CN110217993B - Environment-friendly low-temperature sealing glass and preparation method thereof - Google Patents
Environment-friendly low-temperature sealing glass and preparation method thereof Download PDFInfo
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- CN110217993B CN110217993B CN201910561222.3A CN201910561222A CN110217993B CN 110217993 B CN110217993 B CN 110217993B CN 201910561222 A CN201910561222 A CN 201910561222A CN 110217993 B CN110217993 B CN 110217993B
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- 239000005394 sealing glass Substances 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title abstract description 10
- 239000011521 glass Substances 0.000 claims abstract description 120
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000002994 raw material Substances 0.000 claims abstract description 22
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 19
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000000463 material Substances 0.000 claims abstract description 14
- 238000002844 melting Methods 0.000 claims abstract description 14
- 230000008018 melting Effects 0.000 claims abstract description 14
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(iii) oxide Chemical compound O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 claims abstract description 13
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 11
- 229910052593 corundum Inorganic materials 0.000 claims abstract description 11
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 11
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 11
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 11
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 11
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 11
- 229910001845 yogo sapphire Inorganic materials 0.000 claims abstract description 11
- 239000000156 glass melt Substances 0.000 claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 8
- XOLBLPGZBRYERU-UHFFFAOYSA-N SnO2 Inorganic materials O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims abstract description 7
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000006060 molten glass Substances 0.000 claims abstract description 5
- 238000000498 ball milling Methods 0.000 claims abstract description 4
- 239000008367 deionised water Substances 0.000 claims abstract description 4
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 4
- 239000012634 fragment Substances 0.000 claims abstract description 4
- 239000007788 liquid Substances 0.000 claims abstract description 4
- 238000010791 quenching Methods 0.000 claims abstract description 4
- 230000000171 quenching effect Effects 0.000 claims abstract description 4
- 238000007873 sieving Methods 0.000 claims abstract description 4
- 238000005303 weighing Methods 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 10
- 239000000843 powder Substances 0.000 claims description 5
- 229910003439 heavy metal oxide Inorganic materials 0.000 abstract description 4
- 238000007789 sealing Methods 0.000 description 31
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 26
- 239000000126 substance Substances 0.000 description 22
- 239000011787 zinc oxide Substances 0.000 description 13
- 239000000203 mixture Substances 0.000 description 11
- 150000001340 alkali metals Chemical class 0.000 description 8
- 239000003566 sealing material Substances 0.000 description 8
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 7
- 229910052783 alkali metal Inorganic materials 0.000 description 6
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 6
- 238000004377 microelectronic Methods 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 239000004065 semiconductor Substances 0.000 description 5
- GOLCXWYRSKYTSP-UHFFFAOYSA-N Arsenious Acid Chemical compound O1[As]2O[As]1O2 GOLCXWYRSKYTSP-UHFFFAOYSA-N 0.000 description 4
- XGCTUKUCGUNZDN-UHFFFAOYSA-N [B].O=O Chemical compound [B].O=O XGCTUKUCGUNZDN-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 4
- 239000006066 glass batch Substances 0.000 description 4
- 239000005365 phosphate glass Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 229910000831 Steel Inorganic materials 0.000 description 3
- OBNDGIHQAIXEAO-UHFFFAOYSA-N [O].[Si] Chemical compound [O].[Si] OBNDGIHQAIXEAO-UHFFFAOYSA-N 0.000 description 3
- 238000000137 annealing Methods 0.000 description 3
- LJCFOYOSGPHIOO-UHFFFAOYSA-N antimony pentoxide Inorganic materials O=[Sb](=O)O[Sb](=O)=O LJCFOYOSGPHIOO-UHFFFAOYSA-N 0.000 description 3
- 238000005266 casting Methods 0.000 description 3
- 238000004891 communication Methods 0.000 description 3
- 239000012776 electronic material Substances 0.000 description 3
- 239000004615 ingredient Substances 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 description 3
- KOPBYBDAPCDYFK-UHFFFAOYSA-N Cs2O Inorganic materials [O-2].[Cs+].[Cs+] KOPBYBDAPCDYFK-UHFFFAOYSA-N 0.000 description 2
- FUJCRWPEOMXPAD-UHFFFAOYSA-N Li2O Inorganic materials [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 2
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- AKUNKIJLSDQFLS-UHFFFAOYSA-M dicesium;hydroxide Chemical compound [OH-].[Cs+].[Cs+] AKUNKIJLSDQFLS-UHFFFAOYSA-M 0.000 description 2
