CN110217993A - A kind of Environment-friendlylow-temperature low-temperature seal glass and preparation method thereof - Google Patents
A kind of Environment-friendlylow-temperature low-temperature seal glass and preparation method thereof Download PDFInfo
- Publication number
- CN110217993A CN110217993A CN201910561222.3A CN201910561222A CN110217993A CN 110217993 A CN110217993 A CN 110217993A CN 201910561222 A CN201910561222 A CN 201910561222A CN 110217993 A CN110217993 A CN 110217993A
- Authority
- CN
- China
- Prior art keywords
- glass
- temperature
- environment
- friendlylow
- low
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
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
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/062—Glass compositions containing silica with less than 40% silica by weight
- C03C3/064—Glass compositions containing silica with less than 40% silica by weight containing boron
- C03C3/068—Glass compositions containing silica with less than 40% silica by weight containing boron containing rare earths
-
- 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
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 invention discloses a kind of Environment-friendlylow-temperature low-temperature seal glass, which is prepared according to mass percentage content: 30-50wt.%Bi2O3, 26-45wt.%ZnO, 8-20wt.%B2O3, 1-8wt.%Y2O3, 0.1-5wt.%WO3, 0.1-1wt.%TiO2, 0.1-1wt.%SnO2, 0-5wt.%SiO2, 0-5wt.%Al2O3.The present invention also provides a kind of preparation methods of Environment-friendlylow-temperature low-temperature seal glass, comprising the following steps: by SiO2、Al2O3、B2O3、Bi2O3、ZnO、Y2O3、WO3、TiO2、SnO2Equal oxides weigh raw material by mass percentage, it is put into platinum crucible after mixing, then platinum crucible is melted 1~3 hour at a temperature of 900~1200 DEG C, after glass melting is uniform, melten glass liquid is poured into water quenching in deionized water, then the dry fragment for obtaining glass melt, then the glass after drying is subjected to ball mill grinding, and dried 200 meshes.The invention has the following advantages that being free of environmentally harmful heavy metallic oxide；It is (55~70) × 10 in the glass average thermal linear expansion coefficient of 30-380 DEG C of range‑7/℃；The softening point temperature of glass is less than 400 DEG C.
Description
Technical field
The present invention relates to a kind of bismuthates Environment-friendlylow-temperature low-temperature sealing glass material and preparation method thereof, belong to glass material and
Technical field of electronic materials.
Background technique
Low temperature sealing glass refers to that fusing point is substantially less than the seal glass of simple glass, it can be used as a kind of solder application
In vacuum technique and electronic technology, it is widely used in automotive electronics, household electrical appliance, information communication science and technology, defense military, electronics
The various fields such as slurry, microelectric technique, the energy, aerospace.
At present in low-temperature sealing field, the manufacturing enterprise of domestic semiconductor instrument instrument without shell sealing in for a long time with
To use always the Organic adhesive of epoxy resin to generate at work as seal, sealing materials using this kind of organic material
High temperature can make organic matter aging, cause sealing that gas leakage, the moisture absorption, the danger such as electric leakage occur, environmental protection, chemical stability, water resistance,
The advantage of the not no seal glass of sealing-in stability etc., performance also cannot get the approval of international market.
It is now popular in the world that seal glass is used mainly to have in traditional low temperature sealing glass as seal, sealing materials
The low temperature sealing glass such as plumbite glass, vanadate glass, phosphate glass.Wherein plumbite glass have dielectric loss it is small,
Softening temperature is low, good chemical stability, but plumbite glass is due to containing PbO, so that it is from being prepared into use process
In can generate pollution to human body and environment and poison, the western developed countries such as America and Europe rules and regulations such as RoHS of making laws very early are forbidden
Use environmentally harmful products containing lead；It is 400 DEG C or less gas although vanadate seal glass has lower softening point temperature
Close property is bonded most important material, but vanadate glass is easy crystallization, poor chemical stability, melting process in use
It needs using logical Oxygen Condition, and the V in glass raw material2O5There are chronic toxic action, and V to human body2O5It is that one kind is partly led
Body material, conductivity is higher after being melting into glass, has a negative impact to by the insulation performance of sealing device；Phosphate glass
With good environment friendly, but its softening temperature is high, generally at 400 DEG C or more, and the thermal expansion of phosphate glass
Coefficient is generally larger, and chemical stability is poor.
