CN110372215A - A kind of sealing glass material and preparation method thereof, connection component - Google Patents
A kind of sealing glass material and preparation method thereof, connection component Download PDFInfo
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- CN110372215A CN110372215A CN201910726215.4A CN201910726215A CN110372215A CN 110372215 A CN110372215 A CN 110372215A CN 201910726215 A CN201910726215 A CN 201910726215A CN 110372215 A CN110372215 A CN 110372215A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
- B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
- B32B17/061—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of metal
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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
- C03C29/00—Joining metals with the aid of glass
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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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- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
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Abstract
The embodiment of the present invention provides a kind of sealing glass material and preparation method thereof, connection component, is related to seal, sealing materials technical field, can be used for sealing-in aluminium and aluminium alloy part.The raw material for preparing sealing glass material includes glass network former, glass network intermediate, aluminium oxide, zinc oxide, copper oxide, the first additive, Second addition and third additive；The percentage that weight, the weight of glass network intermediate of glass network former account for the weight of sealing glass material respectively is 30%~60% and 10%~25%；The percentage that the weight of aluminium oxide accounts for the weight of sealing glass material is 1%~10%；The percentage that the weight of zinc oxide accounts for the weight of sealing glass material is 1%~9%；The percentage that the weight of copper oxide accounts for the weight of sealing glass material is 1%~5%；The percentage that the weight of first additive accounts for the weight of sealing glass material is 3%~15%；The percentage that the weight of Second addition accounts for the weight of sealing glass material is 5%~10%；The weight of third additive accounts for the percentage of the weight of sealing glass material less than 5%.
Description
Technical field
The present invention relates to seal, sealing materials technical fields more particularly to a kind of sealing glass material and preparation method thereof, connection
Component.
Background technique
It is continuous with fields electronic technology such as automotive electronics, household electrical appliance, information communication equipment, military affairs and aerospaces
Development, kovar alloy and stainless steel are that the electric connector performance of material has been difficult meet the needs of current electronic industry.Electronics is set
Standby lightweight, precise treatment and functionalization, so that aluminium and aluminum alloy connector are able to fast development.This is because aluminium and aluminium alloy
Soft with quality, ductility is good, the low (2.5g/cm of density3-3.0g/cm3), resistivity is low, and processing and forming is simply at low cost, high temperature
The advantages such as antioxygenic property is strong.
However, the fusing point of fine aluminium is 660 DEG C, within the scope of 0 DEG C -100 DEG C, the thermal expansion coefficient of fine aluminium is 236 × 10-7/
DEG C, the fusing point of aluminium alloy is between 600 DEG C -650 DEG C, within the scope of 0 DEG C -100 DEG C, the thermal expansion coefficient of aluminium alloy is 150 ×
10-7/℃-230×10-7/℃.Since the thermal expansion coefficient of aluminium and aluminium alloy is big, fusing point is low, thus it is difficult to find and aluminium or aluminium
Alloy matched coefficients of thermal expansion, and the lower encapsulating material of sealing temperature, this results in the sealing-in difficulty of aluminium and aluminium alloy part
Increase.
Summary of the invention
The embodiment of the present invention provides a kind of sealing glass material and preparation method thereof, connection component, can be used for sealing-in
Aluminium and aluminium alloy part.
In order to achieve the above objectives, the embodiment of the present invention adopts the following technical scheme that
In a first aspect, providing a kind of sealing glass material, the raw material for preparing the sealing glass material includes: glass network
Form body, glass network intermediate, aluminium oxide, zinc oxide, copper oxide, the first additive, Second addition and third addition
Agent；The material of the glass network former includes phosphorus pentoxide and/or phosphorus-containing compound；The decomposition of the phosphorus-containing compound
Object includes phosphorus pentoxide；The percentage that the weight of the glass network former accounts for the total weight of the sealing glass material is
30%~60%；The material of the glass network intermediate includes one in tin monoxide, stannic oxide and sn-containing compound
Kind is a variety of；The decomposition product of the sn-containing compound includes tin monoxide and/or stannic oxide；The glass network intermediate
The percentage that weight accounts for the total weight of the sealing glass material is 10%~25%；The weight of the aluminium oxide accounts for the sealing-in
The percentage of the total weight of glass material is 1%~10%；The weight of the zinc oxide accounts for the gross weight of the sealing glass material
The percentage of amount is 1%~9%；The percentage that the weight of the copper oxide accounts for the total weight of the sealing glass material is 1%
~5%；First additive includes boron oxide and/or boron-containing compound；The decomposition product of the boron-containing compound includes oxidation
Boron；The percentage that the weight of first additive accounts for the total weight of the sealing glass material is 3%~15%；Described second
Additive includes barium monoxide and/or containing barium compound；The decomposition product of the containing barium compound includes barium monoxide；Second addition
The percentage that the weight of agent accounts for the total weight of the sealing glass material is 5%~10%；The third additive includes oxidation
One of strontium, strontium carbonate, zirconium oxide are a variety of；The weight of the third additive accounts for the total weight of the sealing glass material
Percentage less than 5%.
In some embodiments, the phosphorus-containing compound includes ammonium dihydrogen phosphate.
In some embodiments, the sn-containing compound includes stannous pyrophosphate.
In some embodiments, the containing barium compound includes one of barium carbonate, barium sulfate, barium hydroxide or more
Kind.
In some embodiments, the boron-containing compound includes boric acid.