- XUCJHNOBJLKZNU-UHFFFAOYSA-M dilithium;hydroxide Chemical compound [Li+].[Li+].[OH-] XUCJHNOBJLKZNU-UHFFFAOYSA-M 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000010309 melting process Methods 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229910001953 rubidium(I) oxide Inorganic materials 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 239000006004 Quartz sand Substances 0.000 description 1
- 229910006735 SnO2SnO Inorganic materials 0.000 description 1
- CQBLUJRVOKGWCF-UHFFFAOYSA-N [O].[AlH3] Chemical compound [O].[AlH3] CQBLUJRVOKGWCF-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 239000006121 base glass Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910000416 bismuth oxide Inorganic materials 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 231100000085 chronic toxic effect Toxicity 0.000 description 1
- 239000006184 cosolvent Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000004031 devitrification Methods 0.000 description 1
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 239000006025 fining agent Substances 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 238000007496 glass forming Methods 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- DLINORNFHVEIFE-UHFFFAOYSA-N hydrogen peroxide;zinc Chemical compound [Zn].OO DLINORNFHVEIFE-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 229910001930 tungsten oxide Inorganic materials 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 229940105296 zinc peroxide Drugs 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- 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 environment-friendly low-temperature sealing glass, which is prepared from the following materials in percentage by mass: 30-50 wt.% 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 invention also provides a preparation method of the environment-friendly low-temperature sealing glass, which comprises the following steps: mixing SiO2、Al2O3、B2O3、Bi2O3、ZnO、Y2O3、WO3、TiO2、SnO2Weighing raw materials according to mass percentage, mixing uniformly, putting into a platinum crucible, melting the platinum crucible at 900-1200 ℃ for 1-3 hours, pouring molten glass liquid into deionized water for water quenching after glass is melted uniformly, drying to obtain fragments of glass melt, performing ball milling on the dried glass, crushing, drying and sieving with a 200-mesh sieve. The invention has the following advantages: does not contain heavy metal oxide harmful to the environment; the average linear thermal expansion coefficient of the glass in the range of 30-380 ℃ is (55-70) x 10‑7/° c; the glass has a softening point temperature of less than 400 ℃.
Description
Technical Field
The invention relates to a bismuthate environment-friendly low-temperature sealing glass material and a preparation method thereof, belonging to the technical field of glass materials and electronic materials.
Background
The low-temperature sealing glass is sealing glass with a melting point remarkably lower than that of common glass, can be used as a welding flux to be applied to vacuum technology and electronic technology, and can be widely applied to a plurality of fields of automobile electronics, household appliances, information communication technology, national defense and military, electronic paste, microelectronic technology, energy, aerospace and the like.
In the field of low-temperature sealing, epoxy resin organic adhesives are used as sealing materials for the shellless sealing of domestic semiconductor instrument and meter manufacturing enterprises for a long time, the organic materials are used, the high temperature generated in the work can age the organic matters, so that the sealing is in danger of air leakage, moisture absorption, electric leakage and the like, the sealing glass has no advantages in the aspects of environmental protection, chemical stability, water resistance, sealing stability and the like, and the performance cannot be accepted by the international market.
The sealing glass is popular to be used as a sealing material internationally, and the traditional low-temperature sealing glass mainly comprises low-temperature sealing glass such as lead acid salt glass, vanadate glass, phosphate glass and the like. The lead acid salt glass has the advantages of small dielectric loss, low softening temperature, good chemical stability and the like, but the lead acid salt glass can generate pollution and poison to human bodies and the environment in the process from preparation to use due to the fact that the lead acid salt glass contains PbO, and the lead-containing products harmful to the environment are forbidden to use by the RoHS regulation and other regulations of European and American developed countries for a long time; the vanadate sealing glass has a lower softening point temperature and is the most main material for airtight bonding below 400 ℃, but the vanadate glass is easy to crystallize in the using process and has poor chemical stability, the melting process needs to adopt an oxygen introducing condition, and V in the glass raw materials2O5Has a chronic toxic effect on the human body and V2O5The conductive glass is a semiconductor material, and has high conductivity after being melted into glass, so that the insulating property of a sealed device is negatively influenced; phosphate glass has good environmental friendliness, but the softening temperature of the phosphate glass is high and is generally above 400 ℃, and the phosphate glass has generally large thermal expansion coefficient and poor chemical stability.