With the fast development of modern microelectronic technology and photoelectron technology and device miniaturization and element precise treatment pair
The requirements at the higher level of sealing-in product air-tightness and reliability, especially environmental protection cry grow to even greater heights, and propose to seal glass
More severe requirement: except meeting chemical stability, thermal expansion matching and can be seal etc. in addition to basic demands, sealing-in temperature
Spend it is lower and lower, to be protected to the greatest extent to by sealing device, because excessively high glass transition temperature will lead to glass
The melting temperature sealing of glass increases, and is also unfavorable for the mobility of glass when sealing-in, if poor flow quality, vitreum is impossible to be covered with whole
A sealed space, wetting is insufficient, and sealing strength reduces, and will cause the chronic leakage of sealing device；Its sealing strength is also increasingly
Height, to meet the limit sealing-in condition such as vacuum, negative pressure；In addition, must not be poisonous and harmful containing lead, cadmium etc. in sealing glass composition
Ingredient, to meet the basic demand of electronic and electrical equipment environmental protection.
It needs in the sealing of the semiconductor chips such as hyundai electronics component sealing-in field such as mobile phone, PC computer using high insulation
Value, sealing temperature is low, thermal expansion coefficient and matched glass powder are as seal, sealing materials, but current environment-friendly type seal glass is very
Difficulty reaches requirement,
Seal glass containing alkali metal such as K, Na, conductivity is generally higher, is not suitable for electronics industry use；And with SiO2
Based on glass sealing temperature it is high, softening temperature is all larger than 550 DEG C, therefore is unsuitable for microelectronic industry use.Especially with
The development of mobile phone 5G technology, lightweight, precise treatment and the functionalization of electronic equipment and advanced semiconductor devices are (as true
Pocket part etc.) development and diode extensive application, urgent need and tight is proposed to the seal glass of field of electronic materials
Urgent requirement, it is desirable that glass should have following property:
1) glass not crystallization；
2) low melting point；
3) glass phase is stablized；
4) thermal expansion coefficient is suitable for；
5) chemical stability is good.
Especially mobile phone and microelectronic material industry, in order to protect the oxidation of the metal parts in vacuum device pipe to deform,
It plays a protective role simultaneously to materials such as fluorescent powder, semiconductors on component, it is necessary to carry out sealing-in at a lower temperature, but same
When in order to reach the requirement of vacuum degree, it is desirable that can under 400 DEG C or lower temperature to glass shell or ceramic shell into
Row seal, or be vacuum-evacuated under the conditions of 400 DEG C or so, in order to prevent temperature of the seal, sealing materials in vacuum evacuation
Under not softening transform, it is necessary to make seal, sealing materials that there is thermosetting property, guarantee the at a temperature of not softening transform in vacuum evacuation, so that envelope
Row's technique is addressed.And can stringent limitation in terms of the seal glass of 400 DEG C and following sealing is by raw material, it is available
Oxide is few, and existing sealing glass material has been difficult meet the needs of current electronic industry currently on the market.Low-temperature sealing
Why very low the softening temperature of glass is, related to screening of nuclear charge with electronics or anion, screen of the anion to cation
Cover the structure and its property for largely determining substance.The degree of shielding is related with ionic polarizability first, ion pole
Rate is higher, and the softening temperature of substance is lower, since Bi and Pb are adjacent in the periodic table of elements, has similar physical chemistry
Matter, and Bi3+Due to having very big polarizability, fusion temperature is relatively low, so in the research of Environment-friendlylow-temperature low-temperature seal glass
In, melting temperature sealing is low, electrical insulation capability is good, thermal expansion coefficient adjustable range is wide, price is low, energy is aobvious because having for bismuthate glass
The advantages that work reduces environmental pollution and obtain extensive concern.
Therefore, exploitation sealing temperature is highly desirable in 400 DEG C or so of environment-friendly type bismuthates sealing glass material, and
With boundless market prospects.
Summary of the invention
The object of the present invention is to provide a kind of environment-friendly type, without the low sealing-in glass of heavy metallic oxide and softening temperature
Glass, the present invention also provides a kind of preparation methods of Environment-friendlylow-temperature low-temperature seal glass.
In order to solve the above technical problems, present invention employs following technical solutions:
A kind of Environment-friendlylow-temperature low-temperature seal glass is prepared by following oxide according to mass percent (wt.%):
Further, it is preferable to be prepared by following mass percent (wt.%):
Further, SiO2+Al2O3Total amount≤5wt.%.
Further, without containing any one of alkali and alkaline earth metal ions oxide, alkali metal oxygen here in component
Compound refers to Li2O、Na2O、K2O、Rb2O、Cs2O、Fr2Any one of O etc.；Here alkaline earth oxide refer to MgO,
Any one of CaO, SrO, BaO etc..
Further, component does not contain environmentally harmful metal oxide such as As2O3、Sb2O5、BaO、PbO、Tl2O、
CdO、BeO、V2O5Deng it is any.
Further, glass is (55~70) × 10 in the glass average thermal linear expansion coefficient of 30-380 DEG C of range-7/
℃。
Further, the softening point temperature of glass is less than 400 DEG C.
