CN114477768A - Lead-free low-melting-point sealing glass doped with fusible metal alloy and preparation method thereof - Google Patents
Lead-free low-melting-point sealing glass doped with fusible metal alloy and preparation method thereof Download PDFInfo
- Publication number
- CN114477768A CN114477768A CN202210196815.6A CN202210196815A CN114477768A CN 114477768 A CN114477768 A CN 114477768A CN 202210196815 A CN202210196815 A CN 202210196815A CN 114477768 A CN114477768 A CN 114477768A
- Authority
- CN
- China
- Prior art keywords
- glass
- percent
- lead
- melting
- metal alloy
- 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.)
- Pending
Links
- 239000005394 sealing glass Substances 0.000 title claims abstract description 70
- 229910001092 metal group alloy Inorganic materials 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title abstract description 13
- 239000011521 glass Substances 0.000 claims abstract description 87
- 239000000945 filler Substances 0.000 claims abstract description 27
- 239000000843 powder Substances 0.000 claims description 62
- JWVAUCBYEDDGAD-UHFFFAOYSA-N bismuth tin Chemical compound [Sn].[Bi] JWVAUCBYEDDGAD-UHFFFAOYSA-N 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 17
- 239000006121 base glass Substances 0.000 claims description 16
- 229910052593 corundum Inorganic materials 0.000 claims description 16
- 238000000498 ball milling Methods 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 10
- 229910052797 bismuth Inorganic materials 0.000 claims description 9
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(III) oxide Inorganic materials O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 claims description 9
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 9
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Inorganic materials O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 9
- 238000002844 melting Methods 0.000 claims description 9
- 230000008018 melting Effects 0.000 claims description 9
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 8
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 8
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims description 8
- UPWOEMHINGJHOB-UHFFFAOYSA-N cobalt(III) oxide Inorganic materials O=[Co]O[Co]=O UPWOEMHINGJHOB-UHFFFAOYSA-N 0.000 claims description 8
- 239000010431 corundum Substances 0.000 claims description 8
- 239000012458 free base Substances 0.000 claims description 8
- GALOTNBSUVEISR-UHFFFAOYSA-N molybdenum;silicon Chemical compound [Mo]#[Si] GALOTNBSUVEISR-UHFFFAOYSA-N 0.000 claims description 8
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 8
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 7
- 239000002994 raw material Substances 0.000 claims description 7
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Inorganic materials O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 claims description 6
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims description 5
- 229910052681 coesite Inorganic materials 0.000 claims description 5
- 229910052906 cristobalite Inorganic materials 0.000 claims description 5
- 239000000377 silicon dioxide Substances 0.000 claims description 5
- 229910052682 stishovite Inorganic materials 0.000 claims description 5
- 229910052905 tridymite Inorganic materials 0.000 claims description 5
- 238000005303 weighing Methods 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 239000011812 mixed powder Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 239000006060 molten glass Substances 0.000 claims description 4
- 238000007873 sieving Methods 0.000 claims description 4
- 229910000505 Al2TiO5 Inorganic materials 0.000 claims description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 3
- 239000004110 Zinc silicate Substances 0.000 claims description 3
- 229910052878 cordierite Inorganic materials 0.000 claims description 3
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 claims description 3
- 229910000174 eucryptite Inorganic materials 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 239000003607 modifier Substances 0.000 claims description 3
- AABBHSMFGKYLKE-SNAWJCMRSA-N propan-2-yl (e)-but-2-enoate Chemical compound C\C=C\C(=O)OC(C)C AABBHSMFGKYLKE-SNAWJCMRSA-N 0.000 claims description 3
- 238000012216 screening Methods 0.000 claims description 3
- XSMMCTCMFDWXIX-UHFFFAOYSA-N zinc silicate Chemical compound [Zn+2].[O-][Si]([O-])=O XSMMCTCMFDWXIX-UHFFFAOYSA-N 0.000 claims description 3
- 235000019352 zinc silicate Nutrition 0.000 claims description 3
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 claims description 3
- 229910052845 zircon Inorganic materials 0.000 claims 1
- 238000007789 sealing Methods 0.000 abstract description 38
- 239000000126 substance Substances 0.000 abstract description 18
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 abstract description 3
- 239000002131 composite material Substances 0.000 description 12
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 239000003566 sealing material Substances 0.000 description 5
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 241000282414 Homo sapiens Species 0.000 description 2
- GHPGOEFPKIHBNM-UHFFFAOYSA-N antimony(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Sb+3].[Sb+3] GHPGOEFPKIHBNM-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000007496 glass forming Methods 0.000 description 2
- KTUFCUMIWABKDW-UHFFFAOYSA-N oxo(oxolanthaniooxy)lanthanum Chemical compound O=[La]O[La]=O KTUFCUMIWABKDW-UHFFFAOYSA-N 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000012827 research and development Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910001128 Sn alloy Inorganic materials 0.000 description 1