With the rapid development of modern microelectronic technology and optoelectronic technology, and the miniaturization of devices and the precision of elements, the higher requirements on the air tightness and reliability of sealing products, especially the increasing trend of environmental protection, the sealing glass has more stringent requirements: besides meeting the basic requirements of chemical stability, thermal expansion matching, sealing performance and the like, the sealing temperature of the sealing material is lower and lower, so that a sealed device can be protected to the greatest extent, the sealing temperature of glass is increased due to the excessively high glass softening temperature, the fluidity of the glass during sealing is not facilitated, if the fluidity is poor, a whole sealing space cannot be filled with a glass body, the wetting is insufficient, the sealing strength is reduced, and the sealing device can be leaked chronically; the sealing strength of the sealing material is higher and higher so as to meet the limit sealing conditions of vacuum, negative pressure and the like; in addition, the components of the sealing glass do not contain toxic and harmful components such as lead, cadmium and the like, so that the basic requirements of electronic and electric products on environmental protection are met.
In the field of sealing modern electronic components, such as semiconductor chips of mobile phones, PCs and the like, glass powder with high insulation value, low sealing temperature, thermal expansion coefficient matched with the thermal expansion coefficient is required to be used as a sealing material, but the current environment-friendly sealing glass is difficult to meet the use requirement,
the sealing glass containing K, Na and other alkali metals has generally higher conductivity and is not suitable for the use in the electronic industry; and with SiO2The glass as the main body has high sealing temperature and softening temperature higher than 550 ℃, so the glass is not suitable for the microelectronic industry. Particularly, with the development of the 5G technology of the mobile phone, the light weight, the precision and the functionalization of the electronic equipment, the development of advanced semiconductor devices (such as vacuum devices) and the massive application of diodes, the sealing glass in the field of electronic materials is required to have urgent requirements and urgent requirements, and the glass is required to have the following properties:
1) the glass does not crystallize;
2) a low melting point;
3) the glass phase is stable;
4) the thermal expansion coefficient is appropriate;
5) the chemical stability is good.
Particularly in the industries of mobile phones and microelectronic materials, in order to protect the oxidation deformation of metal parts in vacuum device tubes and protect materials such as fluorescent powder, semiconductors and the like on components, sealing must be carried out at a lower temperature, but in order to meet the requirement of vacuum degree, sealing and sealing of a glass shell or a ceramic shell at a temperature of 400 ℃ or lower or vacuum exhaust at about 400 ℃ is required, in order to prevent the sealing material from softening and deforming at the vacuum exhaust temperature, the sealing material must be made to have thermosetting property, and the sealing material must be ensured to have the vacuum exhaust temperatureThe softening and deformation are avoided, so that the sealing and draining process is solved. The sealing glass capable of sealing at 400 ℃ and below is strictly limited by raw materials, the available oxides are few, and the existing sealing glass material on the market at present is difficult to meet the requirements of the current electronic industry. The softening temperature of the low-temperature sealing glass is very low, and is related to shielding of nuclear charges by electrons or anions, and the shielding of the anions to the cations determines the structure and the properties of the substance to a great extent. The degree of screening is related firstly to the ionic polarizability, the higher the ionic polarizability, the lower the softening temperature of the material, since Bi is adjacent to Pb in the periodic table and has similar physicochemical properties, and Bi3+Because of high polarizability and low melting temperature, bismuthate glass has attracted attention in the research of environment-friendly low-temperature sealing glass because of its advantages of low sealing temperature, good electrical insulation property, wide adjustable range of thermal expansion coefficient, low price, and capability of obviously reducing environmental pollution.
Therefore, the development of the environment-friendly bismuthate sealing glass material with the sealing temperature of about 400 ℃ is very necessary, and the market prospect is very wide.
Disclosure of Invention
The invention aims to provide the environment-friendly sealing glass which does not contain heavy metal oxide and has low softening temperature, and the invention also provides a preparation method of the environment-friendly low-temperature sealing glass.
