CN101456674A - Rare-earth doped leadless and low-melting point sealing glass and its preparation method - Google Patents
Rare-earth doped leadless and low-melting point sealing glass and its preparation method Download PDFInfo
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- CN101456674A CN101456674A CNA2009100604053A CN200910060405A CN101456674A CN 101456674 A CN101456674 A CN 101456674A CN A2009100604053 A CNA2009100604053 A CN A2009100604053A CN 200910060405 A CN200910060405 A CN 200910060405A CN 101456674 A CN101456674 A CN 101456674A
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Abstract
The invention relates to a method for preparing rare earth doped lead-free sealing glass with low melting point, which comprises the following steps: based on raw materials adopted by a Bi2O3-ZnO-B2O3 glass system, adding proper amount of rare earth oxide into the raw materials, and mixing, melting, annealing, grinding and sieving the mixture to obtain the rare earth doped lead-free sealing glass with the low melting point. The sealing glass comprises the following main components by weight portion: 65.22 to 85.22 portions of bismuth oxide, 4.63 to 11.78 portions of boric acid, 5.76 to 10.76 portions of zinc oxide, 0.80 to 2.80 portions of copper oxide, 0.42 to 2.42 portions of cobalt oxide, 3.32 to 8.47 portions of barium carbonate, 0.4 to 1.8 portions of aluminum oxide, and 0.1 to 6.0 portions of rare earth oxide. The method solves the problems that the sealing glass with the low melting point has low sealing temperature, high sealing strength, stable glass structure and the like under lead-free conditions, and has the advantages of simple process, practicability and reliability; and the prepared rare earth doped lead-free sealing glass with the low melting point is particularly suitable for sealing and closing of stainless steel materials, electrons and electric appliances.
Description
Technical field
The present invention relates to glass material, particularly a kind of prescription of rare-earth doped leadless and low-melting point sealing glass and preparation, this material is specially adapted to the sealing-in of stainless steel, electronics, appliance device and airtight.
Background technology
Low-melting point sealing glass is meant the middle layer glass that glass, pottery, metal and matrix material etc. are sealed up each other, and it refers to that fusing point significantly is lower than the seal glass of simple glass.Along with development of modern science and technology, especially the progress at full speed in fields such as vacuum electronic technology, microelectronics, laser and infrared technique, electric light source and high energy physics and aerospace industry, the energy, automotive industry, chemical industry, industrial test, the precise treatment degree of miniaturization of devices, structural element improves constantly, the kind of electronic devices and components is more and more, shape of products also becomes increasingly complex, they are more and more higher to the requirement of the resistance to air loss of sealing-in goods and reliability, and are also more and more higher to the requirement of Working environment.Seal, sealing materials is of a great variety, roughly can be divided into organic materials, inorganic materials and metallic substance three classes on chemical ingredients.Wherein, organic materials comprises organic polymer materials such as Resins, epoxy, organo-silicone rubber, silicone resin, is mainly used in low intermediate temperature sealing; Inorganic materials mainly comprises glass, enamel etc., mainly is applicable to high temperature, resistance to air loss sealing-in; Metallic substance mainly is scolders such as Pb-Sn scolding tin, mainly is applicable to the welding in the electronic product.Glass-like materials is a kind of as seal, sealing materials, because it is being better than organic polymer material aspect resistance to air loss and the thermotolerance, be better than metallic substance again aspect electrical insulation capability, thereby seal glass has its special advantages.
Being of wide application of packaged glass, specifically, it mainly contains the application of following three aspects: 1. as packaged material, as shell encapsulation, coating encapsulation, passivation film etc.; 2. pure seal, sealing materials is used for the mutual sealing-in between pottery, metal and the glass material; 3. add material, as the weighting agent of electronic material to improve the performance of electronic component.Wherein, the application demand of second aspect is the most outstanding.
