CN106495489A - One kind contains P2O5LED low temperature sealing glass - Google Patents
One kind contains P2O5LED low temperature sealing glass Download PDFInfo
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- CN106495489A CN106495489A CN201610965806.3A CN201610965806A CN106495489A CN 106495489 A CN106495489 A CN 106495489A CN 201610965806 A CN201610965806 A CN 201610965806A CN 106495489 A CN106495489 A CN 106495489A
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- temperature sealing
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- 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
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Abstract
The invention discloses a kind of contain P2O5LED low temperature sealing glass and its preparation and application, raw material consists of B2O3、Bi2O3、ZnO、P2O5, its mol ratio is 30 ~ 50：30~50：5~25：5~30.By P2O5Introduce PO4Tetrahedron, stable BO4Tetrahedron, reinforcing glass network stabilization, so as to improve its heat endurance, the material is placed in 1000 hours in 80 DEG C of hot water and can keep good stability.By introducing the B of high concentration2O3With Bi2O3, and its mol ratio is kept for 1：1, the coordinative role of the two is played, makes the softening range of the glass be reduced to 380 435 DEG C；The thermal coefficient of expansion of the adjustable glass of ZnO, and can further improve its sealing property.The glass of the present invention is applied to LED fluorescent powder sealing-in, electronic material and other low-temperature sealing fields.Preparing raw material of the present invention is simple, be easy to get, process stabilizing, low cost, process is simple, feasible, has reached practical and industrialized condition.
Description
Technical field
The invention belongs to seal glass field, and in particular to a kind of containing P2O5LED low temperature sealing glass and its prepare and make
Use method.
Background technology
Low temperature sealing glass（Sealing temperature<600 DEG C), due to its good heat resistance and chemical stability, high machinery is strong
Degree, is widely used in the various fields such as electric slurry, electrovacuum and microelectric technique, the energy, aerospace, automobile, such as luminous two
Pole pipe（LED）In fluorescent material sealing-in, the whether excellent actually used performance for directly resulting in battery of the performance of seal, sealing materials.Envelope
Connect glass and can also be used for the mutual sealing-in between glass, pottery, metal, semiconductor.But, research both at home and abroad at present is commonly used and is contained
The seal, sealing materials of Pb, this will be to environments.Due to Bi adjacent in the periodic table of elements with Pb, with similar physico-chemical
Property, so in the research of lead-free low-temperature glass, melting temperature sealing is low, coefficient of expansion adjustable range because having for bismuthate glass
Wide, price is low, obtain extensive concern the advantages of can substantially reduce environmental pollution.
Patent application 201310259302.6, discloses a kind of low-temperature lead-free glass dust and preparation method thereof, but the body
Another poisonous material Sb is introduced in system, does not solve environmental issue.And patent application 201210366375.0 is also disclosed
Lead-free glass material and preparation method thereof, by P2O5、K2O、Na2O、ZrO2、TiO2Composition design Deng raw material avoids ring
Border is polluted, but the softening range of the glass is 500 ~ 600 DEG C, it is difficult to meet low-temperature sealing especially electronic component low temperature
The requirement of Fast Sintering.At present part is used for the low temperature glass of fluorescent material sealing-in and also has that heat endurance is poor, and easily absorbing water causes
The problem of device aging.
Content of the invention
In order to solve the above problems, the invention provides a kind of contain P2O5LED low temperature sealing glass and its preparation and use
Method, by P2O5Introduce PO4Tetrahedron, using the stable BO of structural similarity4Tetrahedron, reinforcing glass network stabilization, so as to
Its heat endurance is improved, the material is placed in 1000 hours in 80 DEG C of hot water and can keep good stability.Introduce the B of high concentration2O3
With Bi2O3, and its mol ratio is kept for 1：1, the coordinative role of the two is played, is reduced to the softening range of the glass
380-435℃；The thermal coefficient of expansion of the adjustable glass of ZnO, and can further improve its sealing property.
The present invention is implemented by following technical solution：
One kind contains P2O5The raw material of LED low temperature sealing glass consist of B2O3、Bi2O3、ZnO、P2O5, its mol ratio is 30 ~ 50：
30~50：5~25：5~30.
