CN103342451A - Manufacturing method for lead-free sealing glass with transitional expansion coefficient - Google Patents
Manufacturing method for lead-free sealing glass with transitional expansion coefficient Download PDFInfo
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- CN103342451A CN103342451A CN2013102456014A CN201310245601A CN103342451A CN 103342451 A CN103342451 A CN 103342451A CN 2013102456014 A CN2013102456014 A CN 2013102456014A CN 201310245601 A CN201310245601 A CN 201310245601A CN 103342451 A CN103342451 A CN 103342451A
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Abstract
The invention relates to the field of glass new materials, and particularly discloses a manufacturing method for a lead-free sealing glass with a transitional expansion coefficient. The lead-free sealing glass is obtained by using quartz sand, aluminium hydroxide, bismuth trioxide, ferric oxide, sodium carbonate, potassium carbonate, magnesium oxide, calcium carbonate, barium carbonate and zinc oxide as raw materials and through the steps of mixing the above raw materials uniformly, melting the mixed materials and homogenizing to obtain a glass melt, then treating the glass melt by casting, annealing, cutting, buffing, polishing and performing heat treatment under a reduction atmosphere. The manufacturing method for the lead-free sealing glass with the transitional expansion coefficient overcomes various disadvantages in a conventional transitional sealing method, has the advantages of simple sealing process, low cost, easily controllable quality and the like, and is very suitable for situations that the cross section of a to-be-sealed device is in a circle structure.
Description
(1) technical field
The present invention relates to the glass field of new, particularly a kind of manufacture method of excessive expansion coefficient barium crown sealed glass.
(2) background technology
Seal glass is the special glass that a class connects differing materials and seal, the body material that can carry out sealing-in comprises metal, pottery and glass, is widely used in various fields such as electrovacuum and microelectronics, laser and infrared technique, high energy physics, the energy, aerospace, automobile.Along with the miniaturization of instrument component, the precise treatment level of structural group element continues to promote, and 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 requirement to the seal glass quality is also more and more higher.Lead glass has that glass formation range is big, specific refractory power is high and characteristics such as material property is long, be used as sealing glass material for a long time always, but lead glass also enjoys people's attention to the hazardness of human body and environment, and the exploitation of barium crown sealed glass and application have become the common recognition in research and production field.
In the seal glass performance most important be exactly its coefficient of expansion should be complementary by the coefficient of expansion of seal, sealing materials, in general the two should be close as far as possible at room temperature to the coefficient of expansion between the glass annealing upper temperature limit.The control of the difference of the two thermal expansivity is 5 * 10 in the life-time service temperature range
-7K
-1Below, otherwise can in closure, form bigger stress, cause closure to crack or break.In actual production; through regular meeting run into need coefficient of expansion difference is bigger two kinds of situations that material carries out sealing-in; be to adopt the coefficient of expansion to carry out repeatedly transition sealing between the glass between the two traditionally; thermal expansivity between the adjacent materials is slowly transition successively, can not crack too greatly because of coefficient of expansion difference.But the sealing process complexity of this method, quality product are difficult to control, particularly when being ring structure by the cross section of sealing device, adopt the difficulty of transition sealing mode further to increase.
(3) summary of the invention
The present invention provides the manufacture method of the excessive expansion coefficient barium crown sealed glass that a kind of production technique is simple, starting material are easy to get in order to remedy the deficiencies in the prior art.
The present invention is achieved through the following technical solutions:
A kind of manufacture method of excessive expansion coefficient barium crown sealed glass may further comprise the steps:
(1) be raw material with quartz sand, aluminium hydroxide, bismuthous oxide bismuth trioxide, ferric oxide, yellow soda ash, salt of wormwood, magnesium oxide, calcium carbonate barium carbonate and zinc oxide, after above-mentioned raw materials mixed, in kiln, in 1723 ~ 1753K fusion and homogenizing, obtain glass melt;
(2) make glass melt temperature after the material road flow to operate portions be down to 1373 ~ 1423K, be on the cast iron mould of 733K in temperature through the material guiding pipe continuous casting then, obtain the parent glass that thickness is 3 ~ 6cm, parent glass enters in the annealing furnace through cast iron crawling traction, furnace cooling behind the annealing 1.5h under 723 ~ 735K;
(3) obtain the glass transformation temperature T of each sample according to the DSC test result of parent glass
g, parent glass by the specification cutting, after polishing and the polishing, is put into the sealing crucible that carbon dust is housed, sample places above the porous ceramics, does not directly contact with carbon dust, in 1.05 ~ 1.09T
gTemperature insulation 24h.