As seal, sealing materials, glass can specifically be used for: 1. ceramic to ceramic sealing-in, as the magnetic gap of unicircuit, high-density magnetic head, silicon, base, transmitter, MEMS (micro electro mechanical system) (MEMS, Micro-Electro-Mechanical Systems), Micro-Opto-Electro-Mechanical Systems (MOEMS) etc.; 2. metal-metal sealing-in is as electrical heating element, household electrical appliance etc.; 3. glass-glass sealing-in is as panel of color picture tube awl etc.; 4. glass-to-metal seal is as to the demanding electron tube of insulativity, reliability and resistance to air loss, aerospace relay, multi-chip module (McM) etc.
Now the development trend of low-melting point sealing glass mainly contains three: unleaded, sealing-in low temperatureization and micritization.
That forms is unleaded: the plumbiferous glass system of big multi-field employing both at home and abroad at present, PbO content is all very high in most of commercial seal glass, have in addition up to 70%.Along with the enhancing of continuous progress in science and technology and environmental consciousness, plumbous to the mankind murder by poisoning and to the pollution of environment, more and more cause the extensive concern of each side.The soot emissions that contain lead and oxide compound thereof are condensed into micronic dust in air, can swim in the atmosphere for a long time.Can drop to ground greater than 10 microns grits, polluted source and soil.Equally, lead glass also can pollute soil and underground water after discarding.Barium crown sealed glass proposes with respect to leaded seal glass, is a kind of novel environment friendly seal, sealing materials that market potential is arranged very much, and most of performances all can be compared with leaded seal glass even be more superior, and can obviously reduce environmental pollution.
Sealing-in low temperatureization: the sealing temperature of seal glass is the key process parameter and the index of this class material, and the reduction of seal glass sealing temperature helps opto-electronic device and microelectronic device optimization of preparation.Low intermediate temperature sealing can prevent the distortion and the oxidation of metal parts, and simultaneously required sealing temperature is too high, and the flowability of glass melt in the time of will being unfavorable for sealing-in makes vitreum can not be covered with whole sealed space, thereby influences the resistance to air loss of closure.The inner getter that uses of part closure keeps vacuum tightness, and getter needs certain activationary temperature, if but sealing temperature exceed too much, getter will lose efficacy.Based on above reason, must reduce sealing temperature.But the reduction of low temperature seal glass sealing temperature can cause the sealing layer chemical stability to reduce and sealing strength descends, and introduces in glass therefore that whisker strengthens or nanocrystalline modification improves chemical stability and sealing strength has important researching value.
Micritization: the advantage that adopts the crystallinity seal glass: 1. can separate out the kind and the quantity of crystalline phase, thereby regulate the coefficient of expansion and expansion characteristics greatly by adjusting, make it with by the matched coefficients of thermal expansion of closure; 2. in the seal glass after the crystallization, the small crystal of many densifications is surrounded by thin glassy phase, and the general crystallization phases coefficient of expansion is low, thereby glassy phase is subjected to stress, and crystallization phases is subjected to tension stress.And the intensity of fine and close crystallization phases is higher than glassy phase usually, and total intensity of sealing layer is improved like this; 3. in a single day glassy phase can play the effect of stress relaxation, even occur tiny crack in the glass coating, just is passivated and extend to the crystallization phases interface, suppressed the development of tiny crack, thereby improves physical strength and heat-shock resistance; 4. electrical insulation capability is good, and its resistance is worn intensity and is higher than common non-crystalline type seal glass; 5. stable chemical performance has corrosion resisting property preferably, can stand atmospheric erosion for a long time.
The preparation method of existing leaded low-melting point sealing glass is: according to the component design that requires of low melting glass, wherein the main component of glass is PbO, B
2O
3, ZnO, Al
2O
3, SiO
2, K
2O, Bi
2O
3Deng; Carry out weighing by prescription, and mix; Melt in platinum crucible, the temperature of fusion scope is 1000-1200 ℃; The glass metal that fusing is good is cast in the mould, is shaped as certain glass block; With block frit fragmentation, grind to form finely powdered, promptly obtain low-melting point sealing glass.The sealing temperature of prescription different glass is also inequality.