Second aspect provides a kind of preparation method of sealing glass material, comprising: by glass network former, glass web
Network intermediate, aluminium oxide, zinc oxide, copper oxide, the first additive, Second addition and the mixing of third additive, are mixed
Close material；Wherein, the material of the glass network former includes phosphorus pentoxide and/or phosphorus-containing compound；The phosphorous chemical combination
The decomposition product of object includes phosphorus pentoxide；The weight of the glass network former accounts for the total weight of the sealing glass material
Percentage is 30%~60%；The material of the glass network intermediate includes tin monoxide, stannic oxide and stanniferous chemical combination
One of object is a variety of；The decomposition product of the sn-containing compound includes tin monoxide and/or stannic oxide；The glass network
The percentage that the weight of intermediate accounts for the total weight of the sealing glass material is 10%~25%；The weight of the aluminium oxide accounts for
The percentage of the total weight of the sealing glass material is 1%~10%；The weight of the zinc oxide accounts for the seal glass material
The percentage of the total weight of material is 1%~9%；The weight of the copper oxide accounts for the percentage of the total weight of the sealing glass material
Than being 1%~5%；First additive includes boron oxide and/or boron-containing compound；The decomposition product packet of the boron-containing compound
Include boron oxide；The percentage that the weight of first additive accounts for the total weight of the sealing glass material is 3%~15%；Institute
Stating Second addition includes barium monoxide and/or containing barium compound；The decomposition product of the containing barium compound includes barium monoxide；Described
The percentage that the weight of two additives accounts for the total weight of the sealing glass material is 5%~10%；The third additive packet
Include one of strontium oxide strontia, strontium carbonate, zirconium oxide or a variety of；The weight of the third additive accounts for the sealing glass material
The percentage of total weight is less than 5%；The mixture is melted into the predetermined time under the melting temperature of the mixture, is mixed
Close liquid；Cooling and solidifying processing is carried out to the mixed liquor, obtains sealing glass material.
In some embodiments, the melting temperature of the mixture is 1000 DEG C~1200 DEG C.
In some embodiments, the predetermined time is 1 hour~5 hours.
In some embodiments, described that the mixed liquor is carried out cooling and solidifying to handle including: using deionized water water quenching
Method or double Kun milling train cold-rolling practices carry out cooling and solidifying processing to the mixed liquor.
In some embodiments, the average grain diameter of the sealing glass material is 1 μm~20 μm.
In some embodiments, the phosphorus-containing compound includes ammonium dihydrogen phosphate.
In some embodiments, the sn-containing compound includes stannous pyrophosphate.
In some embodiments, the containing barium compound includes one of barium carbonate, barium sulfate, barium hydroxide or more
Kind.
In some embodiments, the boron-containing compound includes boric acid.
The third aspect provides a kind of connection component, including be oppositely arranged the first component, second component and be arranged in institute
State the sealing layer between the first component and the second component；The material of the material of the first component and the second component is equal
Including aluminium and/or aluminium alloy；The material of the sealing layer includes above-mentioned sealing glass material.
The embodiment of the present invention provides a kind of sealing glass material and preparation method thereof, connection component, is preparing seal glass
The raw material of material include: glass network former, glass network intermediate, aluminium oxide, zinc oxide, copper oxide, the first additive,
Second addition and third additive；And the material of glass network former includes phosphorus pentoxide and/or phosphorus-containing compound；
The decomposition product of phosphorus-containing compound includes phosphorus pentoxide；The weight of glass network former accounts for the total weight of sealing glass material
Percentage is 30%~60%；The material of glass network intermediate includes in tin monoxide, stannic oxide and sn-containing compound
It is one or more；The decomposition product of sn-containing compound includes tin monoxide and/or stannic oxide；The weight of glass network intermediate
The percentage for accounting for the total weight of sealing glass material is 10%~25%；The weight of aluminium oxide accounts for the total weight of sealing glass material
Percentage be 1%~10%；The percentage that the weight of zinc oxide accounts for the total weight of sealing glass material is 1%~9%；Oxidation
The percentage that the weight of copper accounts for the total weight of sealing glass material is 1%~5%；First additive includes boron oxide and/or contains
Boron compound；The decomposition product of boron-containing compound includes boron oxide；The weight of first additive accounts for the total weight of sealing glass material
Percentage be 3%~15%；Second addition includes barium monoxide and/or containing barium compound；The decomposition product packet of containing barium compound
Include barium monoxide；The percentage that the weight of Second addition accounts for the total weight of sealing glass material is 5%~10%；Third additive
Including one of strontium oxide strontia, strontium carbonate, zirconium oxide or a variety of；The weight of third additive accounts for the total weight of sealing glass material
Percentage less than 5% in the case where, the softening point of sealing glass material is 300 DEG C~400 DEG C, transition temperature is 288 DEG C~
324 DEG C, sealing temperature is 410 DEG C~550 DEG C, and the specific gravity of sealing glass material is 2~3.6, the thermal expansion of sealing glass material
Coefficient is 150 × 10-7/ DEG C~230 × 10-7/℃.Due to the chemical stabilization of sealing glass material provided in an embodiment of the present invention
Property it is good, sealing temperature is lower, and the similar thermal expansion coefficient of the thermal expansion coefficient of sealing glass material and aluminium and aluminium alloy, because
And sealing glass material provided in an embodiment of the present invention can be used for carrying out matched seal to aluminium and aluminium alloy part.
Further, since lead is not contained in the raw material provided in an embodiment of the present invention for preparing sealing glass material, thus this hair
The sealing glass material that bright embodiment provides is lead-free glass powder.On this basis, due to preparation provided in an embodiment of the present invention
Alkali metal is not contained in the raw material of sealing glass material, thus relative to the relevant technologies, alkali metal is avoided to seal glass material
The electrical property of material and the influence of chemical stability ensure that the electrical property and chemical stability of sealing glass material.
