CN100345786C - Low melting point, low expanding coefficient solder glass seal powder and its preparing method - Google Patents
Low melting point, low expanding coefficient solder glass seal powder and its preparing method Download PDFInfo
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- CN100345786C CN100345786C CNB2004100702034A CN200410070203A CN100345786C CN 100345786 C CN100345786 C CN 100345786C CN B2004100702034 A CNB2004100702034 A CN B2004100702034A CN 200410070203 A CN200410070203 A CN 200410070203A CN 100345786 C CN100345786 C CN 100345786C
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- melting point
- expansion
- low melting
- solder glass
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- 239000011521 glass Substances 0.000 title claims abstract description 71
- 239000000843 powder Substances 0.000 title claims abstract description 49
- 229910000679 solder Inorganic materials 0.000 title claims abstract description 32
- 238000002844 melting Methods 0.000 title claims abstract description 27
- 230000008018 melting Effects 0.000 title claims abstract description 26
- 238000000034 method Methods 0.000 title claims abstract description 14
- 238000002360 preparation method Methods 0.000 claims abstract description 35
- 238000007789 sealing Methods 0.000 claims abstract description 27
- NKZSPGSOXYXWQA-UHFFFAOYSA-N dioxido(oxo)titanium;lead(2+) Chemical compound [Pb+2].[O-][Ti]([O-])=O NKZSPGSOXYXWQA-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000011575 calcium Substances 0.000 claims abstract description 20
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 19
- 229910000174 eucryptite Inorganic materials 0.000 claims abstract description 15
- 239000000945 filler Substances 0.000 claims description 30
- 239000006132 parent glass Substances 0.000 claims description 28
- 238000001816 cooling Methods 0.000 claims description 15
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 11
- 239000002994 raw material Substances 0.000 claims description 11
- 238000005303 weighing Methods 0.000 claims description 11
- 238000000498 ball milling Methods 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 8
- 238000010298 pulverizing process Methods 0.000 claims description 8
- 229910052797 bismuth Inorganic materials 0.000 claims description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 6
- 239000004110 Zinc silicate Substances 0.000 claims description 5
- 239000004567 concrete Substances 0.000 claims description 5
- 238000009413 insulation Methods 0.000 claims description 5
- XSMMCTCMFDWXIX-UHFFFAOYSA-N zinc silicate Chemical compound [Zn+2].[O-][Si]([O-])=O XSMMCTCMFDWXIX-UHFFFAOYSA-N 0.000 claims description 5
- 235000019352 zinc silicate Nutrition 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 4
- 229910052845 zircon Inorganic materials 0.000 claims description 4
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 claims description 4
- 238000000465 moulding Methods 0.000 claims description 3
- 229910052697 platinum Inorganic materials 0.000 claims description 3
- -1 trichroite Chemical compound 0.000 claims description 3
- 238000007873 sieving Methods 0.000 claims description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract 2
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(iii) oxide Chemical compound O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 abstract 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract 1
- 229910052681 coesite Inorganic materials 0.000 abstract 1
- 229910052593 corundum Inorganic materials 0.000 abstract 1
- 229910052906 cristobalite Inorganic materials 0.000 abstract 1
- 239000000377 silicon dioxide Substances 0.000 abstract 1
- 235000012239 silicon dioxide Nutrition 0.000 abstract 1
- 229910052682 stishovite Inorganic materials 0.000 abstract 1
- 229910052905 tridymite Inorganic materials 0.000 abstract 1
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract 1
- 238000002425 crystallisation Methods 0.000 description 4
- 230000008025 crystallization Effects 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 229910002065 alloy metal Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000003566 sealing material Substances 0.000 description 2
- 239000005361 soda-lime glass Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical group [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 229910020617 PbO—B2O3—SiO2 Inorganic materials 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000004031 devitrification Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 239000006058 strengthened glass Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 230000003245 working effect Effects 0.000 description 1
Classifications
-
- 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
- C03C8/02—Frit compositions, i.e. in a powdered or comminuted form
- C03C8/10—Frit compositions, i.e. in a powdered or comminuted form containing lead
-
- 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
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/062—Glass compositions containing silica with less than 40% silica by weight
- C03C3/07—Glass compositions containing silica with less than 40% silica by weight containing lead
- C03C3/072—Glass compositions containing silica with less than 40% silica by weight containing lead containing boron