The present invention provides another technical solution, a kind of preparation method of Environment-friendlylow-temperature low-temperature seal glass, including following step
It is rapid:
Step 1: by SiO2、Al2O3、B2O3、Bi2O3、ZnO、Y2O3、WO3、TiO2、SnO2Equal oxides are by mass percentage
Raw material is weighed, is put into platinum crucible after mixing；
Step 2: and then melt platinum crucible 1~3 hour at a temperature of 900~1200 DEG C, it is uniform to glass melting
Afterwards, melten glass liquid is poured into water quenching in deionized water；
Step 3: and then the dry fragment for obtaining glass melt；
Step 4: the glass after drying is subjected to ball mill grinding again, and dried 200 meshes, obtains low-temperature sealing glass
Glass material powder.
Compared with prior art, the beneficial effects of the present invention are:
(1), the present invention without containing environmentally harmful metal oxide or heavy metallic oxide such as As2O3, Sb2O5,
Any one of BaO, PbO, Tl2O, CdO, BeO, V2O5 etc., it is environmentally protective；
(2), glass softening point temperature of the invention is lower, and the softening point temperature of glass avoids excessive temperature less than 400 DEG C
Destruction to other elements；
(3), seal glass provided by the invention is with good stability in use environment；
(4), thermal expansion coefficient of the invention is suitable for that glass is in the average thermal linear expansion coefficient of 30-380 DEG C of range
(55~70) × 10-7/℃；
(5), the preparation low in raw material price that selects of the present invention, sources multiplicity, it is simple and easy to get to prepare raw material, technique letter
It is monostable fixed, it is at low cost.
Specific embodiment
Below in conjunction with the embodiment of the present invention, technical solution in the embodiment of the present invention is clearly and completely retouched
It states, it is clear that described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.Based on the present invention
In embodiment, every other implementation obtained by those of ordinary skill in the art without making creative efforts
Example, shall fall within the protection scope of the present invention.
The present invention provides a kind of Environment-friendlylow-temperature low-temperature seal glass, is made by following oxide according to mass percent (wt.%)
It is standby to form:
In the present invention, Bi2O3With reduction glass softening point, make glass that there is mobility appropriate and tune in fusing
Thermal expansion coefficient of glass is saved, specific gravity of glass, Bi are increased3+Mainly with [BiO in glass network6] and [BiO3] form exist,
Bi2O3Content mass percent (wt.%) is 30-50, preferably 35-45wt.%, Bi2O3Content be lower than 30wt.%, be not easy
The glass of low softening temperature is obtained, while the chemical-resistant stability of glass can be reduced；Bi2O3When content is higher than 50wt.%, glass
Thermal expansion coefficient will increase.
In the present invention, B2O3It is network former, and constitutes the ingredient of glass skeleton, while being a kind of reduction again
The cosolvent of glass smelting viscosity, and reduce the main component of glass transition temperature.Boron oxygen triangle body [BO3] and boron oxygen four sides
Body [BO4] it is structural component, boron may be with triangle body [BO at different conditions3] or boron oxygen tetrahedron [BO4] exist, in high temperature
It when melting conditions, is generally more difficult to form boron oxygen tetrahedron, and can only exist in a manner of trihedral, but in low temperature, certain
Under the conditions of B3+Have and capture free oxygen and form tetrahedral trend, makes close structure and improve the low temperature viscosity of glass, but due to it
There is the characteristic that high temperature reduces glass viscosity and low temperature improves glass viscosity, also determines that its content range is smaller.B2O3Quality
Percentage (wt.%) is 8-20, preferably 10-18wt.%.B2O3Content be lower than 8wt.%, hydrotropy can not be played the role of,
The chemical stability of glass can be reduced simultaneously；B2O3Content be greater than 20wt.%, the coefficient of expansion and the machinery that can reduce glass be strong
Degree, while be inclined to the split-phase of glass and increasing.
ZnO is glass intermediate oxide, and still, usually it is but with [ZnO6] octahedral form deposits as network outer body
When the free oxygen in glass is enough, it can also be with [ZnO4] tetrahedral form enters in the network structure of glass.ZnO
Mass percent (wt.%) be 26-45, preferably 30-40wt.%.The content of ZnO is lower than 26wt.%, can not play hydrotropy
Effect, while the chemical stability of glass can be reduced；The content of ZnO is greater than 45wt.%, can improve the coefficient of expansion of glass,
It is simultaneously inclined to the split-phase of glass to increase.The introducing of ZnO can be zinc oxide, and a small amount of zinc peroxide ZnO can also be added2。
Y2O3It is rare earth oxide, the thermal expansion coefficient and softening point temperature of glass can be reduced, the chemically-resistant for improving glass is steady
It is qualitative, while the crystallization of glass can be effectively suppressed, reduce sealing temperature.Y2O3Mass percent (wt.%) be 1-8, preferably
2-6wt.%.Y2O3Content be lower than 1wt.%, can not play the role of reducing glass transition temperature, while glass can be reduced
Chemical stability；Y2O3Content be greater than 8wt.%, will increase the tendency towards devitrification of glass.