- 229910003069 TeO2 Inorganic materials 0.000 description 1
- 229910007676 ZnO—SiO2 Inorganic materials 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 239000005388 borosilicate glass Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000009970 fire resistant effect Effects 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000010309 melting process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000005365 phosphate glass Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- YEAUATLBSVJFOY-UHFFFAOYSA-N tetraantimony hexaoxide Chemical compound O1[Sb](O2)O[Sb]3O[Sb]1O[Sb]2O3 YEAUATLBSVJFOY-UHFFFAOYSA-N 0.000 description 1
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
- C03C8/24—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
-
- 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
- C03C12/00—Powdered glass; Bead compositions
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 relates to a lead-free low-melting-point sealing glass doped with fusible metal alloy and a preparation method thereof, wherein the glass comprises the following components by weight percent, 60-85% of the lead-free low-melting-point sealing glass; 8 to 20 percent of low expansion filler; 7 to 20 percent of fusible metal alloy. The expansion coefficient of the lead-free low-melting-point sealing glass is matched with that of platinum group glass, the sealing temperature is less than or equal to 420 ℃, the chemical stability is good, the sealing strength is high, and the preparation is easy. The invention can flexibly adjust the proportion of each component according to different characteristic index requirements, optimize the glass formula and meet the specific requirements of the market on the lead-free low-melting-point sealing glass.
Description
Technical Field
The invention relates to the technical field of glass material preparation, in particular to lead-free low-melting-point sealing glass doped with fusible metal alloy and a preparation method thereof.
Background
The low-melting-point sealing glass is used as one kind of sealing material, and has better air tightness and heat resistance than organic polymer material and better electric insulating performance than metal material, so that the low-melting-point sealing glass has wide application range. With the development of modern science and technology, especially the rapid progress in the fields of vacuum electronic technology, photoelectronic technology, microelectronic semiconductor technology, laser and infrared technology, electric light source, industrial test and the like, the miniaturization of devices and the precision degree of structural elements are continuously improved, the variety of electronic components is more and more, the shape of products is more and more complex, the requirements on the air tightness and the reliability of sealing products are more and more high, and the requirements on working environment are more and more high, so that the requirements on low-melting-point sealing glass are more and more rigorous, the requirements have wide application fields, and meanwhile, the requirements on strong pertinence and special indexes are also met.
In the low-melting-point sealing glass, the lead-containing sealing glass has a series of characteristics of low softening temperature, stable electrical property, good chemical stability and the like. It has wide application in sealing various electronic components. PbO-B is often selected for the preparation of lead-containing sealing glass at home and abroad2O3-ZnO-SiO2Glass systems, but most commercial sealing glasses, have PbO levels as high as 70% or more, and the heavy metals contained in these products can cause serious environmental and human hazards. Meanwhile, a large amount of discarded electronic components cannot be harmlessly treated, and lead ions are gradually dissolved out when the components are corroded by rainwater, air and the like, so that the soil and underground water are seriously polluted, and the living environment of human beings is seriously threatened. Therefore, the application of lead-containing materials worldwide is increasingly restricted. Although the application of the lead-containing low-melting-point sealing glass is strictly limited, the lead-containing low-melting-point sealing glass is not environment-friendly, and almost all the physical and chemical properties of the lead-containing low-melting-point sealing glass are superior to those of lead-free low-melting-point sealing glass. For the field of low melting point sealing glass, the urgent research and development task is to replace lead-containing low melting point sealing glass with lead-free low melting point sealing glass. At present, the development trend of low-melting-point sealing glass is changed into lead-free, low-temperature and practical sealing glass, and if lead-free low-melting-point sealing glass is to completely replace lead-containing low-melting-point sealing glass, the strict requirements of the three types of sealing glass must be met at the same time. At present, the research on lead-free low-melting-point sealing glass mainly focuses on a phosphate glass system, a vanadate glass system, a bismuthate glass system, a borosilicate glass system and the like. Wherein the bismuthate glass can be sealed at low temperatureThe sealing strength is high, and the sealing material has better chemical stability and is concerned, and related patents have been issued by domestic and foreign research and development institutions in the research field.