Detailed description of the invention
Technical solution in order to illustrate the embodiments of the present invention more clearly or in the related technology, below will be to embodiment or phase
Attached drawing needed in technical description is closed to be briefly described, it should be apparent that, the accompanying drawings in the following description is only this
Some embodiments of invention for those of ordinary skill in the art without creative efforts, can be with
It obtains other drawings based on these drawings.
Fig. 1 is a kind of flow diagram of the preparation method of sealing glass material provided in an embodiment of the present invention；
Fig. 2 is a kind of preparation flow schematic diagram of sealing glass material provided in an embodiment of the present invention；
Fig. 3 is a kind of structural schematic diagram of connection component provided in an embodiment of the present invention.
Appended drawing reference:
The 10- first component；20- second component；30- sealing layer.
Specific embodiment
Following will be combined with the drawings in the embodiments of the present invention, and technical solution in the embodiment of the present invention carries out clear, complete
Site preparation description, it is clear that described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.It is based on
Embodiment in the present invention, it is obtained by those of ordinary skill in the art without making creative efforts every other
Embodiment shall fall within the protection scope of the present invention.
The embodiment of the present invention provides a kind of sealing glass material, and the raw material for preparing sealing glass material includes: glass network
Form body (also referred to as glass former), glass network intermediate (also referred to as glass intermediate), aluminium oxide (Al2O3), zinc oxide
(ZnO), copper oxide (CuO), the first additive, Second addition and third additive.
The material of glass network former includes phosphorus pentoxide (P2O5) and/or phosphorus-containing compound；Point of phosphorus-containing compound
Solving object includes phosphorus pentoxide；The weight of glass network former account for the total weight of sealing glass material percentage be 30%~
60%.
Herein, it is contemplated that if the percentage that the weight of glass network former accounts for the total weight of sealing glass material is lower than
When 30%, then glassy state is not easily formed；If the weight of glass network former accounts for the percentage of the total weight of sealing glass material
Than being higher than 60%, then the chemical stability of the sealing glass material formed is poor, therefore in the embodiment of the present invention, glass network shape
The percentage that the weight of adult accounts for the total weight of sealing glass material is 30%~60%.
For phosphorus-containing compound without limiting, generation phosphorus pentoxide can be decomposed by being subject to.It is exemplary, phosphorus-containing compound
It can be ammonium dihydrogen phosphate, phosphoric acid, ammonium phosphate or monoammonium phosphate etc..
On this basis, it is contemplated that further include other miscellaneous if the decomposition product of phosphorus-containing compound is in addition to including phosphorus pentoxide
Prime element, then other impurity elements may will affect chemical stability, thermal expansion coefficient or the softening temperature of sealing glass material
Etc. performances, therefore in some embodiments, the phosphorus-containing compound of selection, the decomposition product after decomposition is by phosphorus pentoxide, Yi Jishui
And/or gas composition.In the case where the decomposition product of phosphorus-containing compound is by phosphorus pentoxide and water and/or gas composition, by
It volatilizees in the gentle cognition of water, thus final only remaining phosphorus pentoxide, other impurity elements are not introduced into, therefore will not influence sealing-in
The performance of glass material.Exemplary, phosphorus-containing compound may include ammonium dihydrogen phosphate.Ammonium dihydrogen phosphate generates five oxidations after decomposing
Two phosphorus and ammonia.
The material of glass network intermediate includes tin monoxide (SnO, also referred to as stannous oxide), stannic oxide (SnO2) with
And one of sn-containing compound or a variety of；The decomposition product of sn-containing compound includes tin monoxide and/or stannic oxide；Glass web
The percentage that the weight of network intermediate accounts for the total weight of sealing glass material is 10%~25%.
Effect of the glass network intermediate in sealing glass material is primarily to glass network former is connected to
Together.In addition, the weight of glass network intermediate account for the total weight of sealing glass material percentage be 10%~25% when, glass
Glass network intermediate can also play the role of reducing sealing glass material softening temperature, and improve the heat of sealing glass material
The effect of the coefficient of expansion.
For sn-containing compound without limiting, generation tin monoxide and/or stannic oxide can be decomposed by being subject to.Example
, sn-containing compound can be stannous pyrophosphate or carbonic acid tin etc..
On this basis, it is contemplated that if the decomposition product of sn-containing compound in addition to including tin monoxide and/or stannic oxide, is gone back
Including other impurity elements, then other impurity elements may will affect the chemical stability of sealing glass material, thermal expansion coefficient
Or the performances such as softening temperature, therefore in some embodiments, the sn-containing compound of selection, the decomposition product after decomposition is by tin monoxide
And/or stannic oxide and water and/or gas composition.Sn-containing compound decomposition product by tin monoxide and/or titanium dioxide
In the case where tin and water and/or gas composition, due to water gentle cognition volatilization, thus final only remaining tin monoxide and/or
Stannic oxide is not introduced into other impurity elements, therefore will not influence the performance of sealing glass material.It is exemplary, sn-containing compound
It may include stannous pyrophosphate.
The percentage that the weight of aluminium oxide accounts for the total weight of sealing glass material is 1%~10%；The weight of zinc oxide accounts for
The percentage of the total weight of sealing glass material is 1%~9%；The weight of copper oxide accounts for the hundred of the total weight of sealing glass material
Divide than being 1%~5%.
Herein, the weight of aluminium oxide account for the total weight of sealing glass material percentage be 1%~10% when, aluminium oxide is not
Can only play the role of improve sealing glass material chemical stability, can also within the scope of sealing temperature stabilized glass body,
Avoid the generation of crystallization.