- C03C3/074—Glass compositions containing silica with less than 40% silica by weight containing lead containing boron containing zinc
- C03C3/0745—Glass compositions containing silica with less than 40% silica by weight containing lead containing boron containing zinc containing more than 50% lead oxide, by weight
-
- 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
- C03C8/02—Frit compositions, i.e. in a powdered or comminuted form
- C03C8/10—Frit compositions, i.e. in a powdered or comminuted form containing lead
- C03C8/12—Frit compositions, i.e. in a powdered or comminuted form containing lead containing titanium or zirconium
-
- 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
- C03C8/245—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 containing more than 50% lead oxide, by weight
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Glass Compositions (AREA)
Abstract
The present invention discloses solder glass sealing powder with low melting point and low expansion and a preparation method thereof. The solder glass sealing powder comprises (40 to 95)% basic glass and (5 to 60)% refractory body stuffing with low expansion, wherein the basic glass comprises the following components: (55 to 88)wt% of PbO, (2 to 15)wt% of B2O3, (0.5 to 8)wt% of Al2O3, (0.5 to 5)wt% of SiO2, (0.1 to 6)wt% of ZnO and (0.1 to 20)wt% of Bi2O3, and the refractory body stuffing with low expansion comprises lead titanate calcium or beta-eucryptite, etc. The preparation method of the solder glass sealing powder comprises the steps that firstly, the basic glass and the refractory body stuffing with low expansion are prepared, are then mixed according to the relation of the weight ratio of a formula and are made into glass sealing powder with low melting point and low expansion coefficient. The product of the present invention has the advantages of high stability, low softening point, easy sealing at low temperature, wide application range and good air tightness of sealing, and the preparation method has the advantages of simple technological process and energy saving.
Description
Technical field
The present invention relates to a kind of solder glass seal powder and preparation method thereof, especially a kind of composite glass seal powder that in parent glass, adds low bulk refractory body filler and preparation method thereof.
Background technology
At present, in fields such as electrooptics, electron device, senser element, according to the resistance to air loss requirement, need carry out sealing-in to various materials, comprise glass and metal, the sealing-in of materials such as glass and glass, glass and pottery, seal, sealing materials commonly used generally is lower than the glass powder of glass with fusing point, in order to improve its stopping property, require the coefficient of expansion of this glass powder lower.
Low melting glass system commonly used at present mainly contains: PbO-ZnO-B
2O
3, PbO-B
2O
3-SiO
2, PbO-V
2O
5-B
2O
3And B
2O
3-ZnO-SiO
2, etc. several systems, though this several systems fusing point is lower, the coefficient of expansion is all very big, generally all in (80-140) * 10
-7/ ℃ about, can not do the low-coefficient glass seal powder.The kind of present low bulk refractory body filler is a lot, and its coefficient of expansion is also different, and commonly used have a beta-eucryptite (86 * 10
-7/ ℃), lead titanate (53 * 10
-7/ ℃), trichroite (10-20 * 10
-7/ ℃), zircon (42 * 10
-7/ ℃) etc., the above coefficient of expansion is theoretical value, and its actual swelling capacity is limited, another filler lead titanate calcium (PbCaTiO
3) negative expansion very capable, it utilizes Ca
2+Ionic replacement part Pb
2+Ion and form a kind of Substitutional type solid solution, and its effect that reduces the coefficient of expansion is more obvious.
So, present glass powder generally is as parent glass with above-mentioned low melting glass, in this parent glass, dose above-mentioned any low bulk refractory body filler, like this, in theory both satisfied low-melting requirement, satisfied more low-expansion requirement again, but, in the utilization of reality, also have weak point, specifically be that reason is: the manufacturing process complexity, product stability is poor, the use processing condition often fluctuate, the coefficient of expansion is difficult to reach theoretical level.Poor with the products air tightness that this kind glass powder welds, gas leakage easily, the life-span is short.
Summary of the invention
Technical problem to be solved by this invention is to propose a kind of low melting point, low-expansion solder glass seal powder and preparation method thereof, make this solder glass seal powder have preferably stability, softening temperature is low, low intermediate temperature sealing is easy, good fluidity, applied widely, the sealing-in resistance to air loss is good, and process for making is simple.
Another technical problem to be solved by this invention is the preparation method who proposes a kind of lead titanate calcium, makes the lead titanate calcium density of manufacturing low, is easy to pulverize, and can better mix with other raw materials.