The method for preparing LED low temperature sealing glass as above is comprised the following steps：
（1）Raw material is well mixed；Found through 880-930 DEG C, temperature retention time 1-4 hour；To the glass metal for melting, carry out
Chilling, obtains glass frit；Then, glass frit is crushed, is ground or ball milling, after sieving, obtain glass powder；
（2）Glass powder and binding agent, dispersant and solvent are mixed into slurry, ball milling dispersion in ball mill；Curtain coating
Shaping, spontaneously dries, is then cut into the idiosome of required form, makes seal glass.
The step（2）Binding agent be epoxy resin, methylcellulose, polyvinyl butyral resin, in polyvinyl alcohol
The mixture of one or more.
The step（2）Dispersant be fish oil, polyacrylic acid, polyvinyl alcohol, one or more in polyacrylamide
Mixture.
The step（2）Solvent be water, ethanol, isopropanol, n-butanol, toluene, dimethylbenzene, the one kind or several in acetone
The mixture that plants.
Seal glass is placed in treats sealing-in position, with the ramp of 1-5 DEG C/min in electric furnace, 300-400 DEG C of insulation
0.5-1 hours, then complete sealing-in with the ramp of 1-5 DEG C/min to 400-480 DEG C of isothermal holding 0.5-1 hour.
The remarkable advantage of the present invention is：
（1）By P2O5Introduce PO4Tetrahedron, using the stable BO of structural similarity4Tetrahedron, reinforcing glass network stabilization, from
And its heat endurance is improved, the material is placed in 1000 hours in 80 DEG C of hot water and can keep good stability；
（2）By introducing the B of high concentration2O3With Bi2O3, and its mol ratio is kept for 1：1, the coordinative role of the two is played, this is made
The softening range of glass is reduced to 380-435 DEG C；
（3）The thermal coefficient of expansion of the adjustable glass of ZnO, and can further improve its sealing property；
（4）The preparing raw material that the present invention is selected is cheap, and sources are various, process stabilizing.From corresponding oxide it is
Source material, makes them uniformly mix, and remains a high proportion of mixing and distribution state in fusing and subsequent heat treatment, prepares former
Material is simple, is easy to get, process stabilizing, low cost, process is simple, feasible, has reached practical and industrialized condition.
Description of the drawings
Fig. 1 is thermal dilatometry of the seal glass of embodiment 1-4 under the conditions of parallel laboratory test.
Fig. 2 is DSC curve of the seal glass of embodiment 1-4 under the conditions of parallel laboratory test.
Specific embodiment
One kind contains P2O5The raw material of LED low temperature sealing glass consist of B2O3、Bi2O3、ZnO、P2O5, its mol ratio be 30 ~
50：30~50：5~25：5~30.
Prepare2O5The method of LED low temperature sealing glass comprise the following steps：
（1）Raw material is well mixed；Found through 880-930 DEG C, temperature retention time 1-4 hour；To the glass metal for melting, carry out
Chilling, obtains glass frit；Then, glass frit is crushed, is ground or ball milling, after sieving, obtain glass powder；
（2）Glass powder and binding agent, dispersant and solvent are mixed into slurry, ball milling dispersion in ball mill；Curtain coating
Shaping, spontaneously dries, is then cut into the idiosome of required form, makes seal glass.
The step（2）Binding agent be epoxy resin, methylcellulose, polyvinyl butyral resin, in polyvinyl alcohol
The mixture of one or more.
The step（2）Dispersant be fish oil, polyacrylic acid, polyvinyl alcohol, one or more in polyacrylamide
Mixture.
The step（2）Solvent be water, ethanol, isopropanol, n-butanol, toluene, dimethylbenzene, the one kind or several in acetone
The mixture that plants.
Seal glass is placed in treats sealing-in position, with the ramp of 1-5 DEG C/min in electric furnace, 300 ~ 400 DEG C of insulations
0.5-1 hours, then complete sealing-in with the ramp of 1-5 DEG C/min to 400-480 DEG C of isothermal holding 0.5-1 hour.