The weight of zinc oxide account for the total weight of sealing glass material percentage be 1%~9% when, zinc oxide can play
Reduce the effect of the fusing point of sealing glass material.
The weight of copper oxide account for the total weight of sealing glass material percentage be 1%~5% when, copper oxide can play
Improve the effect of the wellability and mobility of sealing glass material.
First additive includes boron oxide (B2O3) and/or boron-containing compound；The decomposition product of boron-containing compound includes oxidation
Boron；The percentage that the weight of first additive accounts for the total weight of sealing glass material is 3%~15%.
The weight of first additive account for the total weight of sealing glass material percentage be 3%~15% when, first addition
Agent primarily serves adjusting sealing glass material softening temperature in a certain range, reduces the work of sealing glass material high temperature viscosity
With.
For boron-containing compound without limiting, generation boron oxide can be decomposed by being subject to.Exemplary, boron-containing compound can be with
It is received for boric acid or boric acid.
On this basis, it is contemplated that if the decomposition product of boron-containing compound in addition to including boron oxide, further includes other impurity members
Element, then other impurity elements may will affect the property such as chemical stability, thermal expansion coefficient or softening temperature of sealing glass material
Can, therefore in some embodiments, the boron-containing compound of selection, the decomposition product after decomposition is by boron oxide and water and/or gas
Composition.Boron-containing compound decomposition product by boron oxide and water and/or gas composition in the case where, due to the gentle cognition of water
Volatilization, thus final only remaining boron oxide, are not introduced into other impurity elements, therefore will not influence the performance of sealing glass material.
Exemplary, boron-containing compound may include boric acid.Boric acid generates boron oxide and water after decomposing.
Second addition includes barium monoxide (BaO) and/or containing barium compound；The decomposition product of containing barium compound includes oxidation
Barium；The percentage that the weight of Second addition accounts for the total weight of sealing glass material is 5%~10%.
The weight of Second addition account for the total weight of sealing glass material percentage be 5%~10% when, second addition
The thermal expansion coefficient of sealing glass material can be improved in agent in a certain range, so that it is centainly being expanded with the component to sealing-in
Matched seal is carried out in range differences.
For containing barium compound without limiting, generation barium monoxide can be decomposed by being subject to.Exemplary, containing barium compound can be with
For barium carbonate, barium sulfate or barium hydroxide etc..
On this basis, it is contemplated that if the decomposition product of containing barium compound in addition to including barium monoxide, further includes other impurity members
Element, then other impurity elements may will affect the property such as chemical stability, thermal expansion coefficient or softening temperature of sealing glass material
Can, therefore in some embodiments, the containing barium compound of selection, the decomposition product after decomposition is by barium monoxide and water and/or gas
Composition.Containing barium compound decomposition product by barium monoxide and water and/or gas composition in the case where, due to the gentle cognition of water
Volatilization, thus final only remaining barium monoxide, are not introduced into other impurity elements, therefore will not influence the performance of sealing glass material.
Exemplary, containing barium compound may include one of barium carbonate, barium sulfate, barium hydroxide or a variety of.Barium carbonate produces after decomposing
Raw barium monoxide, carbon dioxide and water.Barium sulfate generates barium monoxide, sulfur dioxide and water after decomposing.Barium hydroxide generates after decomposing
Barium monoxide and water.
Third additive includes strontium oxide strontia (SrO), strontium carbonate (SrCO3), zirconium oxide (ZrO2) one of or it is a variety of；The
The weight of three additives accounts for the percentage of the total weight of sealing glass material less than 5%.
It will be understood by those skilled in the art that strontium carbonate can be decomposed into strontium oxide strontia and carbon dioxide.
Third additive can play fine tuning sealing glass material high temperature viscosity, increase sealing glass material chemical stability
Effect.
The material of glass network former is P in the raw material to prepare sealing glass material below2O5, among glass network
The material of body is SnO, and the material of the first additive is B2O3, the material of Second addition is BaO, and the material of third additive is
SrO and/or ZrO2For, the thermalexpansioncoefficientα of the sealing glass material different to four kinds of constituent contents, softening temperature are (also referred to as
Softening point), water resistant chemical stability detected.Testing result is as shown in table 1.Each component in terms of weight percentage in table 1
Content.
Table 1
Prepare the process of above-mentioned sealing glass material are as follows: it is mixed after weighing above-mentioned each ingredient according to weight percent, and
After being melted 2 hours at 1100 DEG C, carries out water cooling broken method of quenching and be cooled into glass fragment, glass fragment is further pulverized, mistake
Sieve can be obtained sealing glass material.Later, softening temperature, thermal expansion coefficient and the water resistant chemistry of sealing glass material are detected
The parameters such as stability.
It is to be understood that the sealing temperature of sealing glass material is related with the softening temperature of sealing glass material, sealing-in glass
The softening temperature of glass material is lower, and the sealing temperature of sealing glass material is lower.
Based on above-mentioned, in some embodiments, the test side of SJ 689-83 electric-vacuum glass linear expansion coefficient can use
Method detects the thermal expansion coefficients of above-mentioned four kinds of sealing glass materials.
In some embodiments, the test method that can use SJ 690-83 electric-vacuum glass softening point is above-mentioned to detect
The softening temperature of four kinds of sealing glass materials.
In some embodiments, it can use SJ 696-83 electric-vacuum glass water resistant chemistry stability testing method to examine
Survey the water resistant chemical stability of above-mentioned four kinds of sealing glass materials.