A technical problem more to be solved by this invention is the preparation method who proposes a kind of beta-eucryptite, makes the density of beta-eucryptite low, is easy to pulverize, and can better mix with other raw materials.
The present invention realizes by the following technical solutions:
A kind of low melting point, low-expansion solder glass seal powder comprise parent glass and low bulk refractory body filler, it is characterized in that, by weight, parent glass (40-95) %, low bulk refractory body filler (5-60) %.Wherein, described parent glass comprises following by weight the component of forming: PbO (55-88) %, B
2O
3(2-15) %, Al
2O
3(0.5-8) %, SiO
2(0.5-5) %, ZnO (0.1-6) %, Bi
2O
3(0.1-20) %; In order to increase the intermiscibility of filler and parent glass, Fe
2O
3(0-5) % or CuO (0-5) % or CaO (0-5) % or TiO
2(0-10) % or more than one arbitrary combination.
Described low bulk refractory body filler comprise lead titanate calcium or beta-eucryptite on this basis in last one or more the arbitrary combination that can also comprise lead titanate, trichroite, zircon, zinc silicate, ZnOw.
The preparation method of a kind of low melting point, low-expansion coefficient solder glass seal powder comprises the steps:
Step 1, preparation parent glass, concrete process is: the weight ratio according to prescription is carried out weighing, mixing with various raw materials, puts into platinum crucible, at 1000-1200 ℃ down after the insulation fusing in 5-40 minute, moulding, the ball milling back of sieving is standby;
Step 2, preparation low bulk refractory body filler;
Step 3, mix, make low melting point, low-expansion glass sealing powder according to the weight ratio relation of prescription components and the relevant component of adjusting with step 1,2 preparations.
In the present invention, used lead titanate calcium is Powdered, and the pressing mode that lead titanate calcium commonly used is taked in the preparation, make that the density of lead titanate calcium is bigger, be difficult for pulverizing, thereby, the present invention proposes a kind of preparation method of the lead titanate calcium that is easy to pulverize, and concrete steps are as follows:
Step 1, with raw material by stoichiometry weighing, mixing;
Step 2, put into stove, under 850-1000 ℃ temperature, fired 1-2 hour;
Step 3, taking-up cooling;
Step 4, put into stove again and under 1000-1200 ℃ of temperature, fired 1-2 hour;
Step 5, cooling;
Step 6, the filler pulverizing with baking, ball milling, sieve.
In the present invention, used beta-eucryptite is Powdered, and the present invention proposes a kind of preparation method of the beta-eucryptite that is easy to pulverize, and concrete steps are as follows:
Step 1, with raw material by stoichiometry weighing, mixing;
Step 2, put into stove, under 1100-1300 ℃ temperature, fired 3-5 hour;
Step 3, taking-up cooling;
Step 4, put into stove again and under 700-900 ℃ of temperature, fired 1-3 hour;
Step 5, cooling;
Step 6, the filler pulverizing with baking, ball milling, sieve.
The fusing point of solder glass seal powder provided by the invention is low, and the coefficient of expansion is low, good stability, and softening temperature is low, and low easily intermediate temperature sealing is applied widely, as can and cutting down the metal matched seal with DM-305, DM-308 molybdenum group glass in the electronic glass; Can with he-ne laser tube in the sealing-in of reflecting optics deielectric-coating optical window head and glass is arranged; Can with sealing-in, high-boron-silicon glass and low expanding alloy metal sealing-in, soda-lime glass and the expansion alloy metal sealing of solar energy heat collection pipe glass; Can carry out matched seal with pressure transmitter, simultaneously can also with all glass that conform to the coefficient of expansion in this temperature, pottery, metal sealing, the sealing-in resistance to air loss is good.
Preparation method's technological process of solder glass seal powder provided by the invention is simple, and the solder glass seal powder fusing point of manufacturing is lower, the coefficient of expansion is lower, meets the requirements.
In addition, adopt the produced lead titanate calcium of preparation method of lead titanate calcium provided by the invention and beta-eucryptite and beta-eucryptite to be easy to pulverize, not only technological process is simple, and saves the energy.
Embodiment
Below by specific embodiment technical scheme of the present invention is described in detail.
The invention discloses a kind of low melting point, low bulk solder glass seal powder and preparation method thereof, described solder glass seal powder comprises parent glass (40-95) %, low bulk refractory body filler (5-60) %.