The invention patent US2006/01058981 discloses a low-melting-point sealing glass component, which comprises 70-90% Bi by mass percent2O310 to 35 percent of ZnO and 10 to 35 percent of B2O30.1 to 5 percent of Al2O30.1 to 5 percent of CeO20 to 5 percent of CuO and 0 to 0.2 percent of Fe2O3In which CuO + Fe2O3The content is 0.05-5%, the glass of the component does not crystallize at the sealing temperature, and the glass of the system has the defect that a large amount of Al is added into the glass2O3The components obviously improve the sealing temperature of the glass.
Japanese patent laid-open No. 2006143480 discloses a Bi2O3-B2O3The glass component and the sealing material adopting the component basically contain no lead, and the components in mole percentage are as follows: 35 to 60 percent of Bi2O310% -35% of B2O30.1 to 5 percent of WO3. The sealing material adopting the component contains 40-90% of base glass component and 60-10% of low-expansion fire-resistant filler by volume percentage. The disadvantage of this system is that the coefficient of thermal expansion is too high, and the values are 110X 10 before the low-expansion refractory filler is added-7Above/° c, and is prone to crystallization during sealing.
The invention patent CN 101602573A of Chinese measurement institute discloses a bismuthate low-melting-point sealing glass material which adopts Bi2O3-ZnO--B2O3--Sb2O3The glass system comprises the following components in percentage by mass: 71 to 91 percent of Bi2O32 to 20 percent of ZnO and 5 to 25 percent of B2O30.5 to 5 percent of Sb2O3. Also comprises 0 to 3 percent of BaO, 0 to 3 percent of SrO, 0 to 3 percent of CuO and 0 to 3 percent of TeO2And (4) friend making. Prepared lead-free bismuthate glass expansionThe coefficient of expansion is (95.6-104.9) x 10-7The sealing temperature of the glass is higher than that of 480-500 ℃, so that the practical use of the glass is limited.
The existing lead-free low-melting-point sealing glass has performance defects of different degrees, such as high sealing temperature, easy crystallization of glass, poor chemical stability, narrow range of practical application fields and the like.
Disclosure of Invention
The invention mainly aims to provide the lead-free low-melting-point sealing glass which has the expansion coefficient matched with platinum group glass, has the sealing temperature of less than or equal to 420 ℃, good chemical stability and high sealing strength and is easy to prepare and doped with the fusible metal alloy.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
the invention provides a lead-free low-melting-point sealing glass doped with fusible metal alloy, which comprises the following components in percentage by weight, 60-85% of the lead-free low-melting-point sealing glass; 8 to 20 percent of low expansion filler; 7 to 20 percent of fusible metal alloy.
The invention also provides a preparation method of the lead-free low-melting-point sealing glass powder doped with the fusible metal alloy, which comprises the following steps:
the method comprises the following steps:
the method comprises the following steps: weighing raw materials according to the weight percentage of the components, and fully mixing to obtain a batch material, wherein the raw materials are oxides or corresponding compounds;
step two: heating a silicon-molybdenum rod electric furnace to 900-1100 ℃ in advance;
step three: putting the batch mixture in the step one into a corundum crucible, and then putting the corundum crucible into a resistance furnace with the furnace temperature of 200-250 ℃ for preheating;
step four: putting the batch preheated in the step three into a silicon-molybdenum rod electric furnace for glass melting for 1-3 hours;
step five: pouring the molten glass into a tablet press to be pressed into thin glass sheets, and cooling and storing the thin glass sheets;
step six: putting the flaky glass prepared in the step five into a ball milling tank for ball milling;
step seven: sieving and storing the glass powder subjected to ball milling in the step six by using a required screen to obtain lead-free base glass powder;
step eight: the lead-free base glass powder, the low-expansion filler powder and the bismuth-tin metal alloy powder are respectively and independently screened, a screen mesh with 200-240 meshes is used for screening, the powder passing through the screen mesh is fully homogenized and mixed in a high-speed mixer according to the proportion and the mixing time is 80-90 minutes at 80-95 revolutions per minute, and the homogenized and mixed powder is the lead-free low-melting-point sealing glass complex doped with the fusible metal alloy.
