CN103319097A - Low temperature lead-free glass dust and preparation method thereof - Google Patents

Low temperature lead-free glass dust and preparation method thereof Download PDF

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CN103319097A
CN103319097A CN2013102593026A CN201310259302A CN103319097A CN 103319097 A CN103319097 A CN 103319097A CN 2013102593026 A CN2013102593026 A CN 2013102593026A CN 201310259302 A CN201310259302 A CN 201310259302A CN 103319097 A CN103319097 A CN 103319097A
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free glass
glass powder
lead
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于小军
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Shanghai Intelligent Sensor Electronic Technology Co Ltd
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Abstract

The invention relates to low temperature lead-free glass dust and a preparation method thereof. The glass dust comprise the following components as raw materials by weight percent: 30-80% of Bi2O3, 10-60% of B2O3, 0-20% of ZnO, 0-20% of Sb2O3, 0-10% of Al2O3 and 0-7% of alkali metal oxide, wherein the alkali metal oxide is Li2O. The preparation method comprises the following steps: (1) weighing the raw materials in ratio, carrying out ball-milling for 30-60 minutes by taking ethyl alcohol as a medium by using a planet ball grinding mill, then blending uniformly, drying to obtain a uniformly-mixed oxide; (2) after the mixture is melted, pouring the melted mixture into deionized water to obtain glass slag, then drying, and putting the glass slag into a ball-milling pot in the planet ball grinding mill and carrying out ball-milling to obtain a product; and (3) after the ball-milling, sieving the product with a 300-mesh mesh screen to obtain the low temperature lead-free glass dust. The lead-free glass dust prepared by the preparation method disclosed by the invention is low in softening in temperature, high in bonding strength and good in refiring stability.