From table 1 thermalexpansioncoefficientα of four kinds of sealing glass materials, softening temperature, water resistant chemical stability detection knot
Fruit can be seen that the thermal expansion coefficient of above-mentioned four kinds of sealing glass materials and the thermal expansion coefficient of aluminium and aluminium alloy approaches, in this way
One, when using the sealing glass material sealing-in aluminium and aluminium alloy part, matched seal may be implemented.In addition, above-mentioned four kinds of envelopes
The softening temperature for connecing glass material is respectively less than 400 DEG C, seals lower than aluminium and the fusing point of aluminium alloy, thus using the sealing glass material
When connecing aluminium and aluminium alloy part, low-temperature sealing may be implemented.On this basis, the water resistant chemical stability of sealing glass material is big
When being equal to II grade, the chemical stability of sealing glass material is good.Due to the water resistant chemistry of above-mentioned four kinds of sealing glass materials
Stability is at I grade or II grade, therefore the chemical stability of sealing glass material is good.
Sealing glass material provided in an embodiment of the present invention includes: glass network in the raw material for preparing sealing glass material
Form body, glass network intermediate, aluminium oxide, zinc oxide, copper oxide, the first additive, Second addition and third addition
Agent；And the material of glass network former includes phosphorus pentoxide and/or phosphorus-containing compound；The decomposition product of phosphorus-containing compound includes
Phosphorus pentoxide；The percentage that the weight of glass network former accounts for the total weight of sealing glass material is 30%~60%；Glass
The material of glass network intermediate includes one of tin monoxide, stannic oxide and sn-containing compound or a variety of；Stanniferous chemical combination
The decomposition product of object includes tin monoxide and/or stannic oxide；The weight of glass network intermediate accounts for the gross weight of sealing glass material
The percentage of amount is 10%~25%；The percentage that the weight of aluminium oxide accounts for the total weight of sealing glass material is 1%~10%；
The percentage that the weight of zinc oxide accounts for the total weight of sealing glass material is 1%~9%；The weight of copper oxide accounts for seal glass material
The percentage of the total weight of material is 1%~5%；First additive includes boron oxide and/or boron-containing compound；Boron-containing compound
Decomposition product includes boron oxide；The percentage that the weight of first additive accounts for the total weight of sealing glass material is 3%~15%；The
Two additives include barium monoxide and/or containing barium compound；The decomposition product of containing barium compound includes barium monoxide；The weight of Second addition
The percentage that amount accounts for the total weight of sealing glass material is 5%~10%；Third additive includes strontium oxide strontia, strontium carbonate, oxidation
One of zirconium is a variety of；The weight of third additive accounts for the case where percentage of the total weight of sealing glass material is less than 5%
Under, the softening point of sealing glass material is 300 DEG C~400 DEG C, and transition temperature is 288 DEG C~324 DEG C, and sealing temperature is 410 DEG C
~550 DEG C, the specific gravity of sealing glass material is 2~3.6, and the thermal expansion coefficient of sealing glass material is 150 × 10-7/ DEG C~230
×10-7/℃。
In the related technology, the glass system for aluminium and aluminium alloy sealing-in is divided into two major classes, i.e. flint glass and unleaded glass
Glass.As the developed countries such as the U.S., European Union or even some developing countries require to be increasingly stringenter to electronic product lead content,
Flint glass just slowly exits the field.Current unleaded aluminium and aluminium alloy sealing glass material are concentrated mainly on glassy polyphosphate
System.Phosphate glass fusion temperature and sealing temperature are relatively low, and the coefficient of expansion is big, but chemical stability is slightly worse, thus uncomfortable
In the sealing-in of aluminium and aluminium alloy part.
In the related technology, although part is for sealing-in aluminium and the sealing glass material of aluminium alloy, thermal expansion coefficient and aluminium
And the similar thermal expansion coefficient of aluminium alloy, it can satisfy the needs of matched seal, but contain in sealing glass material containing excessively high
The alkali metal of amount, excessively high alkali metal (such as Na2O) content is unfavorable to the electrical property and chemical stability of sealing glass material
's.
The embodiment of the present invention provides a kind of sealing glass material, due to sealing glass material provided in an embodiment of the present invention
Chemical stability is good, and sealing temperature is lower, and the thermal expansion system of the thermal expansion coefficient of sealing glass material and aluminium and aluminium alloy
Number is close, thus sealing glass material provided in an embodiment of the present invention can be used for carrying out matching envelope to aluminium and aluminium alloy part
It connects.
Further, since lead is not contained in the raw material provided in an embodiment of the present invention for preparing sealing glass material, thus this hair
The sealing glass material that bright embodiment provides is lead-free glass powder.On this basis, due to preparation provided in an embodiment of the present invention
Alkali metal is not contained in the raw material of sealing glass material, thus relative to the relevant technologies, alkali metal is avoided to seal glass material
The electrical property of material and the influence of chemical stability ensure that the electrical property and chemical stability of sealing glass material.
The embodiment of the present invention also provides a kind of preparation method of sealing glass material, as shown in Figure 1, comprising:
S100, by glass network former, glass network intermediate, aluminium oxide, zinc oxide, copper oxide, the first additive,
Second addition and the mixing of third additive, obtain mixture.Wherein, the material of glass network former includes five oxidations two
Phosphorus and/or phosphorus-containing compound；The decomposition product of phosphorus-containing compound includes phosphorus pentoxide；The weight of glass network former accounts for sealing-in
The percentage of the total weight of glass material is 30%~60%；The material of glass network intermediate includes tin monoxide, titanium dioxide
One of tin and sn-containing compound are a variety of；The decomposition product of sn-containing compound includes tin monoxide and/or stannic oxide；Glass
The percentage that the weight of glass network intermediate accounts for the total weight of sealing glass material is 10%~25%；The weight of aluminium oxide accounts for envelope
The percentage for connecing the total weight of glass material is 1%~10%；The weight of zinc oxide accounts for the hundred of the total weight of sealing glass material
Divide than being 1%~9%；The percentage that the weight of copper oxide accounts for the total weight of sealing glass material is 1%~5%；First addition
Agent includes boron oxide and/or boron-containing compound；The decomposition product of boron-containing compound includes boron oxide；The weight of first additive accounts for envelope
The percentage for connecing the total weight of glass material is 3%~15%；Second addition includes barium monoxide and/or containing barium compound；Contain
The decomposition product of barium compound includes barium monoxide；The percentage that the weight of Second addition accounts for the total weight of sealing glass material is
5%~10%；Third additive includes one of strontium oxide strontia, strontium carbonate, zirconium oxide or a variety of；The weight of third additive accounts for
The percentage of the total weight of sealing glass material is less than 5%.