By the technical scheme, the invention at least has the following advantages:
1. the original lead-free low-melting-point sealing glass has one or more of the following performance defects of (1) easy crystallization of glass, (2) higher sealing temperature, (3) lower sealing strength, (4) poor chemical stability, and (5) low sealing airtightness. If one or more of the lead-free low melting point sealing glasses occupy, the application range of the lead-free low melting point sealing glasses is limited. The lead-free low-melting-point sealing glass prepared by the invention is used as basic glass in a complex, basically gives consideration to various performance indexes through component optimization design, and has the advantages of stable structure, wide glass forming range, low sealing temperature, high sealing strength, good chemical stability and capability of ensuring the air tightness of sealing components under the lead-free condition.
2. In the invention, as the low-expansion filler powder in the complex, the bismuth niobate filler has excellent low-expansion performance, and when the bismuth niobate filler is mixed into the base glass powder, the sealing temperature of the composite powder is not remarkably improved, and meanwhile, the expansion coefficient of the composite powder is greatly reduced, and the chemical stability of the composite powder is also remarkably improved.
3. The invention is used as the fusible bismuth-tin metal alloy powder in the complex, and has the functions of not obviously improving the expansion coefficient of the composite powder after the fusible bismuth-tin metal alloy powder is uniformly mixed into the basic glass powder and the low-expansion filler powder, simultaneously greatly reducing the sealing temperature of the composite powder, controlling the sealing temperature of glass to be less than or equal to 420 ℃, releasing the residual stress of the sealed device and ensuring the sealing airtightness of the sealed device.
The foregoing is a summary of the present invention, and in order to provide a clear understanding of the technical means of the present invention and to be implemented in accordance with the present specification, the following is a detailed description of the preferred embodiments of the present invention.
Detailed Description
To further illustrate the technical means and effects of the present invention adopted to achieve the intended purpose, the following preferred embodiments describe the detailed implementation, structure, features and effects of the present invention. In the following description, different "one embodiment" or "an embodiment" refers to not necessarily the same embodiment. Furthermore, the particular features, structures, or characteristics may be combined in any suitable manner in one or more embodiments.
The invention provides a lead-free low-melting-point sealing glass doped with fusible metal alloy, which comprises the following components in percentage by weight, 60-85% of the lead-free low-melting-point sealing glass; 8 to 20 percent of low expansion filler; 7 to 20 percent of fusible metal alloy.
The invention consists of three parts of mixing and homogenizing. The first part is composed of lead-free low-melting-point base glass, and the function of the first part is to preferably select base glass powder with excellent comprehensive performance indexes. The second part is composed of low-expansion filler powder, and the function of the second part is to mix the low-expansion filler powder into the basic glass powder, so that the sealing temperature of the composite powder is not remarkably improved, and the expansion coefficient of the composite powder is greatly reduced. The third part is composed of fusible metal alloy, and has the functions of adding the fusible metal alloy into the two kinds of powder, not obviously improving the expansion coefficient of the composite powder, simultaneously greatly reducing the sealing temperature of the composite powder, releasing the residual stress of the sealed device and ensuring the sealing airtightness of the device.
The expansion coefficient of the lead-free low-melting-point sealing glass is matched with that of platinum group glass, the sealing temperature is less than or equal to 420 ℃, the chemical stability is good, the sealing strength is high, and the preparation is easy. The invention can flexibly adjust the proportion of each component according to different characteristic index requirements, optimize the glass formula and meet the specific requirements of the market on the lead-free low-melting-point sealing glass.
