CN103332862B - Lead-free sealing glass with transitional expansion coefficient - Google Patents
Lead-free sealing glass with transitional expansion coefficient Download PDFInfo
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- CN103332862B CN103332862B CN201310245658.4A CN201310245658A CN103332862B CN 103332862 B CN103332862 B CN 103332862B CN 201310245658 A CN201310245658 A CN 201310245658A CN 103332862 B CN103332862 B CN 103332862B
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Abstract
The invention belongs to the field of new glass materials, and particularly discloses lead-free sealing glass with a transitional expansion coefficient. The lead-free sealing glass with the transitional expansion coefficient is prepared by mixing the effective materials of SiO2, Al2O3, Bi2O3, Fe2O3, Na2O, K2O, MgO, CaO, SrO, BaO and ZnO according to a certain weight fraction. The lead-free sealing glass with the transitional expansion coefficient overcomes the defects of the conventional transitional sealing manner, has the advantages that the sealing process is simple, the cost is low and the product quality is easy to control, and is particularly suitable for the situation that the cross section of the device to be sealed is annular.
Description
(1) technical field
The present invention relates to glass field of new, particularly a kind of excessive expansion coefficient barium crown sealed glass.
(2) background technology
Seal glass is that differing materials carries out connecting and the special glass sealed by a class, comprised metal, pottery and glass by the body material of sealing-in, be widely used in electrovacuum and the various fields such as microelectronics, laser and infrared technique, high energy physics, the energy, aerospace, automobile.Along with the miniaturization of instrument component, the precise treatment persistent levels of structural component part promote, the kind of electronic devices and components is more and more many, and the mode of appearance of product is also more and more numerous and diverse, and this is also more and more higher to the requirement of seal glass quality.Lead glass has that glass formation range is large, specific refractory power is high and the feature such as material property is long, for a long time in the widespread use of sealing-in field.But the hazardness of lead glass to human body and environment is also more and more paid close attention to by people, the development & application of barium crown sealed glass has become the common recognition in research and production field.
In seal glass performance the most important be exactly its coefficient of expansion should with by the matched expansion coefficient of seal, sealing materials, in general the two coefficient of expansion between room temperature to the Annealing Temperature of Glass upper limit should be close as far as possible.In life-time service temperature range, the difference of the two thermal expansivity controls 5 × 10
-7k
-1below, otherwise larger stress can be formed in closure, cause closure to crack or break.In actual production; often can run into the situation needing bi-material larger for coefficient of expansion difference to be carried out sealing-in; adopt the coefficient of expansion to carry out repeatedly transition sealing between glass therebetween traditionally; thermal expansivity between adjacent materials is slowly transition successively, can not crack because coefficient of expansion difference is too large.But the sealing process of this method is complicated, quality product is difficult to control.Particularly when being ring structure by the cross section of sealing device, the difficulty of transition sealing mode is adopted to increase further.
(3) summary of the invention
The present invention, in order to make up the deficiencies in the prior art, provides the excessive expansion coefficient barium crown sealed glass that a kind of preparation method is simple, starting material are easy to get.
The present invention is achieved through the following technical solutions:
A kind of excessive expansion coefficient barium crown sealed glass, be made up of effective material of following weight fraction:
SiO
2 46.92~52.18%，Al
2O
3 2.24~2.49%，Bi
2O
3 12.51~19.91%，Fe
2O
3 1.95~2.17%，Na
2O 9.07~10.09%，K
2O 13.79~15.34%，MgO 0~3.83%，CaO 0~5.25%，SrO 0~9.28%，BaO 0~13.52%，ZnO 0~7.44%。
The weight proportion of its preferred each effective material is:
SiO
2 48.10~52.18%，Al
2O
3 2.26~2.40%，Bi
2O
3 16.32~18.01%，Fe
2O
3 2.03~2.10%，Na
2O 9.50~10.00%，K
2O 14.00~15.11%，MgO 3.60~3.80%。
Described effective material SiO
2source be quartz sand, Al
2o
3source be aluminium hydroxide, Li
2the source of O is Quilonum Retard, Na
2the source of O is sodium carbonate, K
2the source of O is salt of wormwood, and the source of CaO is calcium carbonate.