Comprehensively commercial both at home and abroad low-melting point sealing glass can find, most low-melting point sealing glass contains very high PbO (wt%〉50%).The use meeting of plumbous oxide causes very large harm to environment and human body.The research and development leadless and low-melting point sealing glass is imperative.
Summary of the invention
Technical problem to be solved by this invention is: at low-melting point sealing glass unleaded requirement and the not high shortcoming of existing low-melting point sealing glass stability, provide a kind of prescription and preparation method of rare-earth doped leadless and low-melting point sealing glass.
The present invention solves its technical problem and adopts following technical scheme:
Rare-earth doped leadless and low-melting point sealing glass material provided by the invention is with Bi
2O
3-ZnO-B
2O
3Glass system is the basis, mixes the proper amount of rare-earth oxide compound, after their mixing, fusing, annealing, grinding and screening, obtain rare-earth doped leadless and low-melting point sealing glass, this seal glass mainly consists of by weight: 65.22～85.22 parts of bismuth oxides, 4.63～11.78 parts of boric acid, 5.76～10.76 parts in zinc oxide, 0.80～2.80 part of cupric oxide, 0.42～2.42 part of cobalt oxide, 3.32～8.47 parts of barium carbonates, 0.4～1.8 part in aluminum oxide, 0.1～6.0 part of rare earth oxide.
Above-mentioned rare-earth doped leadless and low-melting point sealing glass material provided by the invention is made by the method that comprises batching, mixing, fusing, annealing, grinding and screening step.
Above-mentioned rare-earth doped leadless and low-melting point sealing glass material provided by the invention is characterized in: contain a small amount of, B in glass
2O
3, Al
2O
3, SiO
2Deng glass-former, be used to promote the formation of glass and keep the stable of structure; In glass, add a large amount of Bi
2O
3, be used to reduce the transition temperature (T of glass
g), softening temperature (T
f), temperature of fusion (T
m), in addition, Bi
2O
3Can with B
2O
3, Al
2O
3, SiO
2Form the basic structure of glass together Deng glass-former.In the structure of glass and on, Bi
2O
3The same with PbO, therefore, the Bi in glass
2O
3When content was higher, glass just had the low melting point performance.CuO and Co
2O
3Use, mainly be the color of regulating glass.The particular electrical minor structure of rare earth element makes them show unique physical properties in glass structure.With rare earth oxide CeO
2, Y
2O
3, La
2O
3, Eu
2O
3Or Nd
2O
3Substitute the Bi of part
2O
3, the flowability of glass is increased, chemical stability strengthens, and the thermal expansivity scope of glass is broad more.Therefore, compare, mainly contain following unusual effect with existing low-melting point sealing glass:
One. cancel the use of PbO, made it environmental protection more.
They are two years old. use B
2O
3, Al
2O
3, SiO
2Deng glass-former, kept the formation ability of glass, enlarge the one-tenth glass scope of this system glass, the crystallization of feed glass.
They are three years old. by mixing the rare earth oxide of suitable kind, quantity, the flowability that can regulate glass, chemical stability and thermal expansivity.Resulting leadless and low-melting point sealing glass good fluidity, sealing temperature wide ranges (350 ℃～650 ℃), chemical stability are good, thermal expansivity in very large range can adjust (9.8～12.4 * 10
-6), therefore, adaptability is strong.Be specially adapted to the sealing-in of stainless material, electronics, electrical equipment and airtight.
They are four years old. and technology is simple, practical and reliable.
In a word, the invention solves under the unleaded condition problem such as the sealing temperature of low-melting point sealing glass is low, sealing strength is high, glass structure is stable.Simultaneously, preparation method provided by the invention, not only technology is simple, practical and reliable, and can prepare have good quality, performance and work-ing life mix the rare earth low-melting point sealing glass, this glass is specially adapted to the sealing-in of stainless material, electronics, electrical equipment and airtight.