For phosphorus-containing compound without limiting, generation phosphorus pentoxide can be decomposed by being subject to.It is exemplary, phosphorus-containing compound
It can be ammonium dihydrogen phosphate, phosphoric acid, ammonium phosphate or monoammonium phosphate etc..
On this basis, it is contemplated that further include other miscellaneous if the decomposition product of phosphorus-containing compound is in addition to including phosphorus pentoxide
Prime element, then other impurity elements may will affect chemical stability, thermal expansion coefficient or the softening temperature of sealing glass material
Etc. performances, therefore in some embodiments, the phosphorus-containing compound of selection, the decomposition product after decomposition is by phosphorus pentoxide, Yi Jishui
And/or gas composition.In the case where the decomposition product of phosphorus-containing compound is by phosphorus pentoxide and water and/or gas composition, by
It volatilizees in the gentle cognition of water, thus final only remaining phosphorus pentoxide, other impurity elements are not introduced into, therefore will not influence sealing-in
The performance of glass material.Exemplary, phosphorus-containing compound may include ammonium dihydrogen phosphate.Ammonium dihydrogen phosphate generates five oxidations after decomposing
Two phosphorus and ammonia.
For sn-containing compound without limiting, generation tin monoxide and/or stannic oxide can be decomposed by being subject to.Example
, sn-containing compound can be stannous pyrophosphate or carbonic acid tin etc..
On this basis, it is contemplated that if the decomposition product of sn-containing compound in addition to including tin monoxide and/or stannic oxide, is gone back
Including other impurity elements, then other impurity elements may will affect the chemical stability of sealing glass material, thermal expansion coefficient
Or the performances such as softening temperature, therefore in some embodiments, the sn-containing compound of selection, the decomposition product after decomposition is by tin monoxide
And/or stannic oxide and water and/or gas composition.Sn-containing compound decomposition product by tin monoxide and/or titanium dioxide
In the case where tin and water and/or gas composition, due to water gentle cognition volatilization, thus final only remaining tin monoxide and/or
Stannic oxide is not introduced into other impurity elements, therefore will not influence the performance of sealing glass material.It is exemplary, sn-containing compound
It may include stannous pyrophosphate.
For boron-containing compound without limiting, generation boron oxide can be decomposed by being subject to.Exemplary, boron-containing compound can be with
It is received for boric acid or boric acid.
On this basis, it is contemplated that if the decomposition product of boron-containing compound in addition to including boron oxide, further includes other impurity members
Element, then other impurity elements may will affect the property such as chemical stability, thermal expansion coefficient or softening temperature of sealing glass material
Can, therefore in some embodiments, the boron-containing compound of selection, the decomposition product after decomposition is by boron oxide and water and/or gas
Composition.Boron-containing compound decomposition product by boron oxide and water and/or gas composition in the case where, due to the gentle cognition of water
Volatilization, thus final only remaining boron oxide, are not introduced into other impurity elements, therefore will not influence the performance of sealing glass material.
Exemplary, boron-containing compound may include boric acid.Boric acid generates boron oxide and water after decomposing.
For containing barium compound without limiting, generation barium monoxide can be decomposed by being subject to.Exemplary, containing barium compound can be with
For barium carbonate, barium sulfate or barium hydroxide etc..
On this basis, it is contemplated that if the decomposition product of containing barium compound in addition to including barium monoxide, further includes other impurity members
Element, then other impurity elements may will affect the property such as chemical stability, thermal expansion coefficient or softening temperature of sealing glass material
Can, therefore in some embodiments, the containing barium compound of selection, the decomposition product after decomposition is by barium monoxide and water and/or gas
Composition.Containing barium compound decomposition product by barium monoxide and water and/or gas composition in the case where, due to the gentle cognition of water
Volatilization, thus final only remaining barium monoxide, are not introduced into other impurity elements, therefore will not influence the performance of sealing glass material.
Exemplary, containing barium compound may include one of barium carbonate, barium sulfate, barium hydroxide or a variety of.Barium carbonate produces after decomposing
Raw barium monoxide, carbon dioxide and water.Barium sulfate generates barium monoxide, sulfur dioxide and water after decomposing.Barium hydroxide generates after decomposing
Barium monoxide and water.
Since above-described embodiment is to glass network former, glass network intermediate, aluminium oxide, zinc oxide, oxidation
The effect of copper, the first additive, Second addition and third additive is described in detail, thus no longer superfluous herein
It states.
Herein, glass network former, glass network intermediate, oxidation can be made using the methods of stirring, ultrasonic vibration
Aluminium, zinc oxide, copper oxide, the first additive, Second addition and third additive are uniformly mixed.
S101, mixture melted into the predetermined time under the melting temperature of mixture, obtains mixed liquor.