WO3It can increase the compatibility with parent glass, reduce the softening temperature and sealing temperature of glass, WO3Quality percentage
It is 0.1-5, preferably 1-2wt.%, WO than (wt.%)3Content be lower than 0.1wt.%, fluxing effect, WO can not be played3Contain
Amount is higher than 5wt.%, can reduce the chemical stability and mechanical strength of glass.
TiO2The effect of main stabilization agent can improve the mechanical strength and chemical stability of glass, reduce the soft of glass
Change temperature and sealing temperature, TiO2Mass percent (wt.%) be 0.1-1, TiO2Content be lower than 0.1wt.%, Wu Faqi
To fluxing effect, TiO2Content be higher than 1wt.%, will increase the tendency towards devitrification of glass.
SnO2It is as glass fining agent, for bubble, SnO in fining glass melt2Mass percent (wt.%)
For 0.1-1%.
SiO2It is glass former oxide, SiO2Mass percent (wt.%) be 0-5, SiO2The heat of glass can be reduced
The coefficient of expansion improves thermal stability, chemical stability, mechanical strength of glass etc., but content is higher than 5wt.%, can improve glass
Softening temperature and sealing temperature.
Al2O3Belong to the intermediate oxide of glass, Al3+There are two types of co-ordination states, that is, are located in tetrahedron or octahedron,
When oxygen is enough in glass, aluminum-oxygen tetrahedron [AlO is formed4], continuous network is formed with oxygen-octahedron, when oxygen in glass
When insufficient, alumina octahedral [AlO is formed6], it is in for network outer body in the hole of silica structure network, so centainly containing
Measure range in can and SiO2、B2O3The main body that glass network is formed.Al2O3Mass percent (wt.%) be 0-5, Al2O3Energy
Improve chemical durability of glass, thermal stability, mechanical strength, but Al2O3Content, which is greater than 5wt.%, can dramatically increase glass sealing temperature
Degree and softening temperature, increase the glass melting temperature of glass, while will increase the crystallization tendency of glass.
A kind of Environment-friendlylow-temperature low-temperature seal glass of the present invention, SiO2+Al2O3Total amount be no more than 5wt.%；
A kind of Environment-friendlylow-temperature low-temperature seal glass of the present invention, contains substantially no alkali and alkaline earth metal ions oxide
Any one of, alkali metal oxide here refers to Li2O、Na2O、K2O、Rb2O、Cs2O、Fr2Any one of O etc.；Here
Alkaline earth oxide refer to any one of MgO, CaO, SrO, BaO etc..Because glass is typical ion-conductive material,
Its electrical conduction mechanism be the alkali metal ion movement on the scene pretended under and caused by, the conductivity of glass can improve, so, for
For the more demanding sealing device of insulation performance, alkali metal oxide or alkaline earth oxide are not introduced generally.Further,
A kind of Environment-friendlylow-temperature low-temperature seal glass, which is characterized in that glass is swollen in the glass average linear heat of 30-380 DEG C of range
Swollen coefficient is (55~70) × 10-7/℃；The softening point temperature of glass is less than 400 DEG C.
Low-temperature sealing glass according to the requirement of environment-friendly electronic material, especially for fields such as mobile communication, microelectronics
Glass has been free from alkali metal oxidation to the Property requirements of glass used, a kind of Environment-friendlylow-temperature low-temperature seal glass type of the invention
The bismuthate glass of object, alkaline earth oxide, the glass are any environmentally harmful with being free of in low softening temperature, glass
Heavy metallic oxide such as As2O3、Sb2O5、BaO、PbO、Tl2O、CdO、BeO、V2O5Deng it is any, even if containing and its pettiness
Amount be also due to other glass raw material institutes band.
A kind of preparation method of Environment-friendlylow-temperature low-temperature seal glass of the present invention, comprising the following steps:
Step 1: by SiO2、Al2O3、B2O3、Bi2O3、ZnO、Y2O3、WO3、TiO2、SnO2Equal oxides are by mass percentage
Raw material is weighed, is put into platinum crucible after mixing；
Step 2: and then melt platinum crucible 1~3 hour at a temperature of 900~1200 DEG C, it is uniform to glass melting
Afterwards, melten glass liquid is poured into water quenching in deionized water；
Step 3: and then the dry fragment for obtaining glass melt；
Step 4: the glass after drying is subjected to ball mill grinding again, and dried 200 meshes, obtains low-temperature sealing glass
Glass material powder.