Wherein, described parent glass comprises following by weight the component of forming: PbO 55-88%, B
2O
32-15%, Al
2O
30.5-8%, SiO
20.5-5%, ZnO 0.1-6%, Bi
2O
30.1-20%, described parent glass also comprise following by weight the component of forming: Fe
2O
3(0-5) % or CuO (0-5) % or CaO (0-5) % or TiO
2(0-10) % or more than one arbitrary combination.
Here, when PbO＞88%, degree of crystallization strengthens, and its coefficient of expansion increases; When PbO＜55%, softening temperature increases, and is mobile bad, realizes low sealing temperature difficulty.Best scope is at 60-85%.
Work as B
2O
3＞15% o'clock, softening temperature was caught height, low intermediate temperature sealing difficulty; Work as B
2O
3＜2%: the easy devitrification of glass fusion operation, its best scope is at 8-13%.
Work as Bi
2O
3＞20% o'clock, viscosity increased, and stability is bad, works as Bi
2O
3The vitreum scope that formed in＜0.1% o'clock narrows down, and its best scope is at 0.5-10%.
Work as Al
2O
3＞8%; The glass softening point height, low intermediate temperature sealing difficulty; Work as Al
2O
3＜0.5 o'clock, act on not obviously, its best scope is at 0.5-5%.
Work as SiO
2＞5% o'clock, the softening temperature height of glass, low intermediate temperature sealing difficulty; Work as SiO
2＜0.5% o'clock, the crystallization tendency of glass was strengthened, and its best scope is at 0.5-3%.
When ZnO＞6%, the crystallization of glass tendency is strengthened, the softening temperature height of glass, low intermediate temperature sealing difficulty; When ZnO＜0.1%, act on not obviously, its best scope is at 0.5-6%.
Parent glass in glass sealing powder provided by the invention can also be dosed Fe
2O
3(0-5) % or CuO (0-5) % or CaO (0-5) % or TiO
2(0-10) % or more than one arbitrary combination.
In the present invention, when when less demanding, including only parent glass to the coefficient of expansion.
Described low bulk refractory body filler comprises lead titanate calcium or beta-eucryptite, and, can also comprise one or more arbitrary combination of lead titanate, trichroite, zircon, zinc silicate, ZnOw.
Wherein, the preparation method of ZnOw, trichroite, zinc silicate is a lot, as:
A, zinc silicate (ZnSiO
3) preparation of filler: various raw materials are mixed the back 1440 ℃ of insulations 15 hours down by stoichiometric ratio.To be fired into that filler is pulverized, levigate 350 orders that sieve.
B, trichroite (MgO 2Al
2O
35SlO
2) preparation of filler: various raw materials are mixed the back behind 1550 ℃, 4 hours levigate mistake 100 mesh sieves of melt molding system thin slice by stoichiometric ratio, be incubated 12 hours down at 1000 ℃.Treat levigate mistake 350 mesh sieves after the trichroite crystallization.
The preparation of C, ZnOw (ZnOw) filler: get zinc powder and put into 1200 ℃ of insulations of High Temperature Furnaces Heating Apparatus generation in 30 minutes ZnOw.
In the present invention, described lead titanate calcium makes solder glass seal powder have low-expansion component for being mainly used in, and the method for its making is as follows: [PbCaTiO
3]: by stoichiometry weighing, mixing; Put into stove, under 850-1000 ℃ temperature, fired 1-2 hour; Take out cooling; Putting into stove again fired 1-2 hour under 1000-1200 ℃ of temperature; Cooling; With the filler pulverizing, the ball milling that bake, sieve.
In the present invention, described beta-eucryptite also is to be mainly used in to make solder glass seal powder have low-expansion component, and the method for its making is as follows: [Li
2OAl
2O
32SiO
2]: by stoichiometry weighing, mixing; Put into stove, under 1100-1300 ℃ temperature, fired 3-5 hour; Take out cooling; Putting into stove again fired 1-3 hour under 700-900 ℃ of temperature; Cooling; With the filler pulverizing, the ball milling that bake, sieve.
Below the present invention will be described in detail by specific embodiment.