The preparation process of barium crown sealed glass of the present invention comprises:
(1) according to above-mentioned chemical constitution, accurately take the weight of the corresponding raw material of each composition and mix and make admixtion, admixtion is incubated 2 hours in 1743 ~ 1753K in silicon molybdenum rod furnace, obtained uniform glass metal, the glass metal of homogenizing is cast in the stainless steel mould of preheating, anneal 1 hour at 700 ~ 730K, obtain parent glass that is transparent, uniform bubble-free;
(2) the glass transformation temperature T of each sample is obtained according to the DSC test result of parent glass
g, parent glass is placed in above porous ceramics, then puts into the crucible that carbon dust is housed together, in 1.09T
gtemperature is furnace cooling after 24 hours;
(3) parent glass is after reducing atmosphere thermal treatment, forms on the surface of glass the crystal that a layer thickness is 5 ~ 25 microns, will namely obtain the barium crown sealed glass be and had and cross the coefficient of expansion after crystal layer polishing.
In reducing atmosphere, parent glass is in Surface Crystallization process, and the modification body positively charged ion in glass spreads from inside to outside and participates in crystal growth, causes modification body cation concn to reduce gradually from inside to outside, and then causes thermal expansivity to reduce gradually from inside to outside.The crystal layer thickness slightly difference that the different glass sample formed is separated out due to heat treatment time difference, but between crystal layer and glass, there is obvious interface, surface crystal layer easily peels off, and therefore polishing process is very simple.Glass surface thermal expansivity can be regulated by heat treatment time according to the thermal expansivity of sealing-in substrate material.
The coefficient of expansion of inside glass of the present invention is high and the coefficient of expansion of outside is low, namely the multilayer seal glass in transition sealing mode just can be replaced with one block of glass, overcome the various drawbacks that conventional transition sealing-in mode exists, have the advantages such as sealing process is simple, cost is low, quality product easily controls, being applicable to very much is the situation of ring structure by the cross section of sealing device.
(4) accompanying drawing explanation
Below in conjunction with accompanying drawing, the present invention is further illustrated.
Fig. 1 is the linear expansivity comparison diagram in embodiment 1 before and after parent glass thermal treatment.
(5) embodiment
Be described further lead-free sealing glass material of the present invention below by way of specific embodiment, wherein embodiment 1 is most preferred embodiment.Significant parameter and the performance of embodiment 1 ~ 5 are as shown in the table.
Embodiment 1:
Raw materials used weight part consists of: quartz sand 52.18 parts, 3.85 parts, aluminium hydroxide, bismuthous oxide bismuth trioxide 14.05 parts, ferric oxide 2.17 parts, 3.85 parts, magnesium oxide, 14.53 parts, sodium carbonate, SODIUMNITRATE 4.66 parts, 19.47 parts, salt of wormwood, 5.54 parts, saltpetre.
Manufacture method concrete steps are as follows:
Step 1: be mixed evenly according to above-mentioned raw materials precise, be incubated 2 hours in 1753K in silicon molybdenum rod furnace, obtained uniform glass metal.Uniform glass metal is cast in rapidly in the stainless steel mould of preheating, anneals 1 hour at 720 K, obtain mass foundation glass that is transparent, uniform bubble-free.
Step 2: the glass transformation temperature T obtaining each sample according to the DSC test result of parent glass
g, parent glass is put into the closed crucible that carbon dust is housed, after 803K is incubated 24 hours, is cooled to room temperature.Namely sample after thermal treatment obtains the barium crown sealed glass be and had and cross the coefficient of expansion after polishing.
Embodiment 2:
Raw materials used weight part consists of: quartz sand 51.41 parts, 3.79 parts, aluminium hydroxide, bismuthous oxide bismuth trioxide 13.84 parts, ferric oxide 2.14 parts, 9.46 parts, calcium carbonate, 14.31 parts, sodium carbonate, SODIUMNITRATE 4.59 parts, 19.18 parts, salt of wormwood, 5.46 parts, saltpetre.
Manufacture method concrete steps are as follows:
Step 1: with quartz sand, aluminum oxide, aluminium hydroxide, bismuthous oxide bismuth trioxide, ferric oxide, calcium carbonate, soda ash, SODIUMNITRATE, salt of wormwood etc. for raw material, be mixed evenly according to above-mentioned chemical constitution precise, 2 hours are incubated in 1753K, obtained uniform glass metal in silicon molybdenum rod furnace.Uniform glass metal is cast in rapidly in the stainless steel mould of preheating, anneals 1 hour at 730K, obtain mass foundation glass that is transparent, uniform bubble-free.
