CN101265024A - Low-melting point leadless borophosphate seal glass powder and preparation method thereof - Google Patents
Low-melting point leadless borophosphate seal glass powder and preparation method thereof Download PDFInfo
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- CN101265024A CN101265024A CNA2008100609902A CN200810060990A CN101265024A CN 101265024 A CN101265024 A CN 101265024A CN A2008100609902 A CNA2008100609902 A CN A2008100609902A CN 200810060990 A CN200810060990 A CN 200810060990A CN 101265024 A CN101265024 A CN 101265024A
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Abstract
The invention discloses low melting point lead-free borophosphate sealing glass powder and a preparation method thereof. The sealing glass powder is prepared from (mass percent) parent glass 60-70% and filling material 30-40%. The parent glass comprises R2O 1-20 wt %, B2O3 20-50 wt %, P2O5 30-50 wt %, MO 5-25 wt % and Nb2O5 0-20 wt %, wherein R is Li, Na or K, and M is Mg, Ca, Sr, Ba or Zn. The inventive sealing glass powder has lower sealing temperature (450-550 DEG C) and good chemical stability; and is especially suitable for sealing glass and ceramics or metals.
Description
Technical field
The invention belongs to the electronics chemical field, especially, relate to a kind of low-melting point leadless borophosphate seal glass powder and preparation method thereof.
Background technology
Sealing glass powder is widely used in the mutual sealing-in between the various types of materials in the devices such as photoelectron, and the material that present most of electron device sealing-in is adopted is plumbiferous low-melting point sealing glass, as PbO-ZnO-B
2O
3Or PbO-B
2O
3-SiO
2In glass.These glass have lower sealing temperature and lower thermal expansivity.But the plumbous oxide content that this glass contains is usually up to 30～80wt%.Therefore along with the enhancing of people's environmental consciousness, plumbiferous glass solder will be subjected to increasing restriction, and developing unleaded low-melting point sealing glass becomes and need urgent problem at present.
U.S. Pat 2002019303 has been reported a kind of SnO-P
2O
5The sealing glass powder of-ZnO system, can be used for the sealing-in of 430～500 ℃ of temperature ranges, but in this glass powder, contain more low price SnO, glass found with the sealing-in process in very easily oxidized, need under reducing atmosphere, found and sealing-in, bring very big drawback for the practicability of this glass powder.
Chinese patent 200310103592.1 has been reported a kind of V
2O
5-P
2O
5-Sb
2O
3The glass powder of system, this glass powder can be used for 430～500 ℃ sealing-in, but still contains deleterious V in glass powder
2O
5, and the chemical stability of this glass powder is not so good, thereby limited its practical application.
Summary of the invention
The objective of the invention is at the deficiencies in the prior art, provide a kind of chemical stability good, be easy to prepare low-melting point leadless borophosphate seal glass powder with sealing-in and preparation method thereof.
The objective of the invention is to be achieved through the following technical solutions:
A kind of low-melting point leadless borophosphate seal glass powder, it is that 60～70% parent glass and mass percent are that 30～40% fillers are formed by mass percent.Wherein, described parent glass mainly is the R of 10-20% by mass percent
2The B of O, 20-50%
2O
3, 30-50% P
2O
5, the MO of 5-25% and the Nb of O-20%
2O
5Form.R
2O is Li
2O, Na
2O, K
2A kind of or several mixing arbitrarily among the O; MO is a kind of or several mixing arbitrarily among MgO, CaO, SrO, BaO, the ZnO.
Further, described parent glass preferably is the R of 10-15% by mass percent
2The B of O, 30-45%
2O
3, 35-45% P
2O
5, the MO of 5-15% and the Nb of 0.5-15%
2O
5Form.
Further, also to contain mass percent be that 0.1～10% MnO or mass percent are 0.1～5% SnO to described parent glass.
Further, described filler is one or more combination of tindioxide, aluminium sesquioxide, quartz sand and aluminium titanates; Its coefficient of expansion is-120～60 * 10
-7/ ℃.