(4) parent glass at reducing atmosphere after heat treatment forms a layer thickness and is the crystal of a few to tens of microns on the surface of glass, will namely obtain product after the crystal layer polishing.
Wherein, in the step (1), the parts by weight proportioning of the effective constituent of described raw material is SiO
250.39 ~ 51.96%, Al
2O
32.40 ~ 2.48%, Bi
2O
313.43 ~ 13.85%, Fe
2O
32.10 ~ 2.16%, Na
2O 9.74 ~ 10.05%, K
2O 14.81 ~ 15.27%, and MgO 0 ~ 2.72%%, and CaO 0 ~ 1.52%, and BaO 0 ~ 4.16%, and ZnO 0 ~ 6.41%.
Preparation method of the present invention, in reducing atmosphere, parent glass is in surperficial crystallization process, and the modification body positively charged ion in the glass spreads from inside to outside and participates in crystal growth, cause and modify the minimizing gradually from inside to outside of body cation concn, and then cause thermal expansivity to reduce gradually from inside to outside.
The crystal layer thickness that the different glass samples of forming are separated out owing to the heat treatment time difference has difference slightly, but has tangible interface between crystal layer and the glass, and the surface crystal layer peels off easily, so polishing process is very simple.The glass surface thermal expansivity can be regulated by heat treatment time according to the thermal expansivity of sealing-in substrate material.
After heat treatment the high and outside coefficient of expansion of the coefficient of expansion of glass inside is low, namely just can replace multilayer seal glass in the transition sealing mode with a glass.
More excellent scheme of the present invention is:
In the step (1), the melt temperature of raw material is 1753K.
In the step (2), glass melt temperature after the material road flow to operate portions is down to 1423K, is on the cast iron mould of 733K, to obtain the parent glass that thickness is 6cm in temperature through the material guiding pipe continuous placing then, parent glass enters in the annealing furnace through cast iron crawling traction, anneals under 725K.
In the step (3), sample in retort furnace in 1.09T
gBe cooled to room temperature behind the temperature insulation 24h.
The present invention has overcome the various drawbacks that conventional transition sealing-in mode exists, and has advantages such as sealing process is simple, cost is low, the easy control of quality product, and being fit to by the cross section of sealing device very much is the situation of ring structure.
(4) embodiment
Below be described further by the manufacture method of specific embodiment to a kind of excessive expansion coefficient of the present invention barium crown sealed glass, wherein embodiment 3 is most preferred embodiment.It is as shown in the table that embodiment 1 ~ 5 obtains significant parameter and the performance of glass:
Embodiment 1:
Raw materials used weight part consists of:
51.96 parts of quartz sands, 3.83 parts in aluminium hydroxide, 13.99 parts of bismuthous oxide bismuth trioxides, 2.16 parts of ferric oxide, 14.46 parts in yellow soda ash, 4.64 parts of SODIUMNITRATE, 19.39 parts in salt of wormwood, 5.52 parts in saltpetre, 2.74 parts in magnesium oxide, 2.73 parts in calcium carbonate.
