CN110423007A - The unleaded high stability low temperature sealing glass of alkali-free - Google Patents

The unleaded high stability low temperature sealing glass of alkali-free Download PDF

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Publication number
CN110423007A
CN110423007A CN201910623735.2A CN201910623735A CN110423007A CN 110423007 A CN110423007 A CN 110423007A CN 201910623735 A CN201910623735 A CN 201910623735A CN 110423007 A CN110423007 A CN 110423007A
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China
Prior art keywords
glass
sealing
temperature
free
requiring
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CN201910623735.2A
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Chinese (zh)
Inventor
郑涛
吕景文
郭艳艳
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Changchun University of Science and Technology
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Changchun University of Science and Technology
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Priority to CN201910623735.2A priority Critical patent/CN110423007A/en
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    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B25/00—Annealing glass products
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B5/00—Melting in furnaces; Furnaces so far as specially adapted for glass manufacture
    • C03B5/16—Special features of the melting process; Auxiliary means specially adapted for glass-melting furnaces
    • 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
    • C03C8/24—Fusion seal compositions being frit compositions having non-frit additions, i.e. for use as seals between dissimilar materials, e.g. glass and metal; Glass solders
    • C03C8/245—Fusion seal compositions being frit compositions having non-frit additions, i.e. for use as seals between dissimilar materials, e.g. glass and metal; Glass solders containing more than 50% lead oxide, by weight

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Glass Compositions (AREA)

Abstract

The present invention provides a kind of preparation methods of the unleaded high stability low temperature sealing glass material of alkali-free, the component and mole percent level of the sealing glass material are as follows: phosphorus pentoxide 20 ~ 40%, diboron trioxide 10 ~ 20%, stannous fluoride 30 ~ 50%, stannous oxide 20 ~ 30%, titanium dioxide 5 ~ 20%.Preparation method is: with phosphorus pentoxide, ammonium dihydrogen phosphate, boric acid, stannous oxide, titanium dioxide is raw material, according to the mole percent content of seal glass each component, calculates the mass percent of raw material, raw material is weighed, is put into corundum crucible, is melted at 500-600 DEG C after mixing；It will pulverize after the cast molding of melten glass liquid or water quenching, cross 200 meshes.Sealing glass material of the invention is without poisonous and harmful substances such as lead, cadmium and thalliums, and sealing temperature is low, and minimum to can reach 280 DEG C, chemical stability is excellent, the sealing-in especially suitable for electronic component.