A kind of making method of above-mentioned low-melting point leadless borophosphate seal glass powder comprises the steps:
(1) mass percent is with R
2O 10～20%, P
2O
530～50%, MO 5～25%, B
2O
320～50% and Nb
2O
5The 0-20% thorough mixing is made compound; Wherein R is Li, Na, and a kind of or several mixing arbitrarily among the K, M is Mg, Ca, Sr, Ba, a kind of or several mixing arbitrarily among the Zn;
(2) compound is carried out melting 0.5～2 hour under 800～1200 ℃, after the glass metal cast molding, grind to form parent glass after being ground into parent glass powder or shrend;
(3) mass percent is the filler thorough mixing of 60～70% parent glass and 30～40%, makes low-melting point leadless borophosphate seal glass powder, and described filler is one or more the combination for tindioxide, aluminium sesquioxide, quartz sand and aluminium titanates.
The beneficial effect of the relative prior art of the present invention is: sealing glass powder of the present invention is not leaded, has reduced plumbous harm to environment and human body; Fusing point is low, and glass transformation temperature is 400～350 ℃, and softening temperature is 420～450 ℃, and sealing temperature is lower than 550 ℃, and chemical stability is good, is particularly suitable for the sealing-in of electron device; Thermal expansivity is controlled at 100～140 * 10
-7℃
-1Chemical stability is good, is widely used in the sealing-in between various glass, pottery and the metal.
Embodiment
Composition to the low-melting point leadless seal glass is described below: P
2O
5Be the glass-former of this glass, its optional compositing range is mass percent 30-50%, and its preferred compositing range is mass percent 35-45%.When its content less than 30% the time, then the glass instability is difficult for forming glass; And when its content was higher than 50%, then its water tolerance and weathering resistance were all relatively poor.
In glass is formed, B
2O
3It also is a kind of glass-former, it can reduce the glass smelting temperature, and it is too high to suppress thermal expansion coefficient of glass, can also increase the flowability in the glass smelting process, its optional compositing range is mass percent 20-50%, and its preferred compositing range is mass percent 30-45%.When its content less than 20% the time, can not reduce the softening temperature of glass fully, can not reach the effect of anticipation; And when its content greater than 50% the time, the easy devitrification of glass, softening temperature is too high.
Alkalimetal oxide R
2O can reduce the softening temperature of glass, improve the flowability of glass, make sealing-in fine and close more, its optional compositing range is mass percent 10-20%, but excessive alkalimetal oxide can improve the thermal expansivity of glass, the chemical stability variation that causes glass simultaneously, its preferable range are 1 mass percent 0-15%.
Bivalent metal oxide RO also is the necessary oxide component of this system glass, and its optional compositing range is mass percent 5-25%.Alkaline earth metal oxide can improve the stable of this system glass widely but alkaline earth metal oxide can not add too much, because add the softening temperature and the easy devitrification of glass that will obviously improve glass too much, the preferred compositing range of bivalent metal oxide is mass percent 5-15%.
Nb
2O
5Can repair the network structure of phosphate glass, improve the chemical stability of glass, its optional compositing range is mass percent 0-20%, makes the stability, glass variation too much easily but add, softening temperature raises, and its preferred compositing range is mass percent 0.5-15%.
In sum, low-melting point leadless borophosphate seal glass powder of the present invention comprises that mass percent is that 60～70% parent glass and mass percent are 30～40% fillers.
The parent glass of Unlead low-smelting point borophosphate seal glass powder of the present invention is formed and mass percent comprises R
2O 10-20%, B
2O
320-50%, P
2O
530-50%, MO 5-25% and Nb
2O
50-20%.R wherein
2O is Li
2O, Na
2O, K
2A kind of or several mixing arbitrarily among the O; MO is a kind of or several mixing arbitrarily among MgO, CaO, SrO, BaO, the ZnO; Preferred compositing range is molecular fraction R
2O 10-15%, B
2O
330-45%, P
2O
535-45%, MO 5-15% and Nb
2O
50.5-15%.In addition, also containing mass percent is that 0.1～10% MnO or mass percent are 0.1～5% SnO.
Filler is the one or more combination of tindioxide, aluminium sesquioxide, quartz sand and aluminium titanates.The coefficient of expansion of described filler is-120～60 * 10
-7/ ℃.