The manufacture method concrete steps are as follows:
(1) above-mentioned raw materials is mixed after, in stove, in 1753K fusion and homogenizing, obtain glass melt;
(2) glass melt temperature after the material road flow to operate portions is down to 1423K, be on the cast iron mould of 733K in temperature through the material guiding pipe continuous casting then, obtain the parent glass that thickness is 6cm, parent glass enters in the annealing furnace through cast iron crawling traction, furnace cooling behind 735K annealing 1.5h;
(3) the DSC test result according to parent glass obtains glass transformation temperature T
g, parent glass by specification cutting, after polishing and the polishing, is put into the sealing crucible that carbon dust is housed, sample places above the porous ceramics, directly do not contact with carbon dust, in retort furnace in 1.09T
gBe cooled to room temperature behind the temperature insulation 24h.
(4) glass after the thermal treatment namely gets to be after polishing and has the barium crown sealed glass goods that cross the coefficient of expansion.
Embodiment 2:
Raw materials used weight part consists of:
50.56 parts of quartz sands, 3.73 parts in aluminium hydroxide, 13.61 parts of bismuthous oxide bismuth trioxides, 2.10 parts of ferric oxide, 14.07 parts in yellow soda ash, 4.51 parts of SODIUMNITRATE, 18.87 parts in salt of wormwood, 5.37 parts in saltpetre, 2.66 parts in magnesium oxide, 5.24 parts of barium carbonates.
The manufacture method concrete steps are as follows:
(1) above-mentioned raw materials is mixed after, in stove, in 1723K fusion and homogenizing, obtain glass melt;
(2) glass melt temperature after the material road flow to operate portions is down to 1373K, be on the cast iron mould of 733K in temperature through the material guiding pipe continuous casting then, obtain the parent glass that thickness is 3cm, parent glass enters in the annealing furnace through cast iron crawling traction, furnace cooling behind 723 times annealing 1.5h;
(3) the DSC test result according to parent glass obtains glass transformation temperature T
g, parent glass by specification cutting, after polishing and the polishing, is put into the sealing crucible that carbon dust is housed, sample places above the porous ceramics, directly do not contact with carbon dust, in retort furnace in 1.05T
gBe cooled to room temperature behind the temperature insulation 24h.
(4) glass after the thermal treatment namely gets to be after polishing and has the barium crown sealed glass goods that cross the coefficient of expansion.
Embodiment 3:
Raw materials used weight part consists of:
51.61 parts of quartz sands, 3.81 parts in aluminium hydroxide, 13.90 parts of bismuthous oxide bismuth trioxides, 2.15 parts of ferric oxide, 14.37 parts in yellow soda ash, 4.61 parts of SODIUMNITRATE, 19.26 parts in salt of wormwood, 5.48 parts in saltpetre, 2.72 parts in magnesium oxide, 2.21 parts in zinc oxide.
The manufacture method concrete steps are as follows:
(1) above-mentioned raw materials is mixed after, in stove, in 1753K fusion and homogenizing, obtain glass melt;
(2) glass melt temperature after the material road flow to operate portions is down to 1423K, be on the cast iron mould of 733K in temperature through the material guiding pipe continuous casting then, obtain the parent glass that thickness is 6cm, parent glass enters in the annealing furnace through cast iron crawling traction, furnace cooling behind the annealing 1.5h under 725K;
(3) the DSC test result according to parent glass obtains glass transformation temperature T
g, parent glass by specification cutting, after polishing and the polishing, is put into the sealing crucible that carbon dust is housed, sample places above the porous ceramics, directly do not contact with carbon dust, in retort furnace in 1.09T
gBe cooled to room temperature behind the temperature insulation 24h.
(4) glass after the thermal treatment namely gets to be after polishing and has the barium crown sealed glass goods that cross the coefficient of expansion.
Embodiment 4:
Raw materials used weight part consists of:
50.49 parts of quartz sands, 3.72 parts in aluminium hydroxide, 13.60 parts of bismuthous oxide bismuth trioxides, 2.10 parts of ferric oxide, 14.06 parts in yellow soda ash, 4.51 parts of SODIUMNITRATE, 18.84 parts in salt of wormwood, 5.36 parts in saltpetre, 0.53 part in magnesium oxide, 6.48 parts in zinc oxide.