In order to solve the technical problems, the invention adopts the following technical scheme:
the environment-friendly low-temperature sealing glass is prepared from the following oxides in percentage by mass (wt%):
further, it is preferably prepared from the following mass percentages (wt.%):
further, SiO2+Al2O3The total amount of (B) is less than or equal to 5 wt.%.
Further, any one of alkali metal and alkaline earth metal oxide is not contained in the composition, and the alkali metal oxide herein means Li2O、Na2O、K2O、Rb2O、Cs2O、Fr2O, etc.; the alkaline earth metal oxide herein means any of MgO, CaO, SrO, BaO, and the like.
Further, the composition does not contain metal oxides harmful to the environment such As As2O3、Sb2O5、BaO、PbO、 Tl2O、CdO、BeO、V2O5And the like.
Further, the average linear thermal expansion coefficient of the glass in the range of 30-380 ℃ is (55-70) x 10-7/℃。
Further, the glass has a softening point temperature of less than 400 ℃.
The invention provides another technical scheme, and a preparation method of environment-friendly low-temperature sealing glass comprises the following steps:
the method comprises the following steps: mixing SiO2、Al2O3、B2O3、Bi2O3、ZnO、Y2O3、WO3、TiO2、SnO2Weighing raw materials according to the mass percentage of the oxides, uniformly mixing the raw materials, and putting the mixture into a platinum crucible;
step two: then melting the platinum crucible at 900-1200 ℃ for 1-3 hours, and pouring molten glass liquid into deionized water for water quenching after the glass is uniformly molten;
step three: then drying to obtain fragments of the glass melt;
step four: and then ball-milling and crushing the dried glass, drying and sieving by a 200-mesh sieve to obtain the low-temperature sealing glass material powder.
Compared with the prior art, the invention has the beneficial effects that:
(1) the invention does not contain metal oxides or heavy metal oxides such As As which are harmful to the environment2O3、 Sb2O5、BaO、PbO、Tl2O、CdO、BeO、V2O5And the like, green and environment-friendly;
(2) the glass has a lower softening point temperature which is less than 400 ℃, so that the damage of the excessive temperature to other elements is avoided;
(3) the sealing glass provided by the invention has good stability in a use environment;
(4) the glass has a proper thermal expansion coefficient, and the average linear thermal expansion coefficient of the glass at the temperature of 30-380 ℃ is (55-70) × 10-7/℃；
(5) The preparation raw materials selected by the invention are low in price, various in sources, simple and easily available in preparation raw materials, simple and stable in process and low in cost.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention provides environment-friendly low-temperature sealing glass which is prepared from the following oxides in percentage by mass (wt.%):
in the present invention, Bi2O3Has the functions of lowering the softening point of the glass, enabling the glass to have proper fluidity when being melted, adjusting the thermal expansion coefficient of the glass and increasing the specific gravity of the glass，Bi3+In glass networks mainly [ BiO ]6]And [ BiO ]3]Is present in the form of Bi2O3The content mass percent (wt.%) is 30-50, preferably 35-45 wt.%, Bi2O3Less than 30 wt.%, it is not easy to obtain glass with low softening temperature, and the chemical resistance of the glass is reduced; bi2O3At contents higher than 50 wt.%, the coefficient of thermal expansion of the glass increases.
In the present invention, B2O3Is a glass forming oxide, is also a component for forming a glass framework, is a cosolvent for reducing the melting viscosity of glass, and is also a main component for reducing the softening temperature of the glass. Boron oxygen triangle (BO)3]And boron-oxygen tetrahedron [ BO4]Boron may be in the form of a trigonal [ BO ] under different conditions as a structural element3]Or boron-oxygen tetrahedron [ BO4]In the presence of B, it is difficult to form boron-oxygen tetrahedron under high-temperature melting conditions, but B is present only in the form of trihedron under certain conditions at low temperature3+There is a tendency to abstract free oxygen to form tetrahedron, making the structure compact and increasing the low temperature viscosity of the glass, but its content range is small due to its characteristics of reducing the viscosity of the glass at high temperature and increasing the viscosity of the glass at low temperature. B is2O3Is 8-20, preferably 10-18 wt.%. B is2O3The content of (A) is less than 8 wt.%, which can not play a role of assisting dissolution and can reduce the chemical stability of the glass; b is2O3Greater than 20 wt.%, reduces the coefficient of expansion and mechanical strength of the glass, while increasing the tendency of the glass to phase separate.