Table 1 is the sealing glass composition table in embodiment 1-4（Mole percent）
Embodiment 1：The preparation and sealing-in of material
According to the proportioning of each component of embodiment 1 in table 1, a certain amount of analysis pure raw material is weighed（B2O3、Bi2O3、ZnO、P2O5）,
It is well mixed within 24 hours with planetary ball mill ball milling；Then powder is put into platinum crucible, is placed in the air gas of chamber type electric resistance furnace
In atmosphere, 900 DEG C are heated to 3 DEG C/min, be incubated 1 hour；Then, crucible is taken out, pours melt in deionized water chilling, done
The dry fragment for obtaining glass melt；Grinding, crosses 100 mesh sieves, obtains glass powder.By glass dust and polyvinyl alcohol, fish oil, ethanol
And toluene（Weight ratio is followed successively by 80%, 2%, 1%, 10%, 7%）Slurry is mixed into, ball milling dispersion in ball mill；It is cast into
Type, spontaneously dries, is then cut into the idiosome of required form；Idiosome is placed in and treats sealing-in position, with 2 DEG C/min's in electric furnace
Ramp, is incubated 1 hour at 350 DEG C, then with the ramp of 2 DEG C/min to 420 DEG C of isothermal holdings 1 hour, that is, completes
Sealing-in.The example is to preferably constitute.In the stainless steel grinding tool that melt after by insulation is poured into after preheating, Φ=10mm, d=25mm is obtained
Glass cylinder, tested with the rate of heat addition of 10 DEG C/min on NETZSCH DIL 402EP thermal dilatometers, obtain Glass Transition
Point and softening point.Fig. 1,2 show, add the P of 5% molar fraction2O5Seal glass glass transition point be 326 DEG C, softening point
For 385 DEG C, linear expansion coefficient is 1.41 × 10-5/K.Weight-loss ratio after placing 1000 hours in 80 DEG C of hot water is less than 0.001%.
Embodiment 2：The preparation and sealing-in of material
According to the proportioning of each component of embodiment 2 in table 1, a certain amount of analysis pure raw material is weighed（B2O3、Bi2O3、ZnO、P2O5）,
It is well mixed within 24 hours with planetary ball mill ball milling；Then powder is put into platinum crucible, is placed in the air gas of chamber type electric resistance furnace
In atmosphere, 900 DEG C are heated to 3 DEG C/min, be incubated 1 hour；Then, crucible is taken out, pours melt in deionized water chilling, done
The dry fragment for obtaining glass melt；Grinding, crosses 100 mesh sieves, obtains glass powder.By glass dust and methylcellulose, polyethylene
Alcohol, n-butanol and acetone（Weight ratio is followed successively by 82%, 2%, 2%, 8%, 6%）Slurry is mixed into, ball milling point in ball mill
Dissipate；Flow casting molding, spontaneously dries, is then cut into the idiosome of required form；Idiosome is placed in and treats sealing-in position, in electric furnace with
The ramp of 2 DEG C/min, is incubated 1 hour at 350 DEG C, then little to 420 DEG C of isothermal holdings 1 with the ramp of 2 DEG C/min
When, that is, complete sealing-in.The example is to preferably constitute.In the stainless steel grinding tool that melt after by insulation is poured into after preheating, acquisition Φ=
The glass cylinder of 10mm, d=25mm, is tested with the rate of heat addition of 10 DEG C/min on NETZSCH DIL 402EP thermal dilatometers,
Obtain glass transition point and softening point.Fig. 1,2 show, add the P of 10% molar fraction2O5Seal glass glass transition point
For 336 DEG C, softening point is 394 DEG C, and linear expansion coefficient is 1.33 × 10-5/K.Mistake after placing 1000 hours in 80 DEG C of hot water
Rate is less than 0.001% again.