Description

A kind of low-temperature lead-free glass powder and preparation method thereof
Technical field
The present invention relates to a kind of lead-free glass powder, particularly disclose a kind of low-temperature lead-free glass powder and preparation method thereof, be applied to the aluminum oxide sealing-in and be the electric slurry that substrate is used with the aluminum oxide, belong to technical field of electronic materials.
Background technology
Low-melting-point glass refers to softening temperature (T s) be lower than 600 ℃ a class special purpose glass, be widely used in fields such as vacuum electronic technology, microelectronics, laser and infrared technique, electric light source, high energy physics and aerospace industry, the energy, automotive industry, chemical industry, industrial test, can realize the sealing-in between glass, pottery and the multiple metal.Lead glass has outstanding low temperature softening performance and excellent chemical stability, for many years is used as commercial low-melting-point glass always.But contain a large amount of highly toxic PbO in this type of glass, it uses and just is being subjected to increasing restriction.
Because Bi and Pb belong to the P district in the 6th cycle together, be adjacent element in the periodic table of elements, similar performance, and glass is also more similar at aspects such as viscosity, transition temperature, thermal expansivity, S.Rada, and P.Pascuta, M.Bosca etc. think: Bi 2O 3Be to have ready conditions to form the material of glass, when forming eutectic with other oxide compound, have quite wide glass formation range.Bi in addition 2O 3Can improve corrosion resistance nature and the thermostability of glass, so bismuthate glass is the substitute of lead glass the best.Bismuth glass is in the existing more research of insulating coating glass, seal glass and the electric slurry application aspect glass.Forefathers are more to the research of high bismuth glass, and also the someone is by regulating Bi 2O 3Make low bismuth glass with the amount of BaO.
Because Bi 2O 3With B 2O 3When forming glass together, have very wide glass formation range, the author is by adjusting Bi 2O 3And B 2O 3Amount, in addition in order to improve glass heat stability, at Bi 2O 3-B 2O 3The basis on add an amount of ZnO, Al 2O 3, wish to obtain a kind of low-melting lead-free glass, can be used for aluminum oxide-aluminum oxide sealing-in or be used as with the aluminum oxide is the electric slurry glassy phase of substrate.
There are following deficiency in aluminum oxide sealing-in at present and aluminum oxide substrate with electric slurry glass powder: (1) behind sintering owing to do not match with the aluminum oxide coefficient of expansion or wettability bad, cause stress too big, life-time service ftractures easily, causes electric property to degenerate.(2) though some glass powder performance is good, contain the chemical element harmful to human and environment such as lead, chromium.(3) the heavily burning stability of prepared electric slurry is poor.
Application number is a kind of ruthenium oxide base thick-film resistor paste glass powder for the US4362656 United States Patent (USP) discloses, and contains a large amount of lead in this glass, though every excellent performance does not meet environmental requirement.In order to meet the energy-conserving and environment-protective requirement, improve the adhesive property with substrate, it is a kind of with Bi that application number is that the Chinese patent of 201210446523.x discloses 2O 3, ZnO, B 2O 3, kaolin, TiO 2, SiO 2Be the lead-free glass powder of feedstock production, but because this glass contains TiO 2, easy crystallization when causing this glass powder double sintering heavily burns bad stability.Application number is that 200710041637.5 Chinese patent discloses a kind of with Bi 2O 3, B 2O 3, SiO 2, MgO, Li 2O is the feedstock production lead-free glass powder, and this glass powder has better chemical and thermostability, low-expansion coefficient, and higher mechanical properties, but owing to contain part Si O 2Cause softening temperature still higher.
Summary of the invention
The objective of the invention is to address the deficiencies of the prior art, providing a kind of is substrate electric slurry low-temperature lead-free glass powder and preparation method for the aluminum oxide sealing-in and with the aluminum oxide.
The present invention is achieved in that a kind of low-temperature lead-free glass powder and preparation method thereof, it is characterized in that the raw material of described lead-free glass powder comprises following component and weight percentage: Bi 2O 330～80%, B 2O 310～60%, ZnO 0～20%, Sb 2O 30～20%, Al 2O 30～10%, alkalimetal oxide 0～7%; Described basic oxide are Li 2O.
The component of described lead-free glass powder and weight percentage are: Bi 2O 355%, B 2O 335%, ZnO 8%, Sb 2O 30%, Al 2O 32%, Li 2O 0%.
The component of described lead-free glass powder and weight percentage are: Bi 2O 347.40%, B 2O 330%, ZnO 7%, Sb 2O 314%, Al 2O 31.60%, Li 2O 0%.
The component of described lead-free glass powder and weight percentage are: Bi 2O 356.50%, B 2O 331.70%, ZnO 8.3%, Sb 2O 30%, Al 2O 31.9%, Li 2O 1.6%.
The component of described lead-free glass powder and weight percentage are: Bi 2O 370%, B 2O 320%, ZnO 5%, Sb 2O 32%, Al 2O 32%, Li 2O 1%.
The preparation method of described low-temperature lead-free glass powder may further comprise the steps:
(1) taking by weighing raw material by above-mentioned composition, utilize planetary ball mill, is medium ball milling 30～60min mixing with ethanol, obtains the oxide compound that mixes after the drying;
(2) after the compound fusing, pour into and obtain the glass slag in the deionized water, oven dry then, the ball grinder ball milling in planetary ball mill of packing into;
(3) cross 300 order mesh screens behind the ball milling, just obtain low-temperature lead-free glass powder.
Described lead-free glass powder is to found and be incubated 0.5～2h at 1100～1300 ℃.Lead-free glass powder diameter after the oven dry is the agate ball of 10mm and 5mm, lead-free glass powder and agate ball are with the mixed of 1:3, in agate jar, the weight ratio of agate ball and lead-free glass powder is 2:1～6:1, be medium with ethanol, rotating speed is 300～500 rev/mins, adopts planetary ball mill ball milling 3～12h.The D50 that crosses the lead-free glass powder that obtains behind the 300 order mesh screens is 0～2.5 μ m.