ZnO is a glass intermediate oxide, but usually it is present as [ ZnO ]6]The octahedron form exists as an extranet and can also be present as [ ZnO ] when sufficient free oxygen is present in the glass4]The tetrahedral form enters the network structure of the glass. The mass percent (wt.%) of ZnO is 26-45, preferably 30-40 wt.%. The content of ZnO is less than 26 wt%, so that the ZnO cannot play a role in assisting dissolution and can reduce the chemical stability of the glass; ZnO content of more than 45 wt.% improves the expansion coefficient of the glassWhile increasing the tendency of the glass to phase separate. The ZnO can be introduced into zinc oxide, or small amount of zinc peroxide ZnO can be added2。
Y2O3The rare earth oxide can reduce the thermal expansion coefficient and softening point temperature of the glass, improve the chemical resistance stability of the glass, effectively inhibit the crystallization of the glass and reduce the sealing temperature. Y is2O3Is 1-8, preferably 2-6 wt.%. Y is2O3The content of (a) is less than 1 wt.%, which cannot play a role in lowering the softening temperature of the glass and can also reduce the chemical stability of the glass; y is2O3Greater than 8 wt.%, increases the tendency of the glass to devitrify.
WO3Can increase the compatibility with the base glass and reduce the softening temperature and sealing temperature of the glass, WO3Is 0.1-5, preferably 1-2 wt.%, WO3At a content of less than 0.1 wt.%, fails to exert a fluxing effect, WO3Higher than 5 wt.%, the chemical stability and mechanical strength of the glass are reduced.
TiO2Mainly plays the role of a stabilizer, can improve the mechanical strength and the chemical stability of the glass, reduce the softening temperature and the sealing temperature of the glass, and adopts TiO2Is 0.1-1 wt.%, TiO2The content of (A) is less than 0.1 wt.%, the fluxing effect cannot be achieved, and TiO is2Higher than 1 wt.%, increases the devitrification tendency of the glass.
SnO2SnO used as a fining agent for fining bubbles in molten glass2Is 0.1-1% by mass (wt.%).
SiO2Is a glass former oxide, SiO2Is 0-5 mass percent (wt.%), SiO2The thermal expansion coefficient of the glass can be reduced, the thermal stability, the chemical stability, the mechanical strength and the like of the glass are improved, but the content is higher than 5 wt.%, and the softening temperature and the sealing temperature of the glass are improved.
Al2O3Belonging to the intermediate oxides of glass, Al3+In two coordination states, i.e. inIn tetrahedra or octahedra, when there is sufficient oxygen in the glass, AlO tetrahedra is formed4]Form a continuous network with the silicon-oxygen tetrahedra, and when the glass is deficient in oxygen, form aluminum-oxygen octahedra [ AlO ]6]In the cavities of the silicon-oxygen structure network for the network outer body, so that the silicon-oxygen structure network can be mixed with SiO in a certain content range2、B2O3A body formed by a glass network. Al (Al)2O3Is 0-5 mass% (wt.%), Al2O3Can improve the chemical stability, thermal stability and mechanical strength of the glass, but Al2O3A content of more than 5 wt.% significantly increases the sealing temperature and softening temperature of the glass, raising the melting temperature of the glass and increasing the tendency of the glass to crystallize.
The invention relates to environment-friendly low-temperature sealing glass, namely SiO2+Al2O3Does not exceed 5 wt.%;
the environment-friendly low-temperature sealing glass of the invention does not substantially contain any one of alkali metal and alkaline earth metal oxide, wherein the alkali metal oxide refers to Li2O、Na2O、K2O、Rb2O、Cs2O、Fr2O, etc.; the alkaline earth metal oxide herein refers to any of MgO, CaO, SrO, BaO, and the like. Because glass is a typical ion conductive substance, the conductivity of the glass is improved due to the movement of alkali metal ions under the action of field strength, so that alkali metal oxide or alkaline earth metal oxide is not generally introduced into a sealing device with higher requirement on insulating property. Furthermore, the environment-friendly low-temperature sealing glass is characterized in that the average linear thermal expansion coefficient of the glass at the temperature of 30-380 ℃ is (55-70) multiplied by 10-7/° c; the glass has a softening point temperature of less than 400 ℃.