It is as follows to a kind of parameter that Environment-friendlylow-temperature low-temperature seal glass is measured of the invention and measuring method and instrument:
(1) 20-300 DEG C of mean thermal expansion coefficients α20/300[10-7/℃]；
(2) the expansion softening point temperature T of glassf(℃)；
Wherein, 20-300 DEG C of linear expansion coefficient of glass is measured using horizontal expander instrument, with average linear expansion coefficient table
Show, is measured using method as defined in ISO 7991；The expansion softening point temperature T of glassfIt is obtained by glass thermal expansion curve test
Out.
The chemical composition (wt.%) and glass properties of 1 embodiment of table
The following are raw materials used and ingredient requirement in embodiment is as follows:
Quartz sand (it is high-purity, 150 μm of oversizes be 1% or less, 45 μm of screenings be 30% or less, Fe2O3Content is less than
0.01wt.%), (400 μm of oversizes are 10% for aluminium hydroxide or aluminium oxide (analyzing pure, 50 μm of average grain diameter), boric acid or boric anhydride
Below, 63 μm of screenings are 10% or less), tin oxide (analysis is pure, and 60 μm of oversizes of average grain diameter are 1% or less), bismuth oxide
(analysis is pure), zinc oxide (analysis is pure), yttrium oxide (analysis is pure), tungsten oxide (analysis is pure), titanium oxide (analysis is pure).
Embodiment 1
A kind of Environment-friendlylow-temperature low-temperature seal glass is prepared by following oxide according to mass percent (wt.%):
Firstly, selecting raw material by 1 embodiment of table, 1 glass composition, and require to carry out alkali metal content in glass raw material
Strict control, makes its ingredient meet the glass chemistry composition of table 1, and it is small that 2 are then melted at a temperature of 1050 DEG C using platinum crucible
When, after glass batch is fused into the glass melt of homogeneous, it is 70mm × 70mm that glass melt, which is poured into preheated size,
Castable in the heat-resisting steel mold of × 10mm, then anneals.Its test performance is as shown in table 1,20-300 DEG C of (1) it is flat
Equal linear expansion coefficient 64 × 10-7/℃；(2) 330 DEG C of the expansion softening point temperature of glass.
Embodiment 2
A kind of Environment-friendlylow-temperature low-temperature seal glass is prepared by following oxide according to mass percent (wt.%):
Raw material is selected by 1 embodiment of table, 2 glass composition, and requires strictly to control alkali metal content in glass raw material
System is made its ingredient meet the glass chemistry composition of table 1, is then melted 3 hours at a temperature of 950 DEG C using platinum crucible, to glass
After glass batch melting is at the glass melt of homogeneous, it is 70mm × 70mm × 10mm that glass melt, which is poured into preheated size,
Castable in heat-resisting steel mold, then anneals.The basic performance of sample is shown in table 1.(1) it is averaged for 20-300 DEG C
Linear expansion coefficient 61 × 10-7/℃；(2) 390 DEG C of the expansion softening point temperature of glass.
Embodiment 3
A kind of Environment-friendlylow-temperature low-temperature seal glass is prepared by following oxide according to mass percent (wt.%):
Raw material is selected by 1 embodiment of table, 3 glass composition, and requires strictly to control alkali metal content in glass raw material
System is made its ingredient meet the glass chemistry composition of table 1, is then melted 2.5 hours at a temperature of 1000 DEG C using platinum crucible, to
After glass batch is fused into the glass melt of homogeneous, it is 70mm × 70mm × 10mm that glass melt, which is poured into preheated size,
Heat-resisting steel mold in castable, then anneal.The basic performance of sample is shown in table 1.(1) 20-300 DEG C flat
Equal linear expansion coefficient 69 × 10-7/℃；(2) 340 DEG C of the expansion softening point temperature of glass.
Embodiment 4
A kind of Environment-friendlylow-temperature low-temperature seal glass is prepared by following oxide according to mass percent (wt.%):
Raw material is selected by 1 embodiment of table, 4 glass composition, and requires strictly to control alkali metal content in glass raw material
System makes its ingredient meet the glass chemistry composition of table 1, and uses melting process system and test-strips same as Example 1
Part shows the basic performance of sample in table 1.(1) 20-300 DEG C of average linear expansion coefficient 57 × 10-7/℃；(2) glass
375 DEG C of softening point temperature of expansion.
Embodiment 5
A kind of Environment-friendlylow-temperature low-temperature seal glass is prepared by following oxide according to mass percent (wt.%):
Raw material is selected by 1 embodiment of table, 5 glass composition, and requires strictly to control alkali metal content in glass raw material
System makes its ingredient meet the glass chemistry composition of table 1, and uses melting process system and test-strips same as Example 1
Part shows the basic performance of sample in table 1.(1) 20-300 DEG C of average linear expansion coefficient 68 × 10-7/℃；(2) glass
365 DEG C of softening point temperature of expansion.
The data obtained by embodiment are it is known that a kind of Environment-friendlylow-temperature low-temperature seal glass of the invention has softening temperature
Advantage low, without harmful heavy metal, suitable for fields such as mobile communication, microelectronic material, electric sealing-ins.