Further, the lead-free low-melting-point base glass is Bi2O3-ZnO-B2O3-P2O5The glass system is taken as a basis, and the prepared lead-free low-melting-point sealing glass is taken as the base glass, wherein the lead-free low-melting-point sealing glass comprises the following components in percentage by weight: 55 to 87 percent of Bi2O35% -20% of B2O35 to 20 percent of ZnO and 1 to 10 percent of P2O5。
In the glass system of the present invention, Bi2O3、B2O3、ZnO、P2O5The glass network forming agent can be used as a glass network basic skeleton. High Bi content2O3The content ensures the low softening temperature of the glass, and the proper amount of P2O5The content helps to lower the softening temperature of the glass, reduces the tendency of the glass to devitrify, and does not significantly reduce the chemical stability of the glass. Appropriate amount of B2O3The function of stabilizing the glass network is achieved, and the viscosity is kept stable in the glass melting process. Although ZnO is an intermediate oxide, under conditions sufficient for free oxygen, it forms zinc-oxygen tetrahedra into the glass network.
Further, the lead-free low-melting-point base glass also contains 0.5 to 6 weight percent of SiO glass performance regulator20.1 to 6 percent of Al2O30.1 to 5 percent of BaO and 0.1 to 5 percent of SrO.
In the glass system of the present invention, SiO2、Al2O3BaO and SrO are glass structure modifiers. BaO and SrO not only can reinforce the glass network, but also can provide free oxygen as an intermediate oxide, namely SiO2、Al2O3The broken net of the glass system is repaired to provide assistance.
Further, the lead-free low-melting-point base glass also contains a glass property regulator with the following weight percentage content of 0.5-8 percent of Sb2O30.1 to 6 percent of CuO and 0.1 to 6 percent of Fe2O30.1 to 6 percent of Co2O30.1% -6% of MnO20.2 to 6 percent of La2O30.2 to 6 percent of CeO2。
In the glass system of the present invention, CuO and Fe2O3、Sb2O3、Co2O3、MnO2、La2O3、CeO2Is glass property regulator, CuO, Fe2O3、Co2O3The color of the glass can be adjusted, the wettability of the sealing material and the chemical stability of the base glass can be improved, and the sealing process is facilitated. MnO2、Sb2O3、La2O3、CeO2The electrical property of the glass, especially the volume resistance and the surface resistance can be improved.
Preferably, the lead-free low-melting-point base glass contains the following components in percentage by weight: 70 to 85 percent of Bi2O35% -15% of B2O35 to 15 percent of ZnO and 1 to 6 percent of P2O50.5 to 4 percent of SiO20.1 to 4 percent of Al2O30.1 to 4.5 percent of BaO, 0.1 to 3 percent of SrO and 0.5 to 5 percent of Sb2O30.1 to 5 percent of CuO and 0.1 to 4 percent of Fe2O30.1% -2% of Co2O30.1% -2% of MnO20.2 to 3 percent of La2O30.2 to 3 percent of CeO2。
Further, the low expansion filler is selected from at least one of aluminum titanate, eucryptite, cordierite, zirconite, bismuth niobate, zinc silicate and quartz glass, and has an expansion coefficient ranging from (-110 to 60). times.10-7/℃。
The lead-free base glass powder prepared by the invention has the advantages of low sealing temperature, good chemical stability and proper expansion coefficient. However, in order to expand the application range and obtain more excellent physical and chemical properties, the lead-free glass powder is doped with filler powder with low expansion coefficient, and the filler powder must pass through a 200-240-mesh screen. The filler is in the lead-free low-melting-point sealing glass composite body doped with the fusible metal alloy, and the weight percentage content of the filler is preferably 8-20%.
Further, the fusible metal alloy is a bismuth-tin metal alloy.
The bismuth-tin metal alloy comprises 20-80% of bismuth and 80-20% of tin by mass.
In the preparation of the lead-free low-melting-point sealing glass complex doped with the fusible metal alloy, the complex also comprises bismuth-tin metal alloy powder, the bismuth-tin metal alloy powder must completely pass through a screen with 200-240 meshes, and after the bismuth-tin metal alloy powder is doped, the expansion coefficient of the composite powder is not remarkably improved, and the sealing temperature of the composite powder is greatly reduced. The weight percentage content range of the bismuth-tin metal alloy powder in the lead-free low-melting-point sealing glass complex doped with the fusible metal alloy is preferably 7-20%.