Description

The unleaded high stability low temperature sealing glass of alkali-free
Technical field
The present invention relates to a kind of phosphate-based alkali-free lead-free low-temperature seal glasses and preparation method thereof, more particularly to one kind It is widely used in the phosphate-based alkali-free lead-free low-temperature sealing-in of the instrument and meters such as communication, measurement, transmission, display or electronic component Glass and preparation method thereof.
Background technique
Because the manufacture and use of instrument and meter or electronic component have strict requirements to temperature, so requiring sealing-in mostly The use temperature of glass is low as far as possible.The effects of being generally used for instrument and meter or electronic component connection, sealing-in, coating, sealing Seal glass, it is desirable that its using temperature between 400 ~ 600 DEG C, not more than 700 DEG C, currently, being able to satisfy this requirement Most of seal glass based on the seal glass containing lead oxide.
Studies have shown that lead will inhibit the normal occlusion of the intracorporal protein of people at function after being absorbed by the body, encroach in human body Pivot nerve, causes the diseases such as anaemia and hypertension, especially more very to the infringement of children.Therefore, using barium crown sealed glass generation It is imperative, trend of the times for leaded seal glass.
Leadless and low-melting point sealing glass not only wants unleaded and it is necessary to the leaded seal glass spy low using temperature Property, some particular characteristic requirements of instrument and meter or electronic component are gone back while must satisfy, such as insulating properties, air-tightness, pressure resistance Property, chemical stability etc..
The mole percent of the composition of glass disclosed in U.S. Patent No. 6306783 is SnO:30 ~ 80%, B2O3: 5 ~ 60%, P2O5: 5 ~ 24%, ZnO:0 ~ 25%, WO 3: 3 ~ 20%, MoO3: 3 ~ 5%, TiO2: 0 ~ 15%, ZrO2: 0 ~ 15%, CuO:0 ~ 10%, R2O:2 ~ 35%.The transition temperature of the glass of the system is 280 ~ 380 DEG C, and thermal expansion coefficient is 90 ~ 110 × 10-7/ DEG C, the melting temperature of glass is 450 ~ 500 DEG C, and flow radius is 22 ~ 26mm.
No. 5021366 compositions for disclosing Fluorine-free phosphate glass of U.S. Patent No., mole percent P2O5: 30 ~ 36%, ZrO2: 10 ~ 33%, alkali metal oxide 15 ~ 25%, alkaline earth oxide 15 ~ 25% and aluminium oxide, tin oxide, oxygen Change the components such as lead.The softening temperature of glass is 400 ~ 430 DEG C, and thermal expansion coefficient is 145 ~ 170 × 10-7/ DEG C, the glass of the component Thermal expansion coefficient it is bigger.
The mole percent of the composition of glass disclosed in Japanese Patent No. H7-69672 is P2O5: 25 ~ 50%, SnO:30 ~ 70%, ZnO:0 ~ 25% adds suitable B on this basis2O3, WO3, Li2O etc..Sn0/ZnO in the glass composition of the system Greater than 5:1, the use temperature of glass is 350 ~ 450 DEG C, and thermal expansion coefficient is greater than 120 × 10-7/ DEG C, and use and fill out in patent The method of agent is filled to reduce the coefficient of expansion of glass, but mobility and sealing-in device when the addition of filler influences glass sealing The air-tightness of part.
Chinese patent 201010190237.2 proposes a kind of lead-free low-melting electronic display sealing glass and its preparation side Method.The mass percent containing oxide is ZnO:10 ~ 45wt%, P in the glass basic component2O5: 10 ~ 45%wt%, V2O5: 5 ~ 35% wt%、B2O3: 1 ~ 10% wt%, Al2O3: 1 ~ 10% wt%, Fe2O3: 1 ~ 10% wt%.Wherein have containing mass fraction is no small The V of poison2O5, it is easy to foaming in melting process, it pollutes production environment and reduces raw material availability, limit its practical application.Separately Outside, its glass transition temperature is 300 ~ 360 DEG C, still belongs to higher range, and do not refer to the glass in sealing temperature in patent Under mobility.
A kind of SnO-P is proposed in United States Patent (USP) US20020193032O5The seal glass of-ZnO system, sealing temperature section It is 430 ~ 500 DEG C.But in practical applications, this sealing temperature is higher, when be used for circuit board, the electronic circuits component such as capacitor, When the sealing-in of display (such as plasma display PDP) or substrate, it may appear that when because making device keep the temperature one section under high temperature environment Between and reduce the working performance and service life of device, or even the case where destroy device.
The above patent does not mention chemical stability, because the glass system moisture resistivity one based on phosphate is to poor, An important factor for this is also limitation seal glass service life and use scope.[non-patent literature 1]
Non-patent literature 1:DORISE, WOLFGANG S. Glass for high performance optics and laser technology [J].J. Non-Cryst. Solids, 1991, 129: 19- 30.
Summary of the invention
Technical problem to be solved by the invention is to provide a kind of phosphate-based alkali-free lead-free low-temperature seal glass and its systems Preparation Method is met the demands of production and living with making up the deficiencies in the prior art or defect.
In order to solve the above-mentioned technical problem, the technical solution adopted in the present invention first is that: it is a kind of phosphate-based unleaded low Intermediate temperature sealing glass, component and content are as follows by mole calculating:
P2O5 20~40%
B2O3 10~20%
SnF2 30~50%
SnO 20~30%
TiO2 5~20%
The technical solution adopted in the present invention second is that: a kind of preparation method of phosphate-based lead-free low-temperature seal glass, including Following steps:
(1) introduce the raw material of oxide: phosphorus pentoxide is introduced by phosphorus pentoxide and ammonium dihydrogen phosphate, and boron oxide is drawn by boric acid Enter, remaining component is introduced by respective oxide, according to the compositing range of the molar percentage of seal glass, determines that glass is matched Side, calculates the weight percent of glass, then weighs and is uniformly mixed；