The foregoing is merely presently preferred embodiments of the present invention, is not intended to limit the invention, protection scope of the present invention by
Claims limit.Those skilled in the art can appoint to what the present invention made within the spirit and scope of the present invention
What modification or equivalent replacement, improvement etc., this modification or equivalent replacement, which are also considered as, to be fallen within the scope and spirit of the invention.
Claims (8)
1. a kind of Environment-friendlylow-temperature low-temperature seal glass, which is characterized in that be prepared by following oxide according to mass percent:
2. a kind of Environment-friendlylow-temperature low-temperature seal glass according to claim 1, which is characterized in that preferably pressed by following oxide
It is prepared according to mass percent:
3. a kind of Environment-friendlylow-temperature low-temperature seal glass according to claim 1 or 2, it is characterised in that: the SiO2And Al2O3
Total amount≤5wt.%.
4. a kind of Environment-friendlylow-temperature low-temperature seal glass according to claim 1, which is characterized in that do not contain alkali metal in component
Any one of with alkaline earth oxide, alkali metal oxide here refers to Li2O、Na2O、K2O、Rb2O、Cs2O、Fr2O etc.
Any one of；Here alkaline earth oxide refers to any one of MgO, CaO, SrO, BaO etc..
5. a kind of Environment-friendlylow-temperature low-temperature seal glass according to claim 1, which is characterized in that without containing to environment in component
Harmful metal oxide or heavy metallic oxide such as As2O3、Sb2O5、BaO、PbO、Tl2O、CdO、BeO、V2O5Deng any
Kind.
6. a kind of Environment-friendlylow-temperature low-temperature seal glass according to claim 1, it is characterised in that: in the glass of 30-380 DEG C of range
Glass average thermal linear expansion coefficient is (55~70) × 10-7/℃。
7. a kind of Environment-friendlylow-temperature low-temperature seal glass according to claim 1, it is characterised in that: the softening point temperature < of glass
400℃。
8. a kind of preparation method of Environment-friendlylow-temperature low-temperature seal glass, which comprises the following steps:
Step 1: by SiO2、Al2O3、B2O3、Bi2O3、ZnO、Y2O3、WO3、T iO2、SnO2Equal oxides claim by mass percentage
Content of starting materials is put into platinum crucible after mixing；
Step 2: and then melt platinum crucible 1~3 hour at a temperature of 900~1200 DEG C, it, will after glass melting is uniform
Melten glass liquid pours into water quenching in deionized water；
Step 3: and then the dry fragment for obtaining glass melt；
Step 4: the glass after drying is subjected to ball mill grinding again, and dried 200 meshes, obtains low temperature sealing glass material
Feed powder body.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910561222.3A CN110217993B (en) | 2019-06-26 | 2019-06-26 | Environment-friendly low-temperature sealing glass and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910561222.3A CN110217993B (en) | 2019-06-26 | 2019-06-26 | Environment-friendly low-temperature sealing glass and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110217993A true CN110217993A (en) | 2019-09-10 |
| CN110217993B CN110217993B (en) | 2022-05-27 |
Family
ID=67815093
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910561222.3A Active CN110217993B (en) | 2019-06-26 | 2019-06-26 | Environment-friendly low-temperature sealing glass and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110217993B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111847882A (en) * | 2020-08-10 | 2020-10-30 | 河北曜阳新材料技术有限公司 | Low-temperature sealing glass and preparation method thereof |
| CN114195395A (en) * | 2021-12-08 | 2022-03-18 | 安徽大学 | Low-melting-point lead-free glass powder for passivating and protecting semiconductor and preparation method thereof |
| CN114212995A (en) * | 2021-12-27 | 2022-03-22 | 中建材蚌埠玻璃工业设计研究院有限公司 | Preparation method suitable for OLED sealing solder |
| CN114590999A (en) * | 2022-01-20 | 2022-06-07 | 广西科技大学 | Low-melting-point lead-free glass powder and preparation method thereof |
Citations (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE69020114D1 (en) * | 1989-11-28 | 1995-07-20 | Matsushita Electric Ind Co Ltd | Sealing glass. |