Embodiment
The present invention is with Bi
2O
3-ZnO-B
2O
3Glass system is the basis, mix the proper amount of rare-earth oxide compound, after their mixing, fusing, annealing, grinding and sieve, obtain rare-earth doped leadless and low-melting point sealing glass, this seal glass is (1 part can be 1 gram, 10 grams, 100 grams, 1000 grams etc.) by weight, carry out charge calculation, and obtain charger sheet; The prescription of leadless and low-melting point sealing glass material involved in the present invention sees Table 1.This seal glass mainly consists of: 65.22～85.22 parts of bismuth oxides, 4.63～11.78 parts of boric acid, 5.76～10.76 parts in zinc oxide, 0.80～2.80 part of cupric oxide, 0.42～2.42 part of cobalt oxide, 3.32～8.47 parts of barium carbonates, 0.4～1.8 part in aluminum oxide, 0.1～6.0 part of rare earth oxide.
Described rare-earth doped leadless and low-melting point sealing glass, it forms the raw material that also has following weight parts: 0.1～1.50 part of Vanadium Pentoxide in FLAKES, 0.1～1.4 part of silicon-dioxide.
Described rare-earth doped leadless and low-melting point sealing glass, can make by the raw material of following weight parts: 65.22 parts of bismuth oxides, 4.63 parts of boric acid, 10.76 parts in zinc oxide, 2.80 parts of cupric oxide, 2.42 parts of cobalt oxides, 3.32 parts of barium carbonates, 0.4 part in aluminum oxide, 0.1 part of Vanadium Pentoxide in FLAKES, 0.1 part of silicon-dioxide, 0.1 part of rare earth oxide.
Described rare-earth doped leadless and low-melting point sealing glass, can make by the raw material of following weight parts: 85.22 parts of bismuth oxides, 11.78 parts of boric acid, 5.76 parts in zinc oxide, 0.80 part of cupric oxide, 0.42 part of cobalt oxide, 8.47 parts of barium carbonates, 1.8 parts in aluminum oxide, 1.50 parts of Vanadium Pentoxide in FLAKESs, silica 1 .4 part, 6.0 parts of rare earth oxides.
Described rare-earth doped leadless and low-melting point sealing glass, can make by the raw material of following weight parts: 75.22 parts of bismuth oxides, 8.21 parts of boric acid, 8.26 parts in zinc oxide, 1.80 parts of cupric oxide, 1.42 parts of cobalt oxides, 5.90 parts of barium carbonates, 1.2 parts in aluminum oxide, 0.8 part of Vanadium Pentoxide in FLAKES, 0.75 part of silicon-dioxide, 3.05 parts of rare earth oxides.
Described rare earth oxide can be one or more in cerium oxide, yttrium oxide, lanthanum trioxide, europium sesquioxide, the niobium oxides.
Above-mentioned rare leadless and low-melting point sealing glass material of going up of mixing provided by the invention, make by the method that comprises batching, mixing, fusing, annealing, grinding and screening step:
(1) batching: take by weighing raw material by forming proportioning.
(2) mix: the raw material that takes by weighing is put into shredder mix, grind, till mixing, obtain admixtion.In mixing process, the raw material that takes by weighing was put into grinding machine for grinding 0.5～1 hour, directly only mix.
(3) fusing: admixtion is put into platinum crucible, and the platinum crucible that admixtion will be housed is then put into resistance furnace and heated, and the process that is progressively risen to 1100～1200 ℃ by room temperature is: from room temperature to 500 ℃, temperature rise rate is≤2 ℃/min; 500 ℃ to 1200 ℃, temperature rise rate is≤2 ℃/min, and is incubated 2 hours, and admixtion is fully melted, and obtains melting good glass metal.