For mixture melting temperature without limit, be subject to can make mixture melt.If in view of melting for setting
It is too low to melt temperature, then some materials may not be able to melt completely in mixture；If the melting temperature being arranged is too high, in mixture
Some materials may evaporate.Based on this, in some embodiments, the melting temperature of mixture is 1000 DEG C~1200 DEG C.
Herein, the melting temperature of mixture can be 1000 DEG C, 1100 DEG C or 1200 DEG C etc..
For fusing predetermined time without limit, be subject to can make mixture melt.If too in view of the predetermined time
Short, then some materials may not be able to melt completely in mixture；If the predetermined time is too long, the system of sealing glass material can be reduced
Standby efficiency.Based on this, in some embodiments, the predetermined time is 1 hour (h)~5 hours.
Herein, the predetermined time can be 1h, 3h or 5h etc..
On this basis, mixture can be put into melted ware and is melted.Be melted ware material for example can for ceramics or
Quartz.
S102, cooling and solidifying processing is carried out to mixed liquor, obtains sealing glass material.
Herein, the mode of cooling and solidifying processing is carried out without restriction, two kinds of specific modes presented below to mixed liquor.
The first: carrying out cooling and solidifying processing to mixed liquor using deionized water water quenching.Second: using double Kun milling train cold-rolling practices pair
Mixed liquor carries out cooling and solidifying processing.
It is to be understood that it is in the form of sheets or blocky to carry out the sealing glass material obtained after cooling and solidifying processing to mixed liquor,
I.e. sealing glass material is sheet glass or glass dregs.Based on this, in some embodiments, mixed liquor is carried out at cooling and solidifying
Reason, after obtaining sealing glass material, the preparation method of above-mentioned sealing glass material further include:
Sealing glass material is ground.
Herein, after grinding, sheet glass or glass dregs are pulverized, and in the case, sealing glass material is sealed in powdered
Connecing glass material is sealing glass powder.
It on this basis, in some embodiments, can also be according to sealing glass material grain after obtaining sealing glass powder
The size of diameter is classified sealing glass powder, obtains finished glass powder.
It on this basis, can basis for the average grain diameter of the sealing glass material obtained after grinding without limiting
Different use demands is ground into different partial sizes.In some embodiments, the average grain diameter of sealing glass material be 1 μm~
20μm。
Herein, the average grain diameter of sealing glass material can be 1 μm, 3 μm, 5 μm, 10 μm, 15 μm, 20 μm etc..
Based on above-mentioned, it should be understood that, after sealing glass material is prepared, utilize packaged glass material sealing-in aluminium and aluminium
Before alloy component, it is also necessary to which sealing glass material is fabricated to the forms such as amyloplastid, glass paste or glass paste.Amyloplastid,
It further include other materials, such as glue in glass paste or glass paste in addition to including sealing glass material.
The embodiment of the present invention provides a kind of preparation method of sealing glass material, and the preparation method of sealing glass material has
Ingredient identical with sealing glass material provided by the above embodiment and beneficial effect, since above-described embodiment is to sealing-in glass
The ingredient and beneficial effect of glass material are described in detail, thus details are not described herein again.
The preparation process of sealing glass material is described in detail in a specific embodiment presented below.Fig. 2 is seal glass material
The preparation flow schematic diagram of material.With reference to Fig. 2, raw material (glass network former, glass network of sealing glass material will be first prepared
Intermediate, aluminium oxide, zinc oxide, copper oxide, the first additive, Second addition and third additive) it is uniformly mixed, it is put into
Fusing in ware is melted and obtains mixed liquor；Later, cooling and solidifying processing is carried out to mixed liquor, obtains sheet or block-like seal glass
Material, i.e. sheet glass or glass dregs；Sheet glass or glass dregs are ground, powdered sealing glass material is obtained,
That is glass powder；Sealing glass material is classified according to the size of sealing glass material partial size, finished product can be obtained later
Sealing glass material.
The embodiment of the present invention also provides a kind of connection component, as shown in figure 3, including the first component 10 being oppositely arranged, the
Two components 20 and the sealing layer 30 being arranged between the first component 10 and second component 20；The material of the first component 10 and second
The material of component 20 includes aluminium and/or aluminium alloy；The material of sealing layer 30 includes above-mentioned sealing glass material.
Herein, the material of sealing layer 30 can also include other materials in addition to including above-mentioned sealing glass material, such as
Glue etc..
In addition, the effect of sealing layer 30 is for the first component 10 and second component 20 to link together.
The embodiment of the present invention provides a kind of connection component, including be oppositely arranged the first component 10, second component 20 and
Sealing layer 30 between the first component 10 and second component 20 is set；The material of the first component 10 and the material of second component 20
It include aluminium and/or aluminium alloy；The material of sealing layer 30 includes above-mentioned sealing glass material.Due to above-mentioned sealing glass material
Softening temperature it is lower, chemical stability is excellent, and the thermal expansion of the thermal expansion coefficient of sealing glass material and aluminium and aluminium alloy
Coefficient similar, thus the matched seal of the first component 10 and second component 20 may be implemented.
The above description is merely a specific embodiment, but scope of protection of the present invention is not limited thereto, any
In the technical scope disclosed by the present invention, any changes or substitutions that can be easily thought of by those familiar with the art, all answers
It is included within the scope of the present invention.Therefore, protection scope of the present invention should be with the scope of protection of the claims
It is quasi-.