| JP2005158152A (en) * | 2003-11-26 | 2005-06-16 | Matsushita Electric Ind Co Ltd | Magnetic head |
| US20060105898A1 (en) * | 2004-11-12 | 2006-05-18 | Asahi Techno Glass Corporation | Low melting glass, sealing composition and sealing paste |
| CN101066838A (en) * | 2007-06-05 | 2007-11-07 | 东华大学 | No-lead sealing glass powder with low smelting point and low expansion coefficient and its prepn process |
| CN101113074A (en) * | 2007-06-29 | 2008-01-30 | 东华大学 | Barium crown glass powder for electronic slurry and preparation method thereof |
| JP2008088023A (en) * | 2006-10-03 | 2008-04-17 | Tokan Material Technology Co Ltd | Sealing composition |
| CN101376563A (en) * | 2008-09-28 | 2009-03-04 | 陈培 | Low-melting glass containing nano zinc oxide and preparation thereof |
| CN101376561A (en) * | 2008-09-28 | 2009-03-04 | 陈培 | Low-melting point lead-less glasses powder for frit slurry, and preparation and use thereof |
| CN101528621A (en) * | 2006-10-24 | 2009-09-09 | 日本电气硝子株式会社 | Bismuth-base glass composition and bismuth-base material |
| CN101544470A (en) * | 2009-04-20 | 2009-09-30 | 贵阳晶华电子材料有限公司 | High-bismuth-oxide dielectric material for electrode coating |
| CN101602573A (en) * | 2009-07-21 | 2009-12-16 | 中国计量学院 | A kind of bismuthate lead-free sealing glass material with low melting point and preparation method thereof |
| CN101723589A (en) * | 2008-10-29 | 2010-06-09 | 珠海彩珠实业有限公司 | Lead-free glass powder with low melting point for sealing PDP and preparation method thereof |
| TW201033152A (en) * | 2008-12-12 | 2010-09-16 | Asahi Glass Co Ltd | Sealing glass, glass member having sealing material layer, and electronic device and method for producing the same |
| CN102120693A (en) * | 2010-01-11 | 2011-07-13 | 上海歌灵新材料科技有限公司 | Lead-free sealing glass and preparation method thereof |
| CN106495490A (en) * | 2016-11-01 | 2017-03-15 | 福州大学 | One kind contains SiO2LED low temperature sealing glass |
| CN109867447A (en) * | 2017-12-01 | 2019-06-11 | 成都光明光电股份有限公司 | Devitrified glass and its substrate |
-
2019
- 2019-06-26 CN CN201910561222.3A patent/CN110217993B/en active Active
Patent Citations (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE69020114D1 (en) * | 1989-11-28 | 1995-07-20 | Matsushita Electric Ind Co Ltd | Sealing glass. |
| JP2005158152A (en) * | 2003-11-26 | 2005-06-16 | Matsushita Electric Ind Co Ltd | Magnetic head |
| US20060105898A1 (en) * | 2004-11-12 | 2006-05-18 | Asahi Techno Glass Corporation | Low melting glass, sealing composition and sealing paste |
| JP2008088023A (en) * | 2006-10-03 | 2008-04-17 | Tokan Material Technology Co Ltd | Sealing composition |
| CN101528621A (en) * | 2006-10-24 | 2009-09-09 | 日本电气硝子株式会社 | Bismuth-base glass composition and bismuth-base material |
| CN101066838A (en) * | 2007-06-05 | 2007-11-07 | 东华大学 | No-lead sealing glass powder with low smelting point and low expansion coefficient and its prepn process |
| CN101113074A (en) * | 2007-06-29 | 2008-01-30 | 东华大学 | Barium crown glass powder for electronic slurry and preparation method thereof |
| CN101376561A (en) * | 2008-09-28 | 2009-03-04 | 陈培 | Low-melting point lead-less glasses powder for frit slurry, and preparation and use thereof |
| CN101376563A (en) * | 2008-09-28 | 2009-03-04 | 陈培 | Low-melting glass containing nano zinc oxide and preparation thereof |
| CN101723589A (en) * | 2008-10-29 | 2010-06-09 | 珠海彩珠实业有限公司 | Lead-free glass powder with low melting point for sealing PDP and preparation method thereof |
| TW201033152A (en) * | 2008-12-12 | 2010-09-16 | Asahi Glass Co Ltd | Sealing glass, glass member having sealing material layer, and electronic device and method for producing the same |
| CN101544470A (en) * | 2009-04-20 | 2009-09-30 | 贵阳晶华电子材料有限公司 | High-bismuth-oxide dielectric material for electrode coating |
| CN101602573A (en) * | 2009-07-21 | 2009-12-16 | 中国计量学院 | A kind of bismuthate lead-free sealing glass material with low melting point and preparation method thereof |
| CN102120693A (en) * | 2010-01-11 | 2011-07-13 | 上海歌灵新材料科技有限公司 | Lead-free sealing glass and preparation method thereof |
| CN106495490A (en) * | 2016-11-01 | 2017-03-15 | 福州大学 | One kind contains SiO2LED low temperature sealing glass |
| CN109867447A (en) * | 2017-12-01 | 2019-06-11 | 成都光明光电股份有限公司 | Devitrified glass and its substrate |
Non-Patent Citations (2)
| Title |
|---|
| （苏）阿本: "《玻璃化学》", 31 October 1981, 中国建筑工业出版社 * |