The manufacture method concrete steps are as follows:
(1) above-mentioned raw materials is mixed after, in stove, in 1753K fusion and homogenizing, obtain glass melt;
(2) glass melt temperature after the material road flow to operate portions is down to 1423K, be on the cast iron mould of 733K in temperature through the material guiding pipe continuous casting then, obtain the parent glass that thickness is 3cm, parent glass enters in the annealing furnace through cast iron crawling traction, furnace cooling behind the annealing 1.5h under 725K;
(3) the DSC test result according to parent glass obtains glass transformation temperature T
g, parent glass by specification cutting, after polishing and the polishing, is put into the sealing crucible that carbon dust is housed, sample places above the porous ceramics, directly do not contact with carbon dust, in retort furnace in 1.07T
gBe cooled to room temperature behind the temperature insulation 24h.
(4) glass after the thermal treatment namely gets to be after polishing and has the barium crown sealed glass goods that cross the coefficient of expansion.
Embodiment 5:
Raw materials used weight part consists of:
50.39 parts of quartz sands, 3.72 parts in aluminium hydroxide, 13.57 parts of bismuthous oxide bismuth trioxides, 2.10 parts of ferric oxide, 14.03 parts in yellow soda ash, 4.50 parts of SODIUMNITRATE, 18.80 parts in salt of wormwood, 5.35 parts in saltpetre, 1.32 parts in calcium carbonate, 6.46 parts in zinc oxide.
The manufacture method concrete steps are as follows:
(1) above-mentioned raw materials is mixed after, in stove, in 1743K fusion and homogenizing, obtain glass melt;
(2) glass melt temperature after the material road flow to operate portions is down to 1383K, be on the cast iron mould of 733K in temperature through the material guiding pipe continuous casting then, obtain the parent glass that thickness is 3cm, parent glass enters in the annealing furnace through cast iron crawling traction, furnace cooling behind the annealing 1.5h under 728K;
(3) the DSC test result according to parent glass obtains glass transformation temperature T
g, parent glass by specification cutting, after polishing and the polishing, is put into the sealing crucible that carbon dust is housed, sample places above the porous ceramics, directly do not contact with carbon dust, in retort furnace in 1.07T
gBe cooled to room temperature behind the temperature insulation 24h.
(4) glass after the thermal treatment namely gets to be after polishing and has the barium crown sealed glass goods that cross the coefficient of expansion.
Claims (5)
1. the manufacture method of an excessive expansion coefficient barium crown sealed glass, it is characterized by: may further comprise the steps: (1) is raw material with quartz sand, aluminium hydroxide, bismuthous oxide bismuth trioxide, ferric oxide, yellow soda ash, salt of wormwood, magnesium oxide, calcium carbonate barium carbonate and zinc oxide, after above-mentioned raw materials mixed, in kiln, in 1723 ~ 1753K fusion and homogenizing, obtain glass melt; (2) make glass melt temperature after the material road flow to operate portions be down to 1373 ~ 1423K, be on the cast iron mould of 733K in temperature through the material guiding pipe continuous casting then, obtain the parent glass that thickness is 3 ~ 6cm, parent glass enters in the annealing furnace through cast iron crawling traction, furnace cooling behind the annealing 1.5h under 723 ~ 735K; (3) obtain the glass transformation temperature T of each sample according to the DSC test result of parent glass
g, parent glass by the specification cutting, after polishing and the polishing, is put into the sealing crucible that carbon dust is housed, sample places above the porous ceramics, does not directly contact with carbon dust, in 1.05 ~ 1.09T
gTemperature insulation 24h;
(4) parent glass at reducing atmosphere after heat treatment forms a layer thickness and is the crystal of a few to tens of microns on the surface of glass, will namely obtain product after the crystal layer polishing.
2. the manufacture method of excessive expansion coefficient barium crown sealed glass according to claim 1, it is characterized in that: in the step (1), the parts by weight proportioning of the effective constituent of described raw material is SiO
250.39 ~ 51.96%, Al
2O
32.40 ~ 2.48%, Bi
2O
313.43 ~ 13.85%, Fe
2O
32.10 ~ 2.16%, Na
2O 9.74 ~ 10.05%, K
2O 14.81 ~ 15.27%, and MgO 0 ~ 2.72%%, and CaO 0 ~ 1.52%, and BaO 0 ~ 4.16%, and ZnO 0 ~ 6.41%.