The making method of low-melting point leadless borophosphate seal glass powder of the present invention comprises the steps:
1. by mass percentage with R
2O 10～20%, P
2O
530～50%, MO 5～25%, B
2O
320～50% and Nb
2O
5The 0-20% thorough mixing is made compound; Wherein R is Li, Na, and a kind of or several mixing arbitrarily among the K, M is Mg, Ca, Sr, Ba, a kind of or several mixing arbitrarily among the Zn;
2. compound is carried out melting 0.5～2 hour under 800～1200 ℃, the glass metal cast molding grinds to form the parent glass powder after being ground into parent glass powder or shrend;
3. mass percent is the filler thorough mixing of 60～70% parent glass powder and 30～40%, makes low-melting point leadless borophosphate seal glass powder.
The low-melting point leadless boron phosphate glass that the present invention makes, owing to do not contain heavy metal oxide, as PbO, CdO, V
2O
5Deng, can reduce of the pollution of this type of material effectively, and preparation technology is simple to environment, realize large-scale industrial production easily.
Below in conjunction with specific embodiment the present invention is further described in detail, it is more obvious that purpose of the present invention and effect will become.
In above-mentioned parent glass compositing range, optimize embodiment 1-5 prescription, see Table 1.
Calculate the mass percent of raw material according to the mass percent of oxide compound in the prescription, the raw material that weighs total amount then and be about 50g carries out thorough mixing, and founds according to above-mentioned seal glass preparation method, at last the gained sample is tested.
Testing method is: the transition point Tg of glass, softening temperature Tf, thermalexpansioncoefficient record in high-temperature horizontal expands view, and sample size is 6 * 6 * 50mm
3The water resistance test of glass carries out in 90 ℃ distilled water, will wear into 10 * 10 * 2cm
3Sample be placed in 90 ℃ the distilled water water-bath 10 hours, find water-bath before and after sample quality almost do not change.
Parent glass grind into powder with obtaining mixes with quartz sand, and this mixed powder at 1000 ℃ of left and right sides sintering, is made the sealing glass powder that contains quartz sand filler, adopts mould to be pressed into 6 * 6 * 50mm
3Sample, be used for thermal expansivity test.Wherein when the mass percent of filler quartz sand was 20%, its thermal expansivity was 100 * 10
-7℃
-1When the mass percent of quartz sand was 30%, its thermal expansivity was 92 * 10
-7℃
-1The content of refractory materials in glass powder is high more, and its thermal expansivity is more little.
Table 1
Claims (6)
1. a low-melting point leadless borophosphate seal glass powder is characterized in that, it is that 60～70% parent glass and mass percent are that 30～40% fillers are formed by mass percent.Wherein, described parent glass mainly is the R of 10-20% by mass percent
2The B of O, 20-50%
2O
3, 30-50% P
2O
5, the MO of 5-25% and the Nb of 0-20%
2O
5Form.R
2O is Li
2O, Na
2O, K
2A kind of or several mixing arbitrarily among the O; MO is a kind of or several mixing arbitrarily among MgO, CaO, SrO, BaO, the ZnO.
2. low-melting point leadless borophosphate seal glass powder according to claim 1 is characterized in that, described parent glass preferably is the R of 10-15% by mass percent
2The B of O, 30-45%
2O
3, 35-45% P
2O
5, the MO of 5-15% and the Nb of 0.5-15%
2O
5Form.
3. low-melting point leadless borophosphate seal glass powder according to claim 1 is characterized in that, it is that 0.1～10% MnO or mass percent are 0.1～5% SnO that described parent glass also contains mass percent.
4. low-melting point leadless borophosphate seal glass powder according to claim 1 is characterized in that, described filler is one or more combination of tindioxide, aluminium sesquioxide, quartz sand and aluminium titanates.
5. low-melting point leadless borophosphate seal glass powder according to claim 4 is characterized in that, the coefficient of expansion of described filler is-120～60 * 10
-7/ ℃.
6. the making method of the described low-melting point leadless borophosphate seal glass powder of claim 1 is characterized in that, comprises the steps:
(1) by mass percentage with R
2O 10～20%, P
2O
530～50%, MO 5～25%, B
2O
320～50% and Nb
2O
5The 0-20% thorough mixing is made compound; Wherein R is Li, Na, and a kind of or several mixing arbitrarily among the K, M is Mg, Ca, Sr, Ba, a kind of or several mixing arbitrarily among the Zn.