| 施华: "《电真空材料及工艺 上》", 30 September 1961, 人民教育出版社 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111847882A (en) * | 2020-08-10 | 2020-10-30 | 河北曜阳新材料技术有限公司 | Low-temperature sealing glass and preparation method thereof |
| CN114195395A (en) * | 2021-12-08 | 2022-03-18 | 安徽大学 | Low-melting-point lead-free glass powder for passivating and protecting semiconductor and preparation method thereof |
| CN114212995A (en) * | 2021-12-27 | 2022-03-22 | 中建材蚌埠玻璃工业设计研究院有限公司 | Preparation method suitable for OLED sealing solder |
| CN114212995B (en) * | 2021-12-27 | 2023-10-20 | 中建材玻璃新材料研究院集团有限公司 | Preparation method of OLED sealing solder |
| CN114590999A (en) * | 2022-01-20 | 2022-06-07 | 广西科技大学 | Low-melting-point lead-free glass powder and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110217993B (en) | 2022-05-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110217993A (en) | A kind of Environment-friendlylow-temperature low-temperature seal glass and preparation method thereof | |
| CN110256060B (en) | High-frequency low-dielectric-constant low-temperature co-fired ceramic material and preparation method thereof | |
| CN111018352B (en) | Glass material for titanium and titanium alloy-kovar sealing and preparation method and application thereof | |
| CN103880290B (en) | A kind of preparation method and applications of high expansion coefficient copper sealing glass powder | |
| CN114835404B (en) | Glass powder for low-temperature sintering MLCC end electrode slurry and preparation method thereof | |
| CN106396409A (en) | Low-temperature lead-free glass binder for electronic paste and preparation method thereof | |
| CN106882923B (en) | A kind of devitrified glass and preparation method thereof of resistance to 650 DEG C of high temperature | |
| CN101597136A (en) | A kind of lead-free low-melting sealing glass and preparation method thereof | |
| CN106882922B (en) | A kind of seal glass and preparation method thereof of resistance to 550 DEG C of high temperature | |
| CN101265024A (en) | Low-melting point leadless borophosphate seal glass powder and preparation method thereof | |
| CN114590999B (en) | Low-melting-point lead-free glass powder and preparation method thereof | |
| CN112499978A (en) | Glass powder for low-melting-point electronic paste and preparation method thereof | |
| CN114477768A (en) | Lead-free low-melting-point sealing glass doped with fusible metal alloy and preparation method thereof | |
| CN109399944A (en) | It is a kind of for the glass powder and preparation method of low-temperature sealing and application | |
| JP4789052B2 (en) | Semiconductor encapsulation glass, semiconductor encapsulation envelope, and semiconductor element encapsulation method | |
| CN110423013A (en) | A kind of copper electrocondution slurry glass powder, preparation method and application | |
| CN105731803A (en) | Copper sealing glass powder, preparation method and application thereof, and electrodes of battery | |
| US4704370A (en) | Sealing glass composition | |
| JP4863580B2 (en) | Glass composition, insulating film, and silicon device | |
| CN116730619B (en) | Low-loss microcrystalline glass material for LTCC (Low temperature Co-fired ceramic) and preparation method thereof | |
| CN101376562B (en) | Dielectric layer lead-less glasses material for plasma display screen | |
| CN107010837A (en) | A kind of rare earth doped element leadless and low-melting point sealing glass powder and its manufacture method | |
| WO2022228340A1 (en) | Low dielectric sealing glass powder for miniature radio-frequency glass insulator | |
| CN112551902A (en) | Low-melting-point glass powder containing alkaline earth metal and preparation method and application thereof | |
| CN108975689A (en) | A kind of low-k low dielectric-loss glass |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| CB02 | Change of applicant information |
Address after: 101, building 17, jinhufang, No. 288, Xiongzhou South Road, Liuhe District, Nanjing, Jiangsu Province, 210000 Applicant after: Lumixing Special Glass Technology Co.,Ltd. Address before: 101, building 17, jinhufang, 288 Xiongzhou South Road, Liuhe District, Wuxi City, Jiangsu Province 210000 Applicant before: Lumixing Special Glass Technology Co.,Ltd. |
|
| CB02 | Change of applicant information | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |