development capital input of heavy metal free environmental protection electronic material.
Discovering in recent years, phosphate seal glass can substitute current widely used leaded low-melting sealing glass, are expected to solve the pollution problem of leaded for a long time low-melting sealing glass to environment.
United States Patent (USP) has been announced a kind of phosphate seal glass P5153151 number, and its mole consists of Li 2O:0～15%, Na 2O:0～20%, K 2O:0～10%, ZnO:0～45%, Ag 2O:0～25%, Tl 2O:0～25%, PbO:0～20%, CuO:0～5%, CaO:0～20%, SrO:0～20%, P 2O 5: 24～36%, Al 2O 3: 0～5%, CeO 2: 0～2%, BaO:0～20%, SnO:0～5%, Sb 2O 3: 0～61%, Bi 2O 3: 0～10%, B 2O 3: 0～10%, the transition temperature of this glass is 300～340 ℃, thermal expansivity is 135～180 * 10 -7/ ℃, the shortcoming of this glass is Tl 2The toxicity of O is very big, and simultaneously, the thermal expansivity of glass is bigger, can not be used for, low-expansion sealing-in.
The spy of Hitachi opens flat 2-267137 and has announced a kind of vanadium oxide (V 2O 5) be seal glass, sealing temperature is less than 400 ℃, thermal expansivity 90 * 10 -7/ ℃ below, but in this glass, plumbous oxide is necessary component, can not satisfy unleaded requirement, simultaneously, also contains the oxide compound of hypertoxic thallium.
U.S. Pat P:20020019303 has proposed a kind of P 2O 5The sealing glass powder of-SnO-ZnO system, the sealing temperature of this glass is 430～500 ℃, because this sealing glass powder need be produced and sealing-in under reducing atmosphere, be unfavorable for commercial application, simultaneously owing to contain the more expensive SnO of a large amount of costs, thereby the application of this seal glass has significant limitation.
The molecular fraction that H7-69672 number disclosed glass of Japanese Patent is formed is: P 2O 5: 25～50%, SnO:30～70%, ZnO:0～25%, add B on this basis 2O 3, WO 3, Li 2O etc., the transition temperature of this glass is 350～450 ℃, thermal expansivity is greater than 120 * 10 -7/ ℃, adopt the method for weighting agent to reduce the coefficient of expansion of glass in the patent, but flowability and resistance to air loss when having influence on glass sealing.
United States Patent (USP) has been announced a kind of lead-free phosphate sealed glass No. 5021366, and its mole consists of: P 2O 5: 30～36%, ZrO 2: 0～45%, alkalimetal oxide 15～25%, alkaline earth metal oxide 15～25% also adds components such as aluminum oxide, stannic oxide and a spot of plumbous oxide.The softening temperature of this glass is 400～430 ℃, and thermal expansivity is 145～170 * 10 -7/ ℃, though the softening temperature of this glass is fit to the eutectic sealing-in, the thermal expansivity of this glass is bigger, can not be used for, low-expansion sealing-in, contains a spot of lead simultaneously, requirement that can not adapted to leadlessization is because precious metal ZrO 2Content higher, therefore aspect cost, do not have advantage equally.
Summary of the invention
Main purpose of the present invention is at containing lead, Tl in the above-mentioned seal glass 2The defective of metal oxide containing precious metals such as severe toxicity such as O and tin, zirconium provides a kind of electronic slurry lead-free low melting point glass, and that this low-melting-point glass powder has is unleaded, do not contain precious metal and oxide compound thereof, environmental protection, and the cost performance height has market development prospect widely.
Another object of the present invention is to provide a kind of preparation method of electronic slurry lead-free low melting point glass.
A kind of electronic slurry lead-free low melting point glass of the present invention, its glass is formed and is comprised:
(3) neccessary composition: molar percentage 30～55mol%P 2O 5, 20～55mol%ZnO, 2～10mol%Al 2O 3, 3～15mol%K 2O, 0～1mol%Li 2O;
(4) added ingredients: molar percentage 0～25mol%B 2O 3, 0～10mol%SiO 2, 0～3mol%Fe 2O 3, 0～8mol%CuO;
(3) stabilizing component: molar percentage is not higher than two kinds of oxide compounds of 30% or two or more oxide mixtures is arranged.
Described lead-free low-melting-point glass neccessary composition molar percentage 35～50mol%P 2O 5, 25～50mol%ZnO, 3～8mol%Al 2O 3, 5～7mol%K 2O, 1mol%Li 2O.
Described lead-free low-melting-point glass neccessary composition molar percentage 40～45mol%P 2O 5, 35～45mol%ZnO, 3～5mol%Al 2O 3, 3～15mol%K 2O, 1mol%Li 2O.
Described B 2O 3, Al 2O 3, SiO 2Total molar percentage be 5%～25%.
Described Fe 2O 3, CuO total molar percentage be 0.5%～2.5%.
Described P 2O 5, ZnO total molar percentage be 60%～90%.
Described K 2O: (Fe 2O 3+ CuO) molar ratio scope is 3: 1～7: 1.
The preparation method of a kind of vacuum glass goods barium crown sealed glass of the present invention comprises the following steps:
1. carry out thorough mixing after taking by weighing each raw material according to molar percentage, make compound;
2. the quartz crucible of compound being packed into, and place lid and cover, under 1100 ℃～1300 ℃, be incubated 0.5～2.5 hour;
3. the glass precursor solution to fusing carries out cooling curing, makes vitreum.
Vitreum can be prepared into strip, column, dull and stereotyped dress and powdery according to sealing-in product characteristics and requirement.
Described lead-free low-melting-point glass thermal expansivity is 64～140 * 10 -7/ ℃.
Described lead-free low-melting-point glass sealing temperature is 430～600 ℃.
The present invention is by introducing the raw material of oxide compound: P 2O 5Introduce Al by Vanadium Pentoxide in FLAKES 2O 3Gamma-alumina by median size≤10nm is introduced K 2O, Li 2O introduces B by carbonate separately respectively 2O 3Introduced by boric acid, all the other components are introduced by oxide compound separately, according to the compositing range of the molar percentage of lead-free low-melting-point glass, determine glass formula.
Lead-free phosphate sealed glass powder of the present invention is on the basis of a large amount of experiments, with the theory is according to a kind of novel phosphate glass of creating, test result shows, not only has thermal expansivity suitable and that be easy to adjust, lower softening temperature also has excellent chemical stability, is specially adapted to the high power valve sealing glass powder, aspect unleaded and low-cost, have very strong competitive power especially.
Embodiment
Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiment only to be used to the present invention is described and be not used in and limit the scope of the invention.Should be understood that in addition those skilled in the art can make various changes or modifications the present invention after the content of having read the present invention's instruction, these equivalent form of values fall within the application's appended claims institute restricted portion equally.
Embodiment 1-4
The present invention is described in further detail for composition by specific embodiment.
Table one (mol%)
Figure A20071003893200061
The preparation method of four kinds of cited barium crown sealed glass is identical in the above-mentioned table one.
Weightlessness is that constant temperature was measured after 9 hours in 90 ℃ deionized water.
Thermal expansivity (α) adopts WRP-1 microcomputer thermal dilatometer to measure, and glass sample is the right cylinder sample of  5 * 25mm specification, rises to 300 ℃ by room temperature, and temperature rise rate is 5 ℃/min.Glass transformation temperature (Tg) adopts temperature difference heat analysis-e/or determining among the CRY-IP, and temperature rise rate is 15 ℃/min.The specimen of volume specific resistance is that diameter is 3cm, and thickness is the cylindrical glass sample of 0.5cm.Use earlier the raw spirit wiping before the test, to be dried after again at the circular two-sided electrically conductive graphite breast of smearing of sample, put into 101-1 type electric heating bellows after the drying and heat, the super megger of employing ZC43 type, the high direct voltage testing power supply selects the 250V shelves, probe temperature is 200 ℃.