(2) corundum crucible is selected, in Elema electric furnace, temperature carries out melted, heat preservation 0.5 ~ 1 hour at 550 ~ 750 DEG C；
(3) it to the glass metal melted, casts, and glass sample is put into annealing furnace anneals in time, annealing temperature Degree is 150 ~ 200 DEG C, furnace cooling after heat preservation 1 hour；
(4) glass after annealing presses test request machine-shaping.
The beneficial effects of the present invention are: not containing lead oxide in seal glass of the invention, leaded seal glass is eliminated Pollution and destruction in production or use process to human body and environment can replace leaded seal glass to be used for various electronic components Sealing-in in；Fusing point is low, and 80 ~ 100 DEG C of the softening temperature of glass, 280-400 DEG C of melting temperature sealing range is able to satisfy electronic component Low-temperature sealing requirement；Thermal expansion coefficient is 95 ~ 150 × 10-7/ DEG C within the scope of, chemical stability is good, according to national standard SJT 11035-1996, glass water resistant chemical stability reach 1 grade, and use scope is increased, can be widely used for various glass, Connection, sealing-in, sealing etc. between ceramics and metal parts.
Detailed description of the invention
Fig. 1 is the thermal dilatometry of phosphate low temperature sealing glass example 1, transition temperature and the softening temperature difference of sample For 75 DEG C and 89 DEG C, 280 DEG C of sealing temperature, thermal expansion coefficient 150 × 10-7/℃。
Fig. 2 is the weight-loss ratio of phosphate low temperature sealing glass sample and the relativity of determining ammonium biphosphate content.
Specific embodiment
The present invention is further elaborated combined with specific embodiments below.
According to the compositing range of the molar percentage of above-mentioned leadless and low-melting point sealing glass, glass formula is determined, calculate Out glass weight percent carry out ingredient, according to above-mentioned glass preparation for processing carry out glass be melted, molding and Grinding, tests the sample after processing.
The glass composition (weight percent) of embodiment see the table below 1:
Embodiment 1
Ingredient is carried out by the composition in table 1, since the body resistivity to glass is more demanding, alkali metal is not included in recipe ingredient Oxide.
Glass mixture is placed in corundum crucible, heats and is melted in Elema electric furnace, is rapidly heated to 500 DEG C and keeps the temperature 30 min。
The glass melted is quickly put into Muffle furnace and anneals in the die for molding by preheating, and annealing temperature is 100 DEG C, furnace cooling after heat preservation 1 hour.
After the ground processing of sample after annealing, performance evaluation is carried out.
Embodiment 2
Ingredient is carried out by the composition in table 1, increases the content of stannous fluoride, reduces the content of stannous oxide, reach reduction glass The purpose of transition temperature and softening temperature.
Glass mixture is placed in corundum crucible, heats and is melted in Elema electric furnace, is rapidly heated to 500 DEG C and keeps the temperature 30 min。
The glass melted is quickly put into Muffle furnace and anneals in the die for molding by preheating, and annealing temperature is 100 DEG C, furnace cooling after heat preservation 1 hour.
After the ground processing of sample after annealing, performance evaluation is carried out.
Embodiment 3
Ingredient is carried out by the composition in table 1, increases titanium dioxide proportion, the chemistry of glass can be improved to a certain extent Stability.
Glass mixture is placed in corundum crucible, heats and is melted in Elema electric furnace, is rapidly heated to 500 DEG C and keeps the temperature 30 min。
The glass melted is quickly put into Muffle furnace and anneals in the die for molding by preheating, and annealing temperature is 100 DEG C, furnace cooling after heat preservation 1 hour.
After the ground processing of sample after annealing, performance evaluation is carried out.
Embodiment 4
By in table 1 composition carry out ingredient, increase phosphorus pentoxide proportion, can be improved sample at glass properties.
Glass mixture is placed in corundum crucible, heats and is melted in Elema electric furnace, is rapidly heated to 500 DEG C and keeps the temperature 30 min。
The glass melted is quickly put into Muffle furnace and anneals in the die for molding by preheating, and annealing temperature is 100 DEG C, furnace cooling after heat preservation 1 hour.
After the ground processing of sample after annealing, performance evaluation is carried out.
Embodiment 5
Ingredient is carried out by the composition in table 1, improves the content of stannous oxide, can reduce the thermal expansion coefficient of glass, improves glass The thermal stability of glass.
Glass mixture is placed in corundum crucible, heats and is melted in Elema electric furnace, is rapidly heated to 500 DEG C and keeps the temperature 30 min。
The glass melted is quickly put into Muffle furnace and anneals in the die for molding by preheating, and annealing temperature is 100 DEG C, furnace cooling after heat preservation 1 hour.
After the ground processing of sample after annealing, performance evaluation is carried out.
Embodiment 6
Ingredient is carried out by the composition in table 1, increases the content of stannous fluoride in glass ingredient, reduces the sealing temperature of glass.
Glass mixture is placed in corundum crucible, heats and is melted in Elema electric furnace, is rapidly heated to 500 DEG C and keeps the temperature 30 min。
The glass melted is quickly put into Muffle furnace and anneals in the die for molding by preheating, and annealing temperature is 100 DEG C, furnace cooling after heat preservation 1 hour.
After the ground processing of sample after annealing, performance evaluation is carried out.