Embodiment 3：The preparation and sealing-in of material
According to the proportioning of each component of embodiment 3 in table 1, a certain amount of analysis pure raw material is weighed（B2O3、Bi2O3、ZnO、P2O5）,
It is well mixed within 24 hours with planetary ball mill ball milling；Then powder is put into platinum crucible, is placed in the air gas of chamber type electric resistance furnace
In atmosphere, 900 DEG C are heated to 3 DEG C/min, be incubated 1 hour；Then, crucible is taken out, pours melt in deionized water chilling, done
The dry fragment for obtaining glass melt；Grinding, crosses 100 mesh sieves, obtains glass powder.By glass dust and epoxy resin, polyacrylamide
Amine, isopropanol and toluene（Weight ratio is followed successively by 84%, 1.5%, 0.5%, 9%, 5%）Slurry is mixed into, ball milling in ball mill
Dispersion；Flow casting molding, spontaneously dries, is then cut into the idiosome of required form；Idiosome is placed in and treats sealing-in position, in electric furnace
With the ramp of 2 DEG C/min, 1 hour is incubated at 350 DEG C, then with the ramp of 2 DEG C/min to 430 DEG C of isothermal holdings 1
Hour, that is, complete sealing-in.The example is to preferably constitute.In the stainless steel grinding tool that melt after by insulation is poured into after preheating, acquisition Φ=
The glass cylinder of 10mm, d=25mm, is tested with the rate of heat addition of 10 DEG C/min on NETZSCH DIL 402EP thermal dilatometers,
Obtain glass transition point and softening point.Fig. 1,2 show, add the P of 20% molar fraction2O5Seal glass glass transition point
For 347 DEG C, softening point is 407 DEG C, and linear expansion coefficient is 1.27 × 10-5/K.Mistake after placing 1000 hours in 80 DEG C of hot water
Rate is less than 0.001% again.
Embodiment 4：The preparation and sealing-in of material
According to the proportioning of each component of embodiment 4 in table 1, a certain amount of analysis pure raw material is weighed（B2O3、Bi2O3、ZnO、P2O5）,
It is well mixed within 24 hours with planetary ball mill ball milling；Then powder is put into platinum crucible, is placed in the air gas of chamber type electric resistance furnace
In atmosphere, 900 DEG C are heated to 3 DEG C/min, be incubated 1 hour；Then, crucible is taken out, pours melt in deionized water chilling, done
The dry fragment for obtaining glass melt；Grinding, crosses 100 mesh sieves, obtains glass powder.By glass dust and polyvinyl butyral resin, gather
Acrylic acid, isopropanol and acetone（Weight ratio is followed successively by 83%, 2%, 1%, 9%, 5%）Slurry is mixed into, ball milling in ball mill
Dispersion；Flow casting molding, spontaneously dries, is then cut into the idiosome of required form；Idiosome is placed in and treats sealing-in position, in electric furnace
With the ramp of 2 DEG C/min, 1 hour is incubated at 350 DEG C, then with the ramp of 2 DEG C/min to 450 DEG C of isothermal holdings 1
Hour, that is, complete sealing-in.The example is to preferably constitute.In the stainless steel grinding tool that melt after by insulation is poured into after preheating, acquisition Φ=
The glass cylinder of 10mm, d=25mm, is tested with the rate of heat addition of 10 DEG C/min on NETZSCH DIL 402EP thermal dilatometers,
Obtain glass transition point and softening point.Fig. 1,2 show, add the P of 25% molar fraction2O5Seal glass glass transition point
For 355 DEG C, softening temperature is 431 DEG C, and linear expansion coefficient is 1.23 × 10-5/K.After placing 1000 hours in 80 DEG C of hot water
Weight-loss ratio is about 0.001%.
The present invention is obtained by above-mentioned enforcement can be in low temperature enforcement sealing-in containing P2O5LED fluorescent powder seal glass.Which shows
The effect of work is embodied a concentrated reflection of.
The foregoing is only presently preferred embodiments of the present invention, all impartial changes that is done according to scope of the present invention patent with
Modification, should all belong to the covering scope of the present invention.
Claims (7)
1. a kind of containing P2O5LED low temperature sealing glass, it is characterised in that：Raw material consists of B2O3、Bi2O3、ZnO、P2O5, which rubs
You are than being 30 ~ 50：30~50：5~25：5~30.
2. according to claim 1 containing P2O5LED low temperature sealing glass, it is characterised in that：Raw material B2O3、Bi2O3、ZnO、
P2O5Mol ratio be 30 ~ 45：30~45：5~15：5~25.