Step 2: the glass transformation temperature T obtaining each sample according to the DSC test result of parent glass
g, parent glass is put into the closed crucible that carbon dust is housed, after 821K is incubated 24 hours, is cooled to room temperature.Namely sample after thermal treatment obtains the barium crown sealed glass be and had and cross the coefficient of expansion after polishing.
Embodiment 3:
Raw materials used weight part consists of: quartz sand 49.22 parts, 3.63 parts, aluminium hydroxide, bismuthous oxide bismuth trioxide 13.25 parts, ferric oxide 2.05 parts, Strontium carbonate powder 13.36 parts, 13.7 parts, sodium carbonate, SODIUMNITRATE 4.39 parts, 18.37 parts, salt of wormwood, 5.23 parts, saltpetre.
Manufacture method concrete steps are as follows:
Step 1: with quartz sand, aluminum oxide, aluminium hydroxide, bismuthous oxide bismuth trioxide, ferric oxide, Strontium carbonate powder, soda ash, SODIUMNITRATE, salt of wormwood etc. for raw material, be mixed evenly according to above-mentioned chemical constitution precise, 2 hours are incubated in 1743K, obtained uniform glass metal in silicon molybdenum rod furnace.Uniform glass metal is cast in rapidly in the stainless steel mould of preheating, anneals 1 hour at 710K, obtain mass foundation glass that is transparent, uniform bubble-free.
Step 2: the glass transformation temperature T obtaining each sample according to the DSC test result of parent glass
g, parent glass is put into the closed crucible that carbon dust is housed, after 821K is incubated 24 hours, is cooled to room temperature.Namely sample after thermal treatment obtains the barium crown sealed glass be and had and cross the coefficient of expansion after polishing.
Embodiment 4:
Raw materials used weight part consists of: quartz sand 46.92 parts, 3.46 parts, aluminium hydroxide, bismuthous oxide bismuth trioxide 12.63 parts, ferric oxide 1.95 parts, barium carbonate 17.02 parts, 13.06 parts, sodium carbonate, SODIUMNITRATE 4.19 parts, 17.51 parts, salt of wormwood, 4.98 parts, saltpetre.
Manufacture method concrete steps are as follows:
Step 1: with quartz sand, aluminum oxide, aluminium hydroxide, bismuthous oxide bismuth trioxide, ferric oxide, barium carbonate, soda ash, SODIUMNITRATE, salt of wormwood etc. for raw material, be mixed evenly according to above-mentioned chemical constitution precise, 2 hours are incubated in 1743K, obtained uniform glass metal in silicon molybdenum rod furnace.Uniform glass metal is cast in rapidly in the stainless steel mould of preheating, anneals 1 hour at 700K, obtain mass foundation glass that is transparent, uniform bubble-free.
Step 2: the glass transformation temperature T obtaining each sample according to the DSC test result of parent glass
g, parent glass is put into the closed crucible that carbon dust is housed, after 821K is incubated 24 hours, is cooled to room temperature.Namely sample after thermal treatment obtains the barium crown sealed glass be and had and cross the coefficient of expansion after polishing.
Embodiment 5:
Raw materials used weight part consists of: quartz sand 50.22 parts, 3.7 parts, aluminium hydroxide, bismuthous oxide bismuth trioxide 13.52 parts, ferric oxide 2.09 parts, 7.51 parts, zinc oxide, 13.98 parts, sodium carbonate, SODIUMNITRATE 4.48 parts, 18.74 parts, salt of wormwood, 5.33 parts, saltpetre.
Manufacture method concrete steps are as follows:
Step 1: with quartz sand, aluminum oxide, aluminium hydroxide, bismuthous oxide bismuth trioxide, ferric oxide, zinc oxide, soda ash, SODIUMNITRATE, salt of wormwood etc. for raw material, be mixed evenly according to above-mentioned chemical constitution precise, 2 hours are incubated in 1743K, obtained uniform glass metal in silicon molybdenum rod furnace.Uniform glass metal is cast in rapidly in the stainless steel mould of preheating, anneals 1 hour at 710K, obtain mass foundation glass that is transparent, uniform bubble-free.
Step 2: the glass transformation temperature T obtaining each sample according to the DSC test result of parent glass
g, parent glass is put into the closed crucible that carbon dust is housed, after 821K is incubated 24 hours, is cooled to room temperature.Namely sample after thermal treatment obtains the barium crown sealed glass be and had and cross the coefficient of expansion after polishing.