According to the requirements of environment-friendly electronic materials, in particular to the requirements of low-temperature sealing glass used in the fields of mobile phone communication, microelectronics and the like on the properties of the glass, the environment-friendly low-temperature sealing glass of the invention is bismuthate glass without alkali metal oxide or alkaline earth metal oxide, and the type of the environment-friendly low-temperature sealing glass is bismuthate glass without alkali metal oxide or alkaline earth metal oxideThe glass has a low softening temperature, and the glass does not contain any heavy metal oxide harmful to the environment, such As As2O3、Sb2O5、BaO、PbO、Tl2O、 CdO、BeO、V2O5And the other glass raw materials, even if contained in a very small amount.
The invention relates to a preparation method of environment-friendly low-temperature sealing glass, which comprises the following steps:
the method comprises the following steps: mixing SiO2、Al2O3、B2O3、Bi2O3、ZnO、Y2O3、WO3、TiO2、SnO2Weighing raw materials according to the mass percentage of the oxides, uniformly mixing the raw materials, and putting the mixture into a platinum crucible;
step two: then melting the platinum crucible at 900-1200 ℃ for 1-3 hours, and pouring molten glass liquid into deionized water for water quenching after the glass is uniformly molten;
step three: then drying to obtain fragments of the glass melt;
step four: and then ball-milling and crushing the dried glass, drying and sieving by a 200-mesh sieve to obtain the low-temperature sealing glass material powder.
The parameters and the measuring method and the instrument for the environment-friendly low-temperature sealing glass are as follows:
(1) average coefficient of thermal expansion alpha of 20-300 DEG C20/300[10-7/℃]；
(2) Expansion softening point temperature T of glassf(℃)；
Wherein the linear expansion coefficient of the glass at 20-300 ℃ is measured by a horizontal dilatometer, expressed as the average linear expansion coefficient, and measured by a method specified in ISO 7991; expansion softening point temperature T of glassfThe glass thermal expansion curve test shows that the glass is obtained.
Table 1 chemical composition (wt.%) and glass properties of the examples
The following raw materials and raw material requirements used in the examples are as follows:
quartz sand (high purity, 1% or less of 150 μm oversize, 30% or less of 45 μm undersize, Fe)2O3Less than 0.01 wt.%), aluminum hydroxide or alumina (analytically pure, average particle size 50 μm), boric acid or boric anhydride (10% or less for 400 μm oversize and 10% or less for 63 μm undersize), tin oxide (analytically pure, average particle size 60 μm oversize and 1% or less), bismuth oxide (analytically pure), zinc oxide (analytically pure), yttrium oxide (analytically pure), tungsten oxide (analytically pure), titanium oxide (analytically pure).
Example 1
The environment-friendly low-temperature sealing glass is prepared from the following oxides in percentage by mass (wt%):
firstly, raw materials are selected according to the glass components in the example 1 in the table 1, the alkali metal content in the glass raw materials is required to be strictly controlled, the ingredients of the raw materials meet the glass chemical composition in the table 1, then a platinum crucible is used for melting at 1050 ℃ for 2 hours, after the glass batch is melted into a homogeneous glass melt, the glass melt is poured into a preheated heat-resistant steel mould with the size of 70mm multiplied by 10mm for casting forming, and then annealing is carried out. The test properties are shown in Table 1, (1) the average linear expansion coefficient at 20-300 deg.C is 64X 10-7/° c; (2) the glass has an expansion softening point temperature of 330 ℃.
Example 2
The environment-friendly low-temperature sealing glass is prepared from the following oxides in percentage by mass (wt%):
selecting raw materials according to the glass components in the example 2 in the table 1, strictly controlling the alkali metal content in the glass raw materials to enable the ingredients to meet the glass chemical composition in the table 1, then melting the raw materials for 3 hours at 950 ℃ by using a platinum crucible, pouring the glass melt into a preheated heat-resistant steel die with the size of 70mm multiplied by 10mm after the glass batch is melted into a homogeneous glass melt, casting and forming, and then annealing. The basic properties of the samples are shown in table 1. (1) Average linear expansion coefficient of 61X 10 at 20-300 deg.C-7/° c; (2) the glass has a softening point of 390 ℃ under expansion.