To be particle diameter account for 50% greater than its particle to the physical significance of D50, also accounts for 50%, D50 less than its particle and also be meso-position radius or median particle diameter.The mean particle size of D50 ordinary representation powder.
The invention has the beneficial effects as follows: the 1) lead-free glass powder of the inventive method preparation, softening temperature is low, meets energy conservation and environment protection.2) the lead-free low-temperature glass powder of the inventive method preparation is used for electric slurry and alumina material sealing-in, with the matched coefficients of thermal expansion of substrate, good wettability is arranged, the cohesive strength height.3) utilize the prepared resistance slurry of lead-free low-temperature glass powder of the present invention heavily to burn good stability, side's resistance is heavily burnt velocity of variation in ± 3%.
Description of drawings
Fig. 1 is the embodiment of the invention 1 glass DTA curve.
Fig. 2 is the embodiment of the invention 2 glass DTA curves.
Fig. 3 is the embodiment of the invention 3 glass DTA curves.
Fig. 4 is the embodiment of the invention 4 glass DTA curves.
Embodiment
A kind of low-temperature lead-free glass powder of the present invention and preparation method thereof, the raw material of lead-free glass powder comprises following component and weight percentage: Bi 2O 330～80%, B 2O 310～60%, ZnO 0～20%, Sb 2O 30～20%, Al 2O 30～10%, alkalimetal oxide 0～7%; Described basic oxide are Li 2O.
The preparation method of low-temperature lead-free glass powder may further comprise the steps:
(1) taking by weighing raw material by mentioned component, utilize planetary ball mill, is medium ball milling 30～60min mixing with ethanol, obtains the oxide compound that mixes after the drying;
(2) after the compound fusing, pour into and obtain the glass slag in the deionized water, oven dry then, the ball grinder ball milling in planetary ball mill of packing into;
(3) cross 300 order mesh screens behind the ball milling, just obtain low-temperature lead-free glass powder.
Below in conjunction with specific embodiment, further set forth the present invention, the following examples only are to be not used in restriction composition range of the present invention for explanation the present invention.
4 specific embodiment compositions of the present invention are as shown in table 1 below.
Figure 634742DEST_PATH_IMAGE001
Embodiment 1:
By the composition weight percent of table 1 batching and mix, raw material is joined in the corundum crucible, in the Si-Mo rod resistance furnace, heat and found, glass melting temperature is 1200 ℃, soaking time 30min.
After treating that glass melting evenly, a part is poured moulding in the stainless steel mould that preheating is of a size of 55mm * 6mm * 6mm into, put into retort furnace subsequently in 450 ℃ of annealing, furnace cooling behind the insulation 2h, as shown in table 1 with the PCY horizontal expander instrument test sample coefficient of expansion, another part high-temperature water quenching, and ball milling is to Powdered, sieve through 300 purpose screen clothes, the powder that takes a morsel utilizes HCT-1/2 differential thermal analyzer tested glass softening temperature as shown in table 1, gained DTA curve is seen accompanying drawing 1, and the glass powder after sieving uses for the user through packing.
Embodiment 2:
By the composition weight percent of table 1 batching and mix, raw material is joined in the corundum crucible, in the Si-Mo rod resistance furnace, heat and found, glass melting temperature is 1250 ℃, soaking time 40min.
After treating that glass melting evenly, a part is poured moulding in the stainless steel mould that preheating is of a size of 55mm * 6mm * 6mm into, put into retort furnace subsequently in 450 ℃ of annealing, furnace cooling behind the insulation 2h, as shown in table 1 with the PCY horizontal expander instrument test sample coefficient of expansion, another part high-temperature water quenching, and ball milling is to Powdered, sieve through 300 purpose screen clothes, the powder that takes a morsel utilizes HCT-1/2 differential thermal analyzer tested glass softening temperature as shown in table 1, gained DTA curve is seen accompanying drawing 2, and the glass powder after sieving uses for the user through packing.
Embodiment 3:
By the composition weight percent of table 1 batching and mix, raw material is joined in the corundum crucible, in the Si-Mo rod resistance furnace, heat and found, glass melting temperature is 1150 ℃, soaking time 35min.
After treating that glass melting evenly, a part is poured moulding in the stainless steel mould that preheating is of a size of 55mm * 6mm * 6mm into, put into retort furnace subsequently in 450 ℃ of annealing, furnace cooling behind the insulation 2h, as shown in table 1 with the PCY horizontal expander instrument test sample coefficient of expansion, another part high-temperature water quenching, and ball milling is to Powdered, sieve through 300 purpose screen clothes, the powder that takes a morsel utilizes HCT-1/2 differential thermal analyzer tested glass softening temperature as shown in table 1, gained DTA curve is seen accompanying drawing 3, and the glass powder after sieving uses for the user through packing.
Embodiment 4:
By the composition weight percent of table 1 batching and mix, raw material is joined in the corundum crucible, in the Si-Mo rod resistance furnace, heat and found, glass melting temperature is 1100 ℃, soaking time 60min.
After treating that glass melting evenly, a part is poured moulding in the stainless steel mould that preheating is of a size of 55mm * 6mm * 6mm into, put into retort furnace subsequently in 450 ℃ of annealing, furnace cooling behind the insulation 2h, as shown in table 1 with the PCY horizontal expander instrument test sample coefficient of expansion, another part high-temperature water quenching, and ball milling is to Powdered, sieve through 300 purpose screen clothes, the powder that takes a morsel utilizes HCT-1/2 differential thermal analyzer tested glass softening temperature as shown in table 1, gained DTA curve is seen accompanying drawing 4, and the glass powder after sieving uses for the user through packing.