Example one
In the present embodiment, described solder glass seal powder is by the following component of forming by weight:
Parent glass 61%, low bulk refractory body lead titanate calcium [PbCaTiO
3] 36%, ZnOw [ZnOw] 3%, wherein, parent glass comprises PbO 75.5%, B
2O
312.7%, Al
2O
35.0%, SiO
23.0%, ZnO 1.0%, Bi
2O
30.8%, TiO
22%.Parent glass has increased the content of ZnO, because the chemical property of ZnO is stable, weather resisteant is strong, the place, solder glass seal powder after parent glass has increased ZnO strengthens the adaptability of environment, the erosion of acid resistance, alkalescence can increase the work-ing life of carrying out the goods of sealing-in with seal powder provided by the invention.
The preparation method of described solder glass seal powder is:
Step 1, preparation parent glass, concrete process is: with PbO, B
2O
3, Al
2O
3, SiO
2, ZnO, Bi
2O
3, TiO
2Press above-mentioned weight ratio weighing, mixing, in platinum crucible, after 1000 ℃ insulation was melted in 40 minutes down, cooling, standby after ball milling sieves;
Step 2, preparation lead titanate calcium filler, its method does not repeat them here as previously mentioned;
Step 3, preparation ZnOw filler, its method does not repeat them here as previously mentioned;
Step 4, press parent glass 61%, low bulk refractory body lead titanate calcium [PbCaTiO
3] 36%, the weight ratio of ZnOw [ZnOw] 3%, the components of step 1,2,3 preparations are mixed, make low melting point, low-expansion glass sealing powder.
This low melting point, low-expansion glass sealing powder are carried out the physical properties test, and the room temperature of test records mean thermal expansion coefficients in the time of 250 ℃ be 49 * 10
-7/ ℃; Sealing temperature is 500 ℃, and the sealing-in time is 20 minutes.
Wherein, the measuring method of thermal expansivity is, glass sealing powder to be measured is made rod, and it is of a size of 100 * 10 * 10mm, measures with dilatometer.
The measuring method directly that flows is, take by weighing glass sealing powder 10 grams to be measured, cylindric (the about 100kg/cm ' of pressure) that be pressed into diameter and be 12.5mm places it on 50 * 50 soda-lime glass sheets, under 480 ℃, fired 50 minutes, usually sample can soften mobile, diffuse into button-type, with the diameter of button as measuring mobile yardstick.
Example two
In the present embodiment, described solder glass seal powder is by the following component of forming by weight:
Parent glass 57%: low bulk refractory body filler lead titanate calcium [PbCaTiO3] 42%, ZnOw [ZnOw] 1%, wherein, parent glass comprises the component of following weight ratio: PbO 75.5%, B
2O
312.7%, Al
2O
34.0%, SiO
23.0%, ZnO 2.0%, Bi
2O
30.8%, TiO
22%.
The preparation process of present embodiment is identical with embodiment one, and different is the amount difference of each component, does not repeat them here.
This low melting point, low-expansion glass sealing powder are carried out the physical properties test, and the room temperature of test records mean thermal expansion coefficients in the time of 300 ℃ be 33 * 10
-7/ ℃, sealing temperature is 550 ℃, the sealing-in time is 20 minutes.
Example three
In the present embodiment, described solder glass seal powder is by the following component of forming by weight:
Parent glass 58%; Beta-eucryptite [Li
2OAl
2O
32SiO
2] 42%.Wherein, parent glass comprises the component of following weight ratio: PbO 75.1%, B
2O
39.7%, SiO
21.8%, ZnO 2.4%, Bi
2O
37.3%, Fe
2O
31.3%, CuO 1.2%, TiO
21.2%.
Compare with embodiment two, increased Fe in the basic glass of present embodiment
2O
3, CuO, strengthened glass with by the wetting property of seal, sealing materials.
The preparation process of present embodiment is identical with embodiment one, and different is the amount difference of each component, does not repeat them here.
This low melting point, low-expansion glass sealing powder are carried out the physical properties test, and the room temperature of test records mean thermal expansion coefficients in the time of 300 ℃ be 33 * 10
-7/ ℃, sealing temperature is 550 ℃, the sealing-in time is 20 minutes.
It should be noted last that, above embodiment is only unrestricted in order to technical scheme of the present invention to be described, although the present invention is had been described in detail with reference to preferred embodiment, those of ordinary skill in the art is to be understood that, can make amendment or be equal to replacement technical scheme of the present invention, and not breaking away from the spirit and scope of technical solution of the present invention, it all should be encompassed in the middle of the claim scope of the present invention.