(4) annealing: glass metal is cast in by in the good mould of preheating in advance, makes it to become block glass, then glass is annealed the block glass that obtains annealing.Annealing process is: (350 ℃～400 ℃) insulation is 0.5 hour in annealing holding temperature scope, and the temperature that reduces process furnace then is lower than 80 ℃ until furnace temperature, and the rate of temperature fall of process furnace is controlled at≤1 ℃/min.
(5) grind: the good block glass fragmentation of will annealing earlier, place it in then and grind in the agate shredder, the time of grinding is 4～10 hours.
(6) screening: glass after will grinding is through sieving, and according to the different demands of product, (300 orders, 500 orders, 800 orders etc. can obtain rare-earth doped leadless and low-melting point sealing glass to the screen cloth by different meshes respectively.
Seal glass provided by the invention is used for the sealing-in of stainless material, electronics or electrical equipment and airtight.
The invention will be further described below in conjunction with embodiment, but do not limit the present invention.
Example one:
The one, prepares burden according to the prescription that table 1 provides, and chooses the numerical value of various raw material oxide compounds in each oxide content scope that table 1 provides.Seal glass raw material in the example one by weight, 1 part can be 1 the gram, 10 the gram, 100 the gram, 1000 the gram etc., obtain charger sheet, see attached list 2.
The 2nd, is that raw material carries out weighing according to charger sheet and corresponding measure unit with powder bismuth oxide, aluminum oxide, boric acid, silicon-dioxide, cupric oxide, cobalt oxide, Vanadium Pentoxide in FLAKES, zinc oxide, barium carbonate, cerium oxide, niobium oxides etc.With they together shredder grind, mix.
The 3rd. after each oxide compound of take by weighing put into shredder, open shredder and mixed, grind 0.5～1 hour, till each oxide compound mixes.The admixtion that mixes is put into platinum crucible.
The 4th. the platinum crucible that admixtion will be housed is put into resistance furnace and is heated.The process that is progressively risen to 1200 ℃ by room temperature is: from room temperature to 600 ℃, temperature rise rate is 5 ℃/min; 600 ℃ to 1200 ℃ temperature rise rate≤2 ℃/min, and, glass batch is fully melted 1200 ℃ of insulations 2 hours.Utilize platinum pincers that platinum crucible is pressed from both sides out from process furnace, the method for utilizing cast is cast in glass metal by in the good mould of preheating in advance, makes it to become block glass, then glass is annealed.Annealing schedule is: (350 ℃) insulation is 0.5 hour under the annealing holding temperature, and the temperature that reduces process furnace then is lower than 80 ℃ until furnace temperature, and the rate of temperature fall of process furnace is controlled at≤1 ℃/min.Finally obtained having the black glass of metalluster.
The 5th. the good block glass fragmentation of will annealing, in the agate shredder, to grind, the time of grinding is 4～10 hours.According to the different demands of product, by the screen cloth (300 orders, 500 orders, 800 orders etc.) of different meshes, promptly obtained the leadless and low-melting point sealing glass material respectively.
The 6th. to the performance test that resulting low-melting point sealing glass is correlated with, obtain the performances such as thermal expansivity, transition temperature, softening temperature and sealing temperature scope of glass, see Table 3.
Example two:
The one, prepares burden according to the prescription that table 1 provides, in each oxide content scope that table 1 provides, choose the numerical value of various raw material oxide compounds, the seal glass raw material in the example two by weight, 1 part can be 1 the gram, 10 the gram, 100 the gram, 1000 the gram etc., obtain charger sheet, see attached list 2.
The 2nd, is that raw material carries out weighing according to charger sheet and corresponding measure unit with powder bismuth oxide, aluminum oxide, boric acid, silicon-dioxide, cupric oxide, cobalt oxide, zinc oxide, barium carbonate, cerium oxide, yttrium oxide, lanthanum trioxide, europium sesquioxide, niobium oxides etc.With they together shredder grind, mix.