Claims (2)
1. an excessive expansion coefficient barium crown sealed glass, is characterized by, and is made up: SiO of effective material of following weight fraction
246.92 ~ 52.18%, Al
2o
32.24 ~ 2.49%, Bi
2o
312.51 ~ 19.91%, Fe
2o
31.95 ~ 2.17%, Na
2o 9.07 ~ 10.09%, K
2o 13.79 ~ 15.34%, MgO 0 ~ 3.83%, CaO 0 ~ 5.25%, SrO 0 ~ 9.28%, BaO 0 ~ 13.52%, ZnO 0 ~ 7.44%; After using above-mentioned materials to obtain parent glass, parent glass is put into the closed crucible that carbon dust is housed, be cooled to room temperature in 1.09Tg temperature after 24 hours, namely the sample after thermal treatment obtains the barium crown sealed glass be and had and cross the coefficient of expansion after polishing.
2. excessive expansion coefficient barium crown sealed glass according to claim 1, is characterized in that: described effective material SiO
2source be quartz sand, Al
2o
3source be aluminium hydroxide, Li
2the source of O is Quilonum Retard, Na
2the source of O is sodium carbonate, K
2the source of O is salt of wormwood, and the source of CaO is calcium carbonate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310245658.4A CN103332862B (en) | 2013-06-20 | 2013-06-20 | Lead-free sealing glass with transitional expansion coefficient |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310245658.4A CN103332862B (en) | 2013-06-20 | 2013-06-20 | Lead-free sealing glass with transitional expansion coefficient |
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| Publication Number | Publication Date |
|---|---|
| CN103332862A CN103332862A (en) | 2013-10-02 |
| CN103332862B true CN103332862B (en) | 2015-06-17 |
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|---|---|---|---|
| CN201310245658.4A Expired - Fee Related CN103332862B (en) | 2013-06-20 | 2013-06-20 | Lead-free sealing glass with transitional expansion coefficient |
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Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106242269B (en) * | 2016-07-26 | 2018-05-11 | 齐鲁工业大学 | A kind of adjustable barium crown sealed glass of use temperature range |
| CN110190210A (en) * | 2019-03-12 | 2019-08-30 | 华电电力科学研究院有限公司 | A kind of solid oxide fuel cell structure convenient for edge sealing-in |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1595856A1 (en) * | 2003-02-19 | 2005-11-16 | Yamato Electronic Co., Ltd. | Lead-free glass material for use in sealing and, sealed article and method for sealing using the same |
| CN1830856A (en) * | 2006-03-17 | 2006-09-13 | 东华大学 | Leadless phosphate seal glass and its preparation method |
| CN1944304A (en) * | 2006-11-09 | 2007-04-11 | 北京科技大学 | Sealing micro crystal glass and its sealing method |
| US7585798B2 (en) * | 2003-06-27 | 2009-09-08 | Yamato Electronic Co., Ltd. | Lead-free glass material for use in sealing and, sealed article and method for sealing using the same |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19939789A1 (en) * | 1999-08-21 | 2001-02-22 | Schott Glas | Alkali-free aluminoborosilicate glasses and their uses |
-
2013
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1595856A1 (en) * | 2003-02-19 | 2005-11-16 | Yamato Electronic Co., Ltd. | Lead-free glass material for use in sealing and, sealed article and method for sealing using the same |
| US7585798B2 (en) * | 2003-06-27 | 2009-09-08 | Yamato Electronic Co., Ltd. | Lead-free glass material for use in sealing and, sealed article and method for sealing using the same |
| CN1830856A (en) * | 2006-03-17 | 2006-09-13 | 东华大学 | Leadless phosphate seal glass and its preparation method |
| CN1944304A (en) * | 2006-11-09 | 2007-04-11 | 北京科技大学 | Sealing micro crystal glass and its sealing method |
Non-Patent Citations (2)
| Title |
|---|
| Glass-forming ability, sinterability and thermal properties in the systems RO-BaO-SiO2(R=Mg, Zn);C.Lara等;《Journal of Non-Crystalline Solids》;20041231;第149-155页 * |
| 封接用Li2O-ZnO-Al2O3-SiO2玻璃析晶和热膨胀行为研究;艾传才等;《玻璃与搪瓷》;20091031;第37卷(第5期);第1-5页 * |
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Granted publication date: 20150617 Termination date: 20160620 |