Claims (9)

1. a low-temperature lead-free glass powder is characterized in that the raw material of described lead-free glass powder comprises following component and weight percentage: Bi 2O 330～80%, B 2O 310～60%, ZnO 0～20%, Sb 2O 30～20%, Al 2O 30～10%, alkalimetal oxide 0～7%; Described basic oxide are Li 2O.
2. according to the described low-temperature lead-free glass powder of claim 1, it is characterized in that the component of described lead-free glass powder and weight percentage are: Bi 2O 355%, B 2O 335%, ZnO 8%, Sb 2O 30%, Al 2O 32%, Li 2O 0%.
3. according to the described low-temperature lead-free glass powder of claim 1, it is characterized in that the component of described lead-free glass powder and weight percentage are: Bi 2O 347.40%, B 2O 330%, ZnO 7%, Sb 2O 314%, Al 2O 31.60%, Li 2O 0%.
4. according to the described low-temperature lead-free glass powder of claim 1, it is characterized in that the component of described lead-free glass powder and weight percentage are: Bi 2O 356.50%, B 2O 331.70%, ZnO 8.3%, Sb 2O 30%, Al 2O 31.9%, Li 2O 1.6%.
5. according to the described low-temperature lead-free glass powder of claim 1, it is characterized in that the component of described lead-free glass powder and weight percentage are: Bi 2O 370%, B 2O 320%, ZnO 5%, Sb 2O 32%, Al 2O 32%, Li 2O 1%.
6. the preparation method of any described low-temperature lead-free glass powder in the claim 1～5 may further comprise the steps:
(1) raw material of lead-free glass powder comprises following component and weight percentage: Bi 2O 330～80%, B 2O 310～60%, ZnO 0～20%, Sb 2O 30～20%, Al 2O 30～10%, alkalimetal oxide 0～7%; Described basic oxide are Li 2O takes by weighing raw material by above-mentioned composition, utilizes planetary ball mill, is medium ball milling 30～60min mixing with ethanol, obtains the oxide compound that mixes after the drying;
(2) after the compound fusing, pour into and obtain the glass slag in the deionized water, oven dry then, the ball grinder ball milling in planetary ball mill of packing into;
(3) cross 300 order mesh screens behind the ball milling, just obtain low-temperature lead-free glass powder.
7. according to the preparation method of right 6 described low-temperature lead-free glass powder, it is characterized in that: described lead-free glass powder is to found and be incubated 0.5～2h at 1100～1300 ℃.
8. according to the preparation method of right 6 described low-temperature lead-free glass powder, it is characterized in that: the lead-free glass powder diameter after the oven dry is the agate ball of 10mm and 5mm, lead-free glass powder and agate ball are with the mixed of 1:3, in agate jar, the weight ratio of agate ball and lead-free glass powder is 2:1～6:1, be medium with ethanol, rotating speed is 300～500 rev/mins, adopts planetary ball mill ball milling 3～12h.
9. according to the preparation method of right 6 described low-temperature lead-free glass powder, it is characterized in that: the D50 that crosses the lead-free glass powder that obtains behind the 300 order mesh screens is 0～2.5 μ m.
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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103903677A (en) * 2014-03-18 2014-07-02 上海志感电子科技有限公司 Medium temperature sintering type electro-conduction slurry with lead-free glass powder and preparation method of medium temperature sintering type electro-conduction slurry
CN106477894A (en) * 2016-11-01 2017-03-08 福州大学 A kind of low temperature sealing glass containing Fe and its preparation and application
CN106495490A (en) * 2016-11-01 2017-03-15 福州大学 One kind contains SiO2LED low temperature sealing glass
CN106495487A (en) * 2016-11-01 2017-03-15 福州大学 A kind of low temperature sealing glass and its preparation and application containing Ce
CN106495491A (en) * 2016-11-01 2017-03-15 福州大学 One kind contains Al2O3LED low temperature sealing glass
CN114230187A (en) * 2022-01-19 2022-03-25 西安石油大学 Low-temperature lead-free electronic glass powder for photoelectric sealing
CN115772005A (en) * 2021-09-06 2023-03-10 长春理工大学 Preparation method of lead-free glass powder for silver paste of solar cell