The 3rd. the 3rd step is with example one.
The 4th. the platinum crucible that admixtion will be housed is put into resistance furnace and is heated.The process that is progressively risen to 1150 ℃ by room temperature is: from room temperature to 500 ℃, temperature rise rate is 5 ℃/min; 500 ℃ to 1150 ℃ temperature rise rate≤2 ℃/min, and, glass batch is fully melted 1150 ℃ of insulations 2 hours.Utilize platinum pincers that platinum crucible is pressed from both sides out from process furnace, the method for utilizing cast is cast in glass metal by in the good mould of preheating in advance, makes it to become block glass, then glass is annealed.Annealing schedule is: (380 ℃) insulation is 0.5 hour under the annealing holding temperature, and the temperature that reduces process furnace then is lower than 80 ℃ until furnace temperature, and the rate of temperature fall of process furnace is controlled at≤1 ℃/min.Finally obtained having the black glass of metalluster.
The 5th. the good block glass fragmentation of will annealing, in the agate shredder, to grind, the time of grinding is 4～10 hours.According to the different demands of product, by the screen cloth (300 orders, 500 orders, 800 orders, 1200 orders etc.) of different meshes, promptly obtained the leadless and low-melting point sealing glass material respectively.In addition, can in glass powder, dose turps and Terpineol 350, it is prepared into the ointment of certain viscosity, and in the container of the sealing of packing into, in order to using.
The 6th. the 3rd step is with example one.
Example three:
The one, prepares burden according to the prescription that table 1 provides, and chooses the numerical value of various raw material oxide compounds in each oxide content scope that table 1 provides.Seal glass raw material in the example three by weight, 1 part can be 1 the gram, 10 the gram, 100 the gram, 1000 the gram etc., obtain charger sheet, see attached list 2.
The 2nd, is that raw material carries out weighing according to charger sheet and corresponding measure unit with powder bismuth oxide, aluminum oxide, boric acid, silicon-dioxide, cupric oxide, cobalt oxide, Vanadium Pentoxide in FLAKES, zinc oxide, barium carbonate, cerium oxide etc.With they together shredder grind, mix.
The 3rd. the 3rd step is with example one.
The 4th. the platinum crucible that admixtion will be housed is put into resistance furnace and is heated.The process that is progressively risen to 1100 ℃ by room temperature is: from room temperature to 500 ℃, temperature rise rate is 5 ℃/min; 500 ℃ to 1150 ℃ temperature rise rate≤2 ℃/min, and, glass batch is fully melted 1100 ℃ of insulations 2 hours.Utilize platinum pincers that platinum crucible is pressed from both sides out from process furnace, the method for utilizing cast is cast in glass metal by in the good mould of preheating in advance, makes it to become block glass, then glass is annealed.Annealing schedule is: (380 ℃) insulation is 0.5 hour under the annealing holding temperature, and the temperature that reduces process furnace then is lower than 80 ℃ until furnace temperature, and the rate of temperature fall of process furnace is controlled at≤1 ℃/min.Finally obtained having the black glass of metalluster.
Step is with example one later on.
Example four:
The one, prepares burden according to the prescription that table 1 provides, and chooses the numerical value of various raw material oxide compounds in each oxide content scope that table 1 provides.Seal glass raw material in the example four by weight, 1 part can be 1 the gram, 10 the gram, 100 the gram, 1000 the gram etc., obtain charger sheet, see attached list 2.
The 2nd, is that raw material carries out weighing according to charger sheet and corresponding measure unit with powder bismuth oxide, aluminum oxide, boric acid, silicon-dioxide, cupric oxide, cobalt oxide, Vanadium Pentoxide in FLAKES, zinc oxide, barium carbonate, cerium oxide, yttrium oxide, lanthanum trioxide, europium sesquioxide, niobium oxides etc.With they together shredder grind, mix.
Step is with example one later on.