(2) compound is carried out melting 0.5～2 hour under 800～1200 ℃, after the glass metal cast molding, grind to form parent glass after being ground into parent glass powder or shrend.
(3) mass percent is the filler thorough mixing of 60～70% parent glass and 30～40%, makes low-melting point leadless borophosphate seal glass powder, and described filler is one or more the combination for tindioxide, aluminium sesquioxide, quartz sand and aluminium titanates.
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|---|---|---|---|
| CNA2008100609902A CN101265024A (en) | 2008-04-08 | 2008-04-08 | Low-melting point leadless borophosphate seal glass powder and preparation method thereof |
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|---|---|---|---|
| CNA2008100609902A CN101265024A (en) | 2008-04-08 | 2008-04-08 | Low-melting point leadless borophosphate seal glass powder and preparation method thereof |
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Family
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| CN102584012A (en) * | 2012-02-10 | 2012-07-18 | 南通南京大学材料工程技术研究院 | Low-melting-point optical glass and preparation method thereof |
| CN103274601A (en) * | 2013-06-07 | 2013-09-04 | 福州大学 | Nb2O5-containing seal glass and its preparation and application methods |
| 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 |
| CN104081877A (en) * | 2012-01-30 | 2014-10-01 | 日立化成株式会社 | Electronic component, production method therefor, and sealing material paste used therein |
| CN104118990A (en) * | 2013-04-28 | 2014-10-29 | 京东方科技集团股份有限公司 | Lead-free glass powder, lead-free compound glass powder and application of lead-free glass powder and lead-free compound glass powder and display device |
| CN104520989A (en) * | 2012-07-30 | 2015-04-15 | 日立化成株式会社 | Electronic component, method for producing same, and sealing material paste used in same |
| CN108164144A (en) * | 2016-12-07 | 2018-06-15 | 辽宁法库陶瓷工程技术研究中心 | A kind of low temperature high expansion coefficient titanium alloy seal glass and its preparation method and application |
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| CN104081877A (en) * | 2012-01-30 | 2014-10-01 | 日立化成株式会社 | Electronic component, production method therefor, and sealing material paste used therein |
| CN102584012A (en) * | 2012-02-10 | 2012-07-18 | 南通南京大学材料工程技术研究院 | Low-melting-point optical glass and preparation method thereof |
| US9728341B2 (en) | 2012-07-30 | 2017-08-08 | Hitachi Chemical Company, Ltd. | Electronic component, method for producing same, and sealing material paste used in same |
| US10026923B2 (en) | 2012-07-30 | 2018-07-17 | Hitachi Chemical Company, Ltd. | Electronic component, method for producing same, and sealing material paste used in same |
| CN104520989B (en) * | 2012-07-30 | 2018-06-01 | 日立化成株式会社 | Electronic unit and its preparation method, and the sealing material paste wherein used |
| CN104520989A (en) * | 2012-07-30 | 2015-04-15 | 日立化成株式会社 | Electronic component, method for producing same, and sealing material paste used in same |
| CN104118990A (en) * | 2013-04-28 | 2014-10-29 | 京东方科技集团股份有限公司 | Lead-free glass powder, lead-free compound glass powder and application of lead-free glass powder and lead-free compound glass powder and display device |
| CN103274601B (en) * | 2013-06-07 | 2016-01-06 | 福州大学 | A kind of containing Nb 2o 5seal glass and preparation and application thereof |
| CN103274601A (en) * | 2013-06-07 | 2013-09-04 | 福州大学 | Nb2O5-containing seal glass and its preparation and application methods |
| 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 |
| CN108164144A (en) * | 2016-12-07 | 2018-06-15 | 辽宁法库陶瓷工程技术研究中心 | A kind of low temperature high expansion coefficient titanium alloy seal glass and its preparation method and application |
| CN111003945A (en) * | 2019-12-30 | 2020-04-14 | 西安赛尔电子材料科技有限公司 | Preparation method of sealing glass material and sealing process thereof |
| CN111268911A (en) * | 2020-02-21 | 2020-06-12 | Oppo广东移动通信有限公司 | Welding composition, shell assembly, preparation method and electronic equipment |
| CN111268911B (en) * | 2020-02-21 | 2022-06-07 | Oppo广东移动通信有限公司 | Welding composition, shell assembly, preparation method and electronic equipment |
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Open date: 20080917 |