3. one kind is prepared as claimed in claim 1 containing P2O5LED low temperature sealing glass method, it is characterised in that：Including with
Lower step：
（1）Raw material is well mixed；Found through 880-930 DEG C, temperature retention time 1-4 hour；To the glass metal for melting, carry out
Chilling, obtains glass frit；Then, glass frit is crushed, is ground or ball milling, after sieving, obtain glass powder；
（2）Glass powder and binding agent, dispersant and solvent are mixed into slurry, ball milling dispersion in ball mill；Curtain coating
Shaping, spontaneously dries, is then cut into the idiosome of required form, makes seal glass.
4. according to claim 3 containing P2O5LED low temperature sealing glass preparation method, it is characterised in that：The step
（2）Binding agent be epoxy resin, methylcellulose, polyvinyl butyral resin, the mixing of one or more in polyvinyl alcohol
Thing.
5. according to claim 3 containing P2O5LED low temperature sealing glass preparation method, it is characterised in that：The step
（2）Dispersant be fish oil, polyacrylic acid, polyvinyl alcohol, the mixture of one or more in polyacrylamide.
6. according to claim 3 containing P2O5LED low temperature sealing glass preparation method, it is characterised in that：The step
（2）Solvent be water, ethanol, isopropanol, n-butanol, toluene, dimethylbenzene, the mixture of one or more in acetone.
7. a kind of as claimed in claim 1 containing P2O5LED low temperature sealing glass using method, it is characterised in that：By sealing-in
Glass is placed in treats sealing-in position, with the ramp of 1-5 DEG C/min in electric furnace, 300-400 DEG C of insulation 0.5-1 hour, then
With the ramp of 1-5 DEG C/min to 400-480 DEG C of isothermal holding 0.5-1 hour, that is, complete sealing-in.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610965806.3A CN106495489B (en) | 2016-11-01 | 2016-11-01 | One kind containing P2O5LED low temperature sealing glass |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610965806.3A CN106495489B (en) | 2016-11-01 | 2016-11-01 | One kind containing P2O5LED low temperature sealing glass |
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| Publication Number | Publication Date |
|---|---|
| CN106495489A true CN106495489A (en) | 2017-03-15 |
| CN106495489B CN106495489B (en) | 2019-03-12 |
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ID=58321955
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610965806.3A Expired - Fee Related CN106495489B (en) | 2016-11-01 | 2016-11-01 | One kind containing P2O5LED low temperature sealing glass |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107043216A (en) * | 2017-04-25 | 2017-08-15 | 福州大学 | SiO2Modified low temperature sealing glass and its preparation and application method |
| CN107043215A (en) * | 2017-04-25 | 2017-08-15 | 福州大学 | A kind of low temperature sealing glass of lanthana modification and its preparation and application method |
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| CN102875020A (en) * | 2012-09-27 | 2013-01-16 | 广东风华高新科技股份有限公司 | Lead-free glass material and preparation method thereof |
| CN103553345A (en) * | 2013-09-22 | 2014-02-05 | 江苏瑞德新能源科技有限公司 | Phosphate glass powder for solar cell silver paste |
| CN103739201A (en) * | 2013-12-16 | 2014-04-23 | 福州大学 | Medium-temperature SOFC sealing microcrystalline glass, and preparation method and application method thereof |
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2016
- 2016-11-01 CN CN201610965806.3A patent/CN106495489B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007297266A (en) * | 2006-04-03 | 2007-11-15 | Nippon Electric Glass Co Ltd | Amorphous glass tablet and tablet-integrated evacuation tube |
| CN101973708A (en) * | 2010-10-20 | 2011-02-16 | 北京印刷学院 | Phosphorus-bismuth non-lead low-melting point glass |
| CN102875020A (en) * | 2012-09-27 | 2013-01-16 | 广东风华高新科技股份有限公司 | Lead-free glass material and preparation method thereof |
| CN103553345A (en) * | 2013-09-22 | 2014-02-05 | 江苏瑞德新能源科技有限公司 | Phosphate glass powder for solar cell silver paste |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107043216A (en) * | 2017-04-25 | 2017-08-15 | 福州大学 | SiO2Modified low temperature sealing glass and its preparation and application method |
| CN107043215A (en) * | 2017-04-25 | 2017-08-15 | 福州大学 | A kind of low temperature sealing glass of lanthana modification and its preparation and application method |
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| CN106495489B (en) | 2019-03-12 |
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