Subordinate list
The composition range of table 1 leadless and low-melting point sealing glass material
| Oxide compound | Composition range (part) |
| Bi 2O 3 | 65.22～85.22 |
| B 2O 3 | 3.24～8.24 |
| ZnO | 5.76～10.76 |
| CuO | 0.80～2.80 |
| Co 2O 3 | 0.42～2.42 |
| BaO | 2.58～6.58 |
| P 2O 5 | 0.00～1.50 |
| Al 2O 3 | 0.40～1.80 |
| SiO 2 | 0.00～1.40 |
| CeO 2 | 0.00～1.20 |
| Y 2O 3 | 0.00～1.20 |
| La 2O 3 | 0.00～1.20 |
| Eu 2O 3 | 0.00～1.20 |
| Nd 2O 3 | 0.00～1.20 |
The preparing glass charge list that table 2 example is used
| Oxide compound | Composition range (part) | Material name | Example one usefulness (part) | Example dual-purpose (part) | Example is with three (parts) | Example four-function (part) |
| Bi 2O 3 | 65.22～85.22 | Bismuth oxide | 83.00 | 65.22 | 85.22 | 75.22 |
| B 2O 3 | 3.24～8.24 | Boric acid | 10.35 | 4.63 | 11.78 | 8.21 |
| ZnO | 5.76～10.76 | Zinc oxide | 5.76 | 5.76 | 10.76 | 8.26 |
| CuO | 0.80～2.80 | Cupric oxide | 8.00 | 0.80 | 2.80 | 1.80 |
| Co 2O 3 | 0.42～2.42 | Cobalt oxide | 5.00 | 0.42 | 2.42 | 1.42 |
| BaO | 2.58～6.58 | Barium carbonate | 4.61 | 3.32 | 8.47 | 5.90 |
| P 2O 5 | 0.10～1.50 | Vanadium Pentoxide in FLAKES | 0.20 | 0.10 | 1.50 | 0.80 |
| Al 2O 3 | 0.40～1.80 | Aluminum oxide | 0.40 | 0.40 | 1.80 | 1.10 |
| SiO 2 | 0.0～1.40 | Silicon-dioxide | 0.20 | 0.00 | 1.40 | 0.70 |
| CeO 2 | 0.10～1.20 | Cerium oxide | 0.80 | 0.10 | 1.20 | 0.65 |
| Y 2O 3 | 0.00～1.20 | Yttrium oxide | — | 0.00 | 1.20 | 0.60 |
| La 2O 3 | 0.00～1.20 | Lanthanum trioxide | — | 0.00 | 1.20 | 0.60 |
| Eu 2O 3 | 0.00～1.20 | Europium sesquioxide | — | 0.00 | 1.20 | 0.60 |
| Nd 2O 3 | 0.00～1.20 | Niobium oxides | 0.80 | 0.00 | 1.20 | 0.60 |
The performance index of the low-melting point sealing glass of table 3 preparation
| Sequence number | Performance | Unit | Indication range |
| 1 | Thermal expansivity | 1/K | 9.8～12.4×10 -6 |
| 2 | Transition temperature (T g) | ℃ | 335℃～450℃ |
| 3 | Softening temperature (T f) | ℃ | 400℃～550℃ |
| 4 | The sealing temperature scope | ℃ | 450℃～650℃ |
Claims (10)
1. a leadless and low-melting point sealing glass is characterized in that with Bi
2O
3-ZnO-B
2O
3The raw material that glass system adopts is the basis, mix the proper amount of rare-earth oxide compound again, after their mixing, fusing, annealing, grinding and sieve, obtain rare-earth doped leadless and low-melting point sealing glass, this seal glass by weight, mainly consist of: 65.22～85.22 parts of bismuth oxides, 4.63～11.78 parts of boric acid, 5.76～10.76 parts in zinc oxide, 0.80～2.80 part of cupric oxide, 0.42～2.42 part of cobalt oxide, 3.32～8.47 parts of barium carbonates, 0.4～1.8 part in aluminum oxide, 0.1～6.0 part of rare earth oxide.
2. rare-earth doped leadless and low-melting point sealing glass according to claim 1 is characterized in that the raw material of following weight parts in addition: 0.1～1.50 part of Vanadium Pentoxide in FLAKES, 0.1～1.4 part of silicon-dioxide.
3. leadless and low-melting point sealing glass according to claim 1, it is characterized in that described seal glass made by the raw material of following weight parts: 65.22 parts of bismuth oxides, 4.63 parts of boric acid, 10.76 parts in zinc oxide, 2.80 parts of cupric oxide, 2.42 parts of cobalt oxides, 3.32 parts of barium carbonates, 0.4 part in aluminum oxide, 0.1 part of Vanadium Pentoxide in FLAKES, 0.1 part of silicon-dioxide, 0.1 part of rare earth oxide.
4. leadless and low-melting point sealing glass according to claim 1, it is characterized in that described seal glass made by the raw material of following weight parts: 85.22 parts of bismuth oxides, 11.78 parts of boric acid, 5.76 parts in zinc oxide, 0.80 part of cupric oxide, 0.42 part of cobalt oxide, 8.47 parts of barium carbonates, 1.8 parts in aluminum oxide, 1.50 parts of Vanadium Pentoxide in FLAKESs, silica 1 .4 part, 6.0 parts of rare earth oxides.
5. leadless and low-melting point sealing glass according to claim 1, it is characterized in that described seal glass made by the raw material of following weight parts: 75.22 parts of bismuth oxides, 8.21 parts of boric acid, 8.26 parts in zinc oxide, 1.80 parts of cupric oxide, 1.42 parts of cobalt oxides, 5.90 parts of barium carbonates, 1.2 parts in aluminum oxide, 0.8 part of Vanadium Pentoxide in FLAKES, 0.75 part of silicon-dioxide, 3.05 parts of rare earth oxides.
6. according to claim 1,3,4 or 5 described leadless and low-melting point sealing glass, it is characterized in that: rare earth oxide is a kind of in cerium oxide, yttrium oxide, lanthanum trioxide, europium sesquioxide, the niobium oxides, or multiple.
7. preparation method according to the described leadless and low-melting point sealing glass of arbitrary claim in the claim 1 to 6 is characterized in that adopting the method that may further comprise the steps:
(1) batching: take by weighing raw material by forming proportioning;
(2) mix: the raw material that takes by weighing is put into shredder mix, grind, till mixing, obtain admixtion;
(3) fusing: admixtion is put into platinum crucible, and the platinum crucible that admixtion will be housed is then put into resistance furnace and is heated, and progressively rises to 1100～1200 ℃ by room temperature, and is incubated 2 hours, and admixtion is fully melted, and obtains glass metal;
(4) annealing: glass metal is cast in by in the good mould of preheating in advance, makes it to become block glass, then glass is annealed the block glass that obtains annealing;
(5) grind: the good block glass fragmentation of will annealing earlier, place it in then and grind in the agate shredder, the time of grinding is 4～10 hours;
(6) screening: the glass after will grinding obtains rare-earth doped leadless and low-melting point sealing glass through screening.
8. the preparation method of leadless and low-melting point sealing glass according to claim 7 is characterized in that in mixing process, and the raw material that takes by weighing was put into grinding machine for grinding 0.5～1 hour.
9. the preparation method of leadless and low-melting point sealing glass according to claim 7 is characterized in that progressively rising to 1200 ℃ process by room temperature is: from room temperature to 500 ℃, temperature rise rate is≤2 ℃/min; 500 ℃ to 1200 ℃, temperature rise rate is≤5 ℃/min.
10. the preparation method of leadless and low-melting point sealing glass according to claim 7 is characterized in that: rare-earth doped leadless and low-melting point sealing glass is used for the sealing-in of stainless material, electronics or electrical equipment and airtight.
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