The invention also provides a preparation method of the lead-free low-melting-point sealing glass doped with the fusible metal alloy, which comprises the following steps:
the method comprises the following steps: weighing raw materials according to the weight percentage of the components, and fully mixing to obtain a batch material, wherein the raw materials are oxides or corresponding compounds;
step two: heating a silicon-molybdenum rod electric furnace to 900-1100 ℃ in advance;
step three: putting the batch mixture in the step one into a corundum crucible, and then putting the corundum crucible into a resistance furnace with the furnace temperature of 200-250 ℃ for preheating for 30-60 minutes;
step four: putting the batch preheated in the step three into a silicon-molybdenum rod electric furnace for glass melting for 1-3 hours;
step five: pouring the molten glass into a tablet press to be pressed into thin glass sheets, and cooling and storing the thin glass sheets;
step six: putting the flaky glass prepared in the step five into a ball milling tank for ball milling;
step seven: sieving and storing the glass powder subjected to ball milling in the step six by using a required screen to obtain lead-free base glass powder;
step eight: the lead-free base glass powder, the low-expansion filler powder and the bismuth-tin metal alloy powder are respectively and independently screened, a screen with 200-240 meshes is used for screening, the powder passing through the screen is fully homogenized and mixed in a high-speed mixer according to the proportion and the mixing time of 80-90 minutes at 80-95 rpm, and the homogenized and mixed powder is the lead-free low-melting-point sealing glass complex doped with the fusible metal alloy.
The preparation method provided by the invention is simple and practical in process, and can be used for preparing the lead-free low-melting-point sealing glass doped with the fusible metal alloy, which is green, environment-friendly, large-scale in production and excellent in various performance indexes. The method not only makes the manufacturing process of the glass powder simple and easy, but also has no pollution to the environment in the whole process manufacturing process.
The present invention will be described in further detail with reference to specific examples.
Examples 1 to 7 are specific examples of the preparation of a lead-free low-melting-point sealing glass doped with a fusible metal alloy according to the present invention. The corresponding raw materials are weighed according to the weight percentage of each component for each example to total about 150 g, namely the lead-free low-melting-point sealing glass is weighed to total about 150 g, and the implementation results and the performance data of each example are shown in Table 1.
The process of the lead-free low-melting-point sealing glass doped with the fusible metal alloy is carried out according to the following steps:
the method comprises the following steps: accurately weighing oxides or corresponding compounds according to the following chemical components and weight percentage of the lead-free low-melting-point sealing glass, and fully mixing: 70 to 90 percent of Bi2O35% -15% of B2O35 to 15 percent of ZnO and 1 to 6 percent of P2O50.5 to 4 percent of SiO20.1 to 4 percent of Al2O30.1 to 4.5 percent of BaO, 0.1 to 3 percent of SrO and 0.5 to 5 percent of Sb2O30.1 to 5 percent of CuO and 0.1 to 4 percent of Fe2O30.1% -2% of Co2O30.1% -2% of MnO20.2 to 3 percent of La2O30.2 to 3 percent of CeO2。
Step two: the temperature of the silicon-molybdenum rod electric furnace is increased to 900-1100 ℃ in advance.
Step three: and (3) putting the batch in the first step into a corundum crucible, and then putting the corundum crucible into a resistance furnace with the furnace temperature of 200-250 ℃ for preheating for 30-60 minutes.
Step four: and (4) putting the batch preheated in the step three into a silicon-molybdenum rod electric furnace for glass melting for 1-3 hours.
Step five: pouring the molten glass into a tablet press to be pressed into thin glass sheets, and cooling and storing.
Step six: and D, putting the flaky glass prepared in the step five into a ball milling tank for ball milling.
Step seven: and (4) sieving the glass powder subjected to ball milling in the step six by using a 200-240-mesh screen, and storing the sieved glass powder.
Step eight: selecting one or more combinations of the following low-expansion filler powder passing through a 200-240-mesh screen, wherein the filler is one or more combinations of aluminum titanate, eucryptite, cordierite, zirconite, bismuth niobate, zinc silicate and quartz glass, and the expansion coefficient range of the filler is (110-60) multiplied by 10 < -7 >/DEG C.
Step nine: the following fusible bismuth-tin metal alloy powder passing through a 200-240-mesh screen is selected, and the weight percentage of the fusible bismuth-tin metal alloy powder is 20-80% of bismuth and 80-20% of tin.