Example 3
The environment-friendly low-temperature sealing glass is prepared from the following oxides in percentage by mass (wt.%):
selecting raw materials according to the glass components in the example 3 in the table 1, strictly controlling the alkali metal content in the glass raw materials to enable the ingredients to meet the glass chemical composition in the table 1, then melting the raw materials for 2.5 hours at the temperature of 1000 ℃ by using a platinum crucible, pouring the glass melt into a preheated heat-resistant steel die with the size of 70mm multiplied by 10mm after the glass batch is melted into a homogeneous glass melt, casting and forming, and then annealing. The basic properties of the samples are shown in table 1. (1) Average linear expansion coefficient of 69 x 10 at 20-300 DEG C-7/° c; (2) the glass has an expansion softening point temperature of 340 ℃.
Example 4
The environment-friendly low-temperature sealing glass is prepared from the following oxides in percentage by mass (wt%):
the glass compositions of example 4 in Table 1 were selected and required to be added to the glass raw materialsThe alkali metal content was so tightly controlled that the batch satisfied the glass chemical composition of table 1, and the basic properties of the samples are shown in table 1 using the same melting process regime and test conditions as in example 1. (1) Average linear expansion coefficient of 57 x 10 at 20-300 DEG C-7/° c; (2) the glass has an expansion softening point of 375 ℃.
Example 5
The environment-friendly low-temperature sealing glass is prepared from the following oxides in percentage by mass (wt%):
the glass compositions of example 5 of Table 1 were selected and the alkali metal content of the glass batch was strictly controlled so that the batch met the glass chemistry of Table 1, and the same melting schedule and test conditions as in example 1 were used, and the basic properties of the samples are shown in Table 1. (1) Average linear expansion coefficient of 68 x 10 at 20-300 DEG C-7/° c; (2) the glass has a swelling softening point of 365 ℃.
The data obtained by the embodiment shows that the environment-friendly low-temperature sealing glass has the advantages of low softening temperature and no harmful heavy metal, and is suitable for the fields of mobile phone communication, microelectronic materials, electronic and electrical sealing and the like.
The above-mentioned embodiments are only preferred embodiments of the present invention, and the present invention is not limited thereto, and the protection scope of the present invention is defined by the claims. Any modification or equivalent replacement, improvement and the like of the present invention can be made by those skilled in the art within the spirit and scope of the present invention, and such modification or equivalent replacement is also considered to fall within the scope of the present invention.
Claims (4)
1. The environment-friendly low-temperature sealing glass is characterized by being prepared from the following oxides in percentage by mass:
Bi2O3 42.0%
ZnO 34.0%
B2O3 9.0%
Y2O3 6.0%
WO3 2.0%
TiO2 1.0%
SnO2 1.0%
SiO2 1.0%
Al2O3 4.0%。
2. the environment-friendly low-temperature sealing glass according to claim 1, wherein: the average linear thermal expansion coefficient of the glass in the range of 20-300 ℃ is 68 multiplied by 10-7/℃。
3. The environment-friendly low-temperature sealing glass according to claim 1, wherein: the softening point temperature of the glass was 365 ℃.
4. The method for preparing the environment-friendly low-temperature sealing glass according to claim 1, which comprises the following steps:
the method comprises the following steps: mixing SiO2、Al2O3、B2O3、Bi2O3、ZnO、Y2O3、WO3、TiO2、SnO2Weighing raw materials according to mass percentage, uniformly mixing, and putting into a platinum crucible;
step two: then melting the platinum crucible at 1050 ℃ for 2 hours, pouring molten glass liquid into deionized water for water quenching after the glass is uniformly molten;
step three: then drying to obtain fragments of the glass melt;
step four: and then ball-milling and crushing the dried glass, drying and sieving by a 200-mesh sieve to obtain the low-temperature sealing glass material powder.
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| CN111847882B (en) * | 2020-08-10 | 2022-08-19 | 福州瑞克布朗医药科技有限公司 | Low-temperature sealing glass and preparation method thereof |
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| CN114590999B (en) * | 2022-01-20 | 2023-05-05 | 广西科技大学 | Low-melting-point lead-free glass powder and preparation method thereof |
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| CN117735841A (en) * | 2023-12-18 | 2024-03-22 | 西安稀有金属材料研究院有限公司 | Sealing glass, preparation method thereof and electronic component |
| CN120573949A (en) * | 2025-08-05 | 2025-09-02 | 湖南衡义材料科技有限公司 | A low-melting-point sealing glass strip and its preparation method and application |
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