Claims (15)
1. a kind of sealing glass material, which is characterized in that the raw material for preparing the sealing glass material includes: that glass network is formed
Body, glass network intermediate, aluminium oxide, zinc oxide, copper oxide, the first additive, Second addition and third additive；
The material of the glass network former includes phosphorus pentoxide and/or phosphorus-containing compound；Point of the phosphorus-containing compound
Solving object includes phosphorus pentoxide；The weight of the glass network former accounts for the percentage of the total weight of the sealing glass material
It is 30%~60%；
The material of the glass network intermediate includes one of tin monoxide, stannic oxide and sn-containing compound or more
Kind；The decomposition product of the sn-containing compound includes tin monoxide and/or stannic oxide；The weight of the glass network intermediate accounts for
The percentage of the total weight of the sealing glass material is 10%~25%；
The percentage that the weight of the aluminium oxide accounts for the total weight of the sealing glass material is 1%~10%；The zinc oxide
Weight account for the sealing glass material total weight percentage be 1%~9%；The weight of the copper oxide accounts for the sealing-in
The percentage of the total weight of glass material is 1%~5%；
First additive includes boron oxide and/or boron-containing compound；The decomposition product of the boron-containing compound includes boron oxide；
The percentage that the weight of first additive accounts for the total weight of the sealing glass material is 3%~15%；
The Second addition includes barium monoxide and/or containing barium compound；The decomposition product of the containing barium compound includes barium monoxide；
The percentage that the weight of the Second addition accounts for the total weight of the sealing glass material is 5%~10%；
The third additive includes one of strontium oxide strontia, strontium carbonate, zirconium oxide or a variety of；The weight of the third additive
The percentage of the total weight of the sealing glass material is accounted for less than 5%.
2. sealing glass material according to claim 1, which is characterized in that the phosphorus-containing compound includes biphosphate
Ammonium.
3. sealing glass material according to claim 1, which is characterized in that the sn-containing compound includes pyrophosphoric acid Asia
Tin.
4. sealing glass material according to claim 1, which is characterized in that the containing barium compound includes barium carbonate, sulphur
One of sour barium, barium hydroxide are a variety of.
5. sealing glass material according to claim 1, which is characterized in that the boron-containing compound includes boric acid.
6. a kind of preparation method of sealing glass material characterized by comprising
By glass network former, glass network intermediate, aluminium oxide, zinc oxide, copper oxide, the first additive, the second addition
Agent and the mixing of third additive, obtain mixture；Wherein, the material of the glass network former includes phosphorus pentoxide
And/or phosphorus-containing compound；The decomposition product of the phosphorus-containing compound includes phosphorus pentoxide；The weight of the glass network former
The percentage for accounting for the total weight of the sealing glass material is 30%~60%；The material of the glass network intermediate includes one
One of tin oxide, stannic oxide and sn-containing compound are a variety of；The decomposition product of the sn-containing compound includes an oxidation
Tin and/or stannic oxide；The percentage that the weight of the glass network intermediate accounts for the total weight of the sealing glass material is
10%~25%；The percentage that the weight of the aluminium oxide accounts for the total weight of the sealing glass material is 1%~10%；It is described
The percentage that the weight of zinc oxide accounts for the total weight of the sealing glass material is 1%~9%；The weight of the copper oxide accounts for institute
The percentage for stating the total weight of sealing glass material is 1%~5%；First additive includes boron oxide and/or containing boronation
Close object；The decomposition product of the boron-containing compound includes boron oxide；The weight of first additive accounts for the sealing glass material
Total weight percentage be 3%~15%；The Second addition includes barium monoxide and/or containing barium compound；The baric
The decomposition product of compound includes barium monoxide；The weight of the Second addition accounts for the percentage of the total weight of the sealing glass material
Than being 5%~10%；The third additive includes one of strontium oxide strontia, strontium carbonate, zirconium oxide or a variety of；The third adds
The weight of agent is added to account for the percentage of the total weight of the sealing glass material less than 5%；
The mixture is melted into the predetermined time under the melting temperature of the mixture, obtains mixed liquor；
Cooling and solidifying processing is carried out to the mixed liquor, obtains sealing glass material.
7. the preparation method of sealing glass material according to claim 6, which is characterized in that the melting temperature of the mixture
Degree is 1000 DEG C~1200 DEG C.
8. the preparation method of sealing glass material according to claim 6, which is characterized in that the predetermined time is 1 small
When~5 hours.
9. the preparation method of sealing glass material according to claim 6, which is characterized in that it is described to the mixed liquor into
Row cooling and solidifying is handled
Cooling and solidifying processing is carried out to the mixed liquor using deionized water water quenching or double Kun milling train cold-rolling practices.
10. the preparation method of sealing glass material according to claim 6, which is characterized in that the sealing glass material
Average grain diameter be 1 μm~20 μm.
11. the preparation method of sealing glass material according to claim 6, which is characterized in that the phosphorus-containing compound packet
Include ammonium dihydrogen phosphate.
12. the preparation method of sealing glass material according to claim 6, which is characterized in that the sn-containing compound packet
Include stannous pyrophosphate.
13. the preparation method of sealing glass material according to claim 6, which is characterized in that the containing barium compound packet
Include one of barium carbonate, barium sulfate, barium hydroxide or a variety of.
14. the preparation method of sealing glass material according to claim 6, which is characterized in that the boron-containing compound packet
Include boric acid.
15. a kind of connection component, which is characterized in that including be oppositely arranged the first component, second component and be arranged described
Sealing layer between the first component and the second component；
The material of the material of the first component and the second component includes aluminium and/or aluminium alloy；The material of the sealing layer
Material includes sealing glass material as described in any one in claim 1-5.
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| CN201910726215.4A CN110372215A (en) | 2019-08-07 | 2019-08-07 | A kind of sealing glass material and preparation method thereof, connection component |
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| CN201910726215.4A CN110372215A (en) | 2019-08-07 | 2019-08-07 | A kind of sealing glass material and preparation method thereof, connection component |
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