Claims (8)

1. a kind of phosphate-based alkali-free lead-free low-temperature seal glass, it is characterised in that: its component and content are by mole meter It calculates as follows:
P2O5 20~40%
B2O3 10~20%
SnF2 30~50%
SnO 20~30%
TiO2 5~20%。
2. a kind of preparation method of phosphate-based alkali-free lead-free low-temperature seal glass, it is characterised in that specific step is as follows:
(1) introduce the raw material of oxide: phosphorus pentoxide is introduced by phosphorus pentoxide and ammonium dihydrogen phosphate, and boron oxide is drawn by boric acid Enter, remaining component is introduced by respective oxide, according to the compositing range of the molar percentage of seal glass, determines that glass is matched Side, calculates the weight percent of glass, then weighs and is uniformly mixed；
(2) corundum crucible is selected, in Elema electric furnace, temperature carries out melted, heat preservation 0.5 ~ 1 hour at 550 ~ 750 DEG C；
(3) it to the glass metal melted, casts, and glass sample is put into annealing furnace anneals in time, annealing temperature Degree is 150 ~ 200 DEG C, furnace cooling after heat preservation 1 hour；
(4) glass after annealing presses test request machine-shaping.
3. requiring the sealing glass material according to right 1, which is characterized in that be free of in the component of prepared seal glass There is alkali metal oxide.
4. requiring the sealing glass material according to right 1, which is characterized in that be free of in the component of prepared seal glass There is lead.
5. requiring the sealing glass material according to right 1, which is characterized in that the transition temperature of prepared seal glass exists 80~90℃。
6. requiring the sealing glass material according to right 1, which is characterized in that the softening temperature of prepared seal glass exists 90~110℃。
7. requiring the sealing glass material according to right 1, which is characterized in that the sealing temperature of prepared seal glass exists 270~280℃。
8. requiring the sealing glass material according to right 1, which is characterized in that the weight-loss ratio of prepared seal glass is 0.
CN201910623735.2A 2019-07-15 2019-07-15 The unleaded high stability low temperature sealing glass of alkali-free Pending CN110423007A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112876073A (en) * 2021-01-29 2021-06-01 中国科学院上海光学精密机械研究所 Luminescent glass and preparation method thereof
CN113735437A (en) * 2021-09-06 2021-12-03 清华大学 Forming method of high-temperature gas cooled reactor electrical penetration piece glass sealing material
CN114620935A (en) * 2022-02-22 2022-06-14 中国科学院上海光学精密机械研究所 Containing NH4+Low-melting-point tin-chlorine phosphate glass and preparation method thereof

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6306783B1 (en) * 1998-04-06 2001-10-23 Nippon Electric Glass Co., Ltd. Tin borophosphate glass comprising SnO, B2O3, and P2O5 as main components and sealing material using the glass
CN102432173A (en) * 2011-09-02 2012-05-02 长春理工大学 Phosphate sealing glass with ultra-low expansion softening temperature and preparation method thereof
CN107117819A (en) * 2017-06-06 2017-09-01 长春理工大学 Unleaded high bulk resistivity low temperature sealing glass
CN108473363A (en) * 2016-01-08 2018-08-31 Yej玻璃株式会社 Tin fluoride system frit and its manufacturing method
CN109721250A (en) * 2016-12-01 2019-05-07 天津理工大学 The method for preparing luminescent glass ceramic with glass powder with low melting point

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6306783B1 (en) * 1998-04-06 2001-10-23 Nippon Electric Glass Co., Ltd. Tin borophosphate glass comprising SnO, B2O3, and P2O5 as main components and sealing material using the glass
CN102432173A (en) * 2011-09-02 2012-05-02 长春理工大学 Phosphate sealing glass with ultra-low expansion softening temperature and preparation method thereof
CN108473363A (en) * 2016-01-08 2018-08-31 Yej玻璃株式会社 Tin fluoride system frit and its manufacturing method
CN109721250A (en) * 2016-12-01 2019-05-07 天津理工大学 The method for preparing luminescent glass ceramic with glass powder with low melting point
CN107117819A (en) * 2017-06-06 2017-09-01 长春理工大学 Unleaded high bulk resistivity low temperature sealing glass

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112876073A (en) * 2021-01-29 2021-06-01 中国科学院上海光学精密机械研究所 Luminescent glass and preparation method thereof
CN113735437A (en) * 2021-09-06 2021-12-03 清华大学 Forming method of high-temperature gas cooled reactor electrical penetration piece glass sealing material
CN114620935A (en) * 2022-02-22 2022-06-14 中国科学院上海光学精密机械研究所 Containing NH4+Low-melting-point tin-chlorine phosphate glass and preparation method thereof

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