Claims (9)

1, a kind of electronic slurry lead-free low melting point glass, its glass is formed and is comprised:
(1) neccessary composition: molar percentage 30～55mol%P 2O 5, 20～55mol%ZnO, 2～10mol%Al 2O 3, 3～15mol%K 2O, 0～1mol%Li 2O;
(2) added ingredients: molar percentage 0～25mol%B 2O 3, 0～10mol%SiO 2, 0～3mol%Fe 2O 3, 0～8mol%CuO;
(3) stabilizing component: molar percentage is not higher than two kinds of oxide compounds of 30% or two or more oxide mixtures is arranged.
2, a kind of electronic slurry lead-free low melting point glass according to claim 1 is characterized in that: described lead-free low-melting-point glass neccessary composition molar percentage 35～50mol%P 2O 5, 25～50mol%ZnO, 3～8mol%Al 2O 3, 5～7mol%K 2O, 1mol%Li 2O.
3, a kind of electronic slurry lead-free low melting point glass according to claim 1 and 2 is characterized in that: described lead-free low-melting-point glass neccessary composition molar percentage 40～45mol%P 2O 5, 35～45mol%ZnO, 3～5mol%Al 2O 3, 3～15mol%K 2O, 1mol%Li 2O.
4, a kind of electronic slurry lead-free low melting point glass according to claim 1 is characterized in that: described B 2O 3, Al 2O 3, SiO 2Total molar percentage be 5%～25%.
5, a kind of electronic slurry lead-free low melting point glass according to claim 1 is characterized in that: described Fe 2O 3, CuO total molar percentage be 0.5%～2.5%.
6, a kind of electronic slurry lead-free low melting point glass according to claim 1 is characterized in that: described P 2O 5, ZnO total molar percentage be 60%～90%.
7, a kind of electronic slurry lead-free low melting point glass according to claim 1 is characterized in that: described K 2O: (Fe 2O 3+ CuO) molar ratio scope is 3: 1～7: 1.
8, a kind of preparation method of vacuum glass goods barium crown sealed glass comprises the following steps:
1. carry out thorough mixing after taking by weighing each raw material according to molar percentage, make compound;
2. the quartz crucible of compound being packed into is placed lid and is covered, and 1100 ℃～1300 ℃, is incubated 0.5～2.5 hour;
3. the glass precursor solution to fusing carries out cooling curing, makes vitreum.
9, according to the described a kind of electronic slurry lead-free low melting point glass of claim 1-9, it is characterized in that: described lead-free low-melting-point glass thermal expansivity is 64～140 * 10 -7/ ℃, sealing temperature is 430～600 ℃.
CNA2007100389325A 2007-03-30 2007-03-30 Electronic slurry lead-free low melting point glass and preparing method Pending CN101058478A (en)