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US20060128549A1 (en) * 2004-12-09 2006-06-15 B.G. Negev Technologies And Applications Ltd. Lead-free phosphate glasses
CN101066839A (en) * 2007-06-05 2007-11-07 东华大学 No-lead glass powder for electrode coating and its prepn process
CN102190442A (en) * 2010-03-12 2011-09-21 郑庆云 Low-melting-point glass powder for vacuum glass sealing, and preparation method thereof
CN102245525A (en) * 2008-12-12 2011-11-16 旭硝子株式会社 Sealing glass, glass member having sealing material layer, and electronic device and method for producing the same

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JP2005350322A (en) * 2004-06-14 2005-12-22 Ohara Inc Yb-CONTAINING GLASS
US20060128549A1 (en) * 2004-12-09 2006-06-15 B.G. Negev Technologies And Applications Ltd. Lead-free phosphate glasses
CN101066839A (en) * 2007-06-05 2007-11-07 东华大学 No-lead glass powder for electrode coating and its prepn process
CN102245525A (en) * 2008-12-12 2011-11-16 旭硝子株式会社 Sealing glass, glass member having sealing material layer, and electronic device and method for producing the same
CN102190442A (en) * 2010-03-12 2011-09-21 郑庆云 Low-melting-point glass powder for vacuum glass sealing, and preparation method thereof

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103903677A (en) * 2014-03-18 2014-07-02 上海志感电子科技有限公司 Medium temperature sintering type electro-conduction slurry with lead-free glass powder and preparation method of medium temperature sintering type electro-conduction slurry
CN106477894A (en) * 2016-11-01 2017-03-08 福州大学 A kind of low temperature sealing glass containing Fe and its preparation and application
CN106495490A (en) * 2016-11-01 2017-03-15 福州大学 One kind contains SiO2LED low temperature sealing glass
CN106495487A (en) * 2016-11-01 2017-03-15 福州大学 A kind of low temperature sealing glass and its preparation and application containing Ce
CN106495491A (en) * 2016-11-01 2017-03-15 福州大学 One kind contains Al2O3LED low temperature sealing glass
CN106495490B (en) * 2016-11-01 2019-02-22 福州大学 One kind containing SiO2LED low temperature sealing glass
CN106495491B (en) * 2016-11-01 2019-05-10 福州大学 One kind containing Al2O3LED low temperature sealing glass
CN115772005A (en) * 2021-09-06 2023-03-10 长春理工大学 Preparation method of lead-free glass powder for silver paste of solar cell
CN114230187A (en) * 2022-01-19 2022-03-25 西安石油大学 Low-temperature lead-free electronic glass powder for photoelectric sealing

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Application publication date: 20130925