Claims (11)
1, a kind of low melting point, low-expansion solder glass seal powder comprise parent glass and low bulk refractory body filler, it is characterized in that, by weight, parent glass 40%-95%, low bulk refractory body filler 5%-60%;
Wherein, described parent glass comprises following by weight the component of forming: PbO 55%-88%, B
2O
32%-15%, Al
2O
30.5%-8%, SiO
20.5%-5%, ZnO 0.1%-6%, Bi
2O
30.1%-20%;
Described low bulk refractory body filler comprises lead titanate calcium or beta-eucryptite;
Described lead titanate calcium is made by following steps: raw material is pressed stoichiometry weighing, mixing; Put into stove, under 850 ℃-1000 ℃ temperature, fired 1-2 hour; Take out cooling; Putting into stove again fired 1-2 hour under 1000 ℃ of-1200 ℃ of temperature; Cooling; With the filler pulverizing, the ball milling that bake, sieve;
Described beta-eucryptite is made by following steps: raw material is pressed stoichiometry weighing, mixing; Put into stove, under 1100 ℃-1300 ℃ temperature, fired 3-5 hour; Take out cooling; Putting into stove again fired 1-3 hour under 700 ℃ of-900 ℃ of temperature; Cooling; With the filler pulverizing, the ball milling that bake, sieve.
2, low melting point according to claim 1, low-expansion solder glass seal powder is characterized in that, described parent glass also comprises following by weight the component of forming: Fe
2O
30-5% or CuO 0-5% or CaO 0-5% or TiO
20-10% or more than one arbitrary combination.
3, low melting point according to claim 1, low-expansion solder glass seal powder, it is characterized in that described low bulk refractory body filler also comprises one or more arbitrary combination of lead titanate, trichroite, zircon, zinc silicate, ZnOw.
4, low melting point according to claim 1, low-expansion solder glass seal powder is characterized in that, the weight ratio of described PbO is 65%-80%.
5, low melting point according to claim 1, low-expansion solder glass seal powder is characterized in that, described B
2O
3Weight ratio be 8%-13%.
6, low melting point according to claim 2, low-expansion solder glass seal powder is characterized in that, described Bi
2O
3Weight ratio at 0.5%-10%.
7, low melting point according to claim 1, low-expansion solder glass seal powder is characterized in that, described Al
2O
3Weight ratio at 0.5%-5%.
8, low melting point according to claim 1, low-expansion solder glass seal powder is characterized in that, described SiO
2Weight ratio at 0.5%-3%.
9, low melting point according to claim 1, low-expansion solder glass seal powder is characterized in that, the weight ratio of described ZnO is at 0.5%-6%.
10, the preparation method of the described a kind of low melting point of claim 1, low-expansion coefficient solder glass seal powder is characterized in that:
Step 1, preparation parent glass, concrete process is: the weight ratio according to prescription is carried out weighing, mixing with various raw materials, puts into platinum crucible, at 1000 ℃-1200 ℃ down after the insulation fusing in 5-40 minute, moulding, the ball milling back of sieving is standby;
Step 2, preparation low bulk refractory body filler;
Step 3, mix, make low melting point, low-expansion glass sealing powder according to the weight ratio relation of prescription components and the relevant component of adjusting with step 1,2 preparations.
11, a kind of preparation method of beta-eucryptite is characterized in that, may further comprise the steps:
Step 1, with raw material by stoichiometry weighing, mixing;
Step 2, put into stove, under 1100 ℃-1300 ℃ temperature, fired 3-5 hour;
Step 3, taking-up cooling;
Step 4, put into stove again and under 700 ℃ of-900 ℃ of temperature, fired 1-3 hour;
Step 5, cooling;
Step 6, the filler pulverizing with baking, ball milling, sieve.
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| CNB2004100702034A CN100345786C (en) | 2004-07-30 | 2004-07-30 | Low melting point, low expanding coefficient solder glass seal powder and its preparing method |
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| CN100345786C true CN100345786C (en) | 2007-10-31 |
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Assignee: BEIJNG ASAHI ELECTRONIC GLASS Co.,Ltd. Assignor: BOE TECHNOLOGY GROUP Co.,Ltd. Contract fulfillment period: 2009.5.18 to 2024.7.30 Contract record no.: 2009990000530 Denomination of invention: Low melting point, low expanding coefficient solder glass seal powder and its preparing method Granted publication date: 20071031 License type: Exclusive license Record date: 20090520 |
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