3. the manufacture method of excessive expansion coefficient barium crown sealed glass according to claim 1, it is characterized in that: in the step (1), the melt temperature of raw material is 1753K.
4. the manufacture method of excessive expansion coefficient barium crown sealed glass according to claim 1, it is characterized in that: in the step (2), glass melt temperature after the material road flow to operate portions is down to 1423K, be on the cast iron mould of 733K in temperature through the material guiding pipe continuous placing then, obtain the parent glass that thickness is 6cm, parent glass enters in the annealing furnace through cast iron crawling traction, anneals under 725K.
5. the manufacture method of excessive expansion coefficient barium crown sealed glass according to claim 1 is characterized in that: in the step (3), sample in retort furnace in 1.09T
gBe cooled to room temperature behind the temperature insulation 24h.
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| CN201310245601.4A CN103342451B (en) | 2013-06-20 | 2013-06-20 | Manufacturing method for lead-free sealing glass with transitional expansion coefficient |
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| CN201310245601.4A CN103342451B (en) | 2013-06-20 | 2013-06-20 | Manufacturing method for lead-free sealing glass with transitional expansion coefficient |
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| CN103342451B CN103342451B (en) | 2015-03-25 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111039579A (en) * | 2019-12-31 | 2020-04-21 | 沧州天瑞星光热技术有限公司 | Low-temperature annealing process for reducing stress of glass-metal sealing structure |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002060241A (en) * | 2000-08-18 | 2002-02-26 | Asahi Techno Glass Corp | Glass for sealing tungsten |
| JP2002068774A (en) * | 2000-06-16 | 2002-03-08 | Asahi Techno Glass Corp | GLASS SUITABLE FOR SEALING Fe-Ni-Co BASED ALLOY |
| CN101597136A (en) * | 2009-07-23 | 2009-12-09 | 苏州恒仓红外光学材料研发中心有限责任公司 | A kind of lead-free low-melting sealing glass and preparation method thereof |
| TWI342078B (en) * | 2006-01-27 | 2011-05-11 | Samsung Mobile Display Co Ltd | Organic light emitting display of mother substrate unit and method of fabricating the same |
-
2013
- 2013-06-20 CN CN201310245601.4A patent/CN103342451B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002068774A (en) * | 2000-06-16 | 2002-03-08 | Asahi Techno Glass Corp | GLASS SUITABLE FOR SEALING Fe-Ni-Co BASED ALLOY |
| JP2002060241A (en) * | 2000-08-18 | 2002-02-26 | Asahi Techno Glass Corp | Glass for sealing tungsten |
| TWI342078B (en) * | 2006-01-27 | 2011-05-11 | Samsung Mobile Display Co Ltd | Organic light emitting display of mother substrate unit and method of fabricating the same |
| CN101597136A (en) * | 2009-07-23 | 2009-12-09 | 苏州恒仓红外光学材料研发中心有限责任公司 | A kind of lead-free low-melting sealing glass and preparation method thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111039579A (en) * | 2019-12-31 | 2020-04-21 | 沧州天瑞星光热技术有限公司 | Low-temperature annealing process for reducing stress of glass-metal sealing structure |
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Denomination of invention: A manufacturing method of lead-free sealing glass with transition expansion coefficient Effective date of registration: 20211206 Granted publication date: 20150325 Pledgee: Yantai financing guarantee Group Co.,Ltd. Pledgor: SHANDONG KANGYOU GLASS MATERIAL Co.,Ltd. Registration number: Y2021980014210 |
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Date of cancellation: 20220808 Granted publication date: 20150325 Pledgee: Yantai financing guarantee Group Co.,Ltd. Pledgor: SHANDONG KANGYOU GLASS MATERIAL Co.,Ltd. Registration number: Y2021980014210 |
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