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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103449724A (en) * 2013-08-23 2013-12-18 青岛光路玻璃器件有限公司 Leadless low-temperature sealing glass
CN105330144A (en) * 2015-09-29 2016-02-17 洛阳暖盈电子技术有限公司 Low conductivity lead-free glass
CN109455940A (en) * 2019-01-11 2019-03-12 福州布朗新材料技术有限公司 A kind of soft lead-free low-temperature seal glass and preparation method thereof
CN109486245A (en) * 2018-11-09 2019-03-19 常州常发制冷科技有限公司 Anti-corrosion inflation type heat exchanger and its application
CN110028242A (en) * 2018-01-11 2019-07-19 Ａｇｃ株式会社 Glass, glass powder, electroconductive paste and solar battery
CN112142334A (en) * 2020-08-31 2020-12-29 浙江工业大学 Environment-friendly low-melting-point glass powder
CN114685152A (en) * 2020-12-28 2022-07-01 山东国瓷功能材料股份有限公司 Low-temperature co-fired ceramic material for millimeter wave antenna module and preparation method thereof
CN114787094A (en) * 2020-10-07 2022-07-22 康宁股份有限公司 Glass and glass-ceramic and method for producing same

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1562833A (en) * 2004-03-19 2005-01-12 中国科学院上海光学精密机械研究所 Oxygen-fluorin silicic acid glass with Er/Yb heavy metal mixed into, and preparation method
CN1830856A (en) * 2006-03-17 2006-09-13 东华大学 Leadless phosphate seal glass and its preparation method

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1562833A (en) * 2004-03-19 2005-01-12 中国科学院上海光学精密机械研究所 Oxygen-fluorin silicic acid glass with Er/Yb heavy metal mixed into, and preparation method
CN1830856A (en) * 2006-03-17 2006-09-13 东华大学 Leadless phosphate seal glass and its preparation method

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103449724A (en) * 2013-08-23 2013-12-18 青岛光路玻璃器件有限公司 Leadless low-temperature sealing glass
CN105330144A (en) * 2015-09-29 2016-02-17 洛阳暖盈电子技术有限公司 Low conductivity lead-free glass
CN110028242A (en) * 2018-01-11 2019-07-19 Ａｇｃ株式会社 Glass, glass powder, electroconductive paste and solar battery
CN110028242B (en) * 2018-01-11 2023-06-13 Ａｇｃ株式会社 Glass, glass powder, conductive paste, and solar cell
CN109486245A (en) * 2018-11-09 2019-03-19 常州常发制冷科技有限公司 Anti-corrosion inflation type heat exchanger and its application
CN109455940A (en) * 2019-01-11 2019-03-12 福州布朗新材料技术有限公司 A kind of soft lead-free low-temperature seal glass and preparation method thereof
CN109455940B (en) * 2019-01-11 2021-09-21 河北曜阳新材料技术有限公司 Soft lead-free low-temperature sealing glass and preparation method thereof
CN112142334A (en) * 2020-08-31 2020-12-29 浙江工业大学 Environment-friendly low-melting-point glass powder
CN114787094A (en) * 2020-10-07 2022-07-22 康宁股份有限公司 Glass and glass-ceramic and method for producing same
CN114787094B (en) * 2020-10-07 2023-12-01 康宁股份有限公司 Glass and glass-ceramic and method for producing same
CN114685152A (en) * 2020-12-28 2022-07-01 山东国瓷功能材料股份有限公司 Low-temperature co-fired ceramic material for millimeter wave antenna module and preparation method thereof
CN114685152B (en) * 2020-12-28 2022-11-04 山东国瓷功能材料股份有限公司 Low-temperature co-fired ceramic material for millimeter wave antenna module and preparation method thereof

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