Step ten: accurately weighing and mixing the lead-free base glass powder prepared in the step seven, the low-expansion filler powder selected in the step eight and the fusible bismuth-tin metal alloy powder selected in the step nine according to the proportion that the lead-free base glass powder accounts for 60-85 wt%, the low-expansion filler powder accounts for 8-20 wt% and the fusible bismuth-tin metal alloy powder accounts for 7-20 wt%, and fully homogenizing and mixing the materials in a high-speed mixer according to the rotation speed of 80-95 r/min and the mixing time of 80-90 min. The homogenized and mixed powder is the lead-free low-melting-point sealing glass complex doped with the fusible metal alloy.
The performance test method of the glass samples of examples 1 to 7 was as follows:
1. coefficient of expansion: the method is carried out by adopting Chinese electronic industry standard SJ/T11036-96;
2. softening temperature: the method is carried out by adopting Chinese electronic industry standard SJ/T11038-96;
3. sealing temperature: the method is carried out by adopting Chinese electronic industry standard SJ/T11038-96;
4. diameter of the flow column: the method is carried out by adopting the standard SJ-3232.3-89 of the ministry of mechanical and electronic industry of China;
5. water-resistant chemical stability test: the water resistance test of glass is carried out in distilled water at 90 ℃, and a glass sample ground into 10X 10mm is placed in distilled water at 90 ℃ for 24 hours in a water bath, and after drying, the weight loss g per square centimeter is weighed.
The invention can realize the adjustment of expansion coefficient and sealing temperature by adjusting the components of the glass powder, the types and the contents of the fillers and the proportion of the bismuth-tin alloy, thereby being suitable for the sealing and welding among various glass, ceramics, metals and alloys.
TABLE 1 chemical composition and Property data for the examples
As shown in Table 1, the glass transition temperature of the lead-free low-melting-point sealing glass doped with the fusible metal alloy is 335-375 ℃, and the average thermal expansion coefficient of 25-300 ℃ is (83.38-95.34) multiplied by 10-7The sealing process does not crystallize at/deg.C, and sealing can be carried out at the temperature of 420-460 deg.C. The invention solves the problems of stable structure, wide glass forming range, low sealing temperature, high sealing strength, good chemical stability, guarantee of air tightness of sealing components and parts and the like of the low-melting-point sealing glass under the lead-free condition.
Although the present invention has been described with reference to a preferred embodiment, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (10)
1. A lead-free low-melting-point sealing glass doped with fusible metal alloy is characterized in that: the lead-free low-melting-point glass comprises, by weight, 60-85% of lead-free low-melting-point base glass; 8 to 20 percent of low expansion filler; 7 to 20 percent of fusible metal alloy.
2. The lead-free low-melting-point sealing glass doped with a fusible metal alloy as claimed in claim 1, wherein said lead-free low-melting-point base glass is Bi2O3-ZnO-B2O3-P2O5The glass system is taken as a basis, and the prepared lead-free low-melting-point sealing glass is taken as the base glass, wherein the lead-free low-melting-point sealing glass comprises the following components in percentage by weight: 55 to 87 percent of Bi2O35% -20% of B2O35 to 20 percent of ZnO and 1 to 10 percent of P2O5。
3. The sealing glass of claim 2, wherein the base glass further comprises 0.5-6 wt% SiO as a glass property modifier20.1 to 6 percent of Al2O30.1 to 5 percent of BaO and 0.1 to 5 percent of SrO.
4. The sealing glass of claim 3, wherein the base glass further comprises 0.5-8 wt% Sb as a glass property modifier2O30.1% -6%CuO, 0.1-6% Fe2O30.1 to 6 percent of Co2O30.1% -6% of MnO20.2 to 6 percent of La2O30.2 to 6 percent of CeO2。
5. The lead-free low-melting-point sealing glass doped with the fusible metal alloy as claimed in claim 4, wherein the lead-free low-melting-point base glass contains the following components in percentage by weight: 70 to 85 percent of Bi2O35% -15% of B2O35 to 15 percent of ZnO and 1 to 6 percent of P2O50.5 to 4 percent of SiO20.1 to 4 percent of Al2O30.1 to 4.5 percent of BaO, 0.1 to 3 percent of SrO and 0.5 to 5 percent of Sb2O30.1 to 5 percent of CuO and 0.1 to 4 percent of Fe2O30.1% -2% of Co2O30.1% -2% of MnO20.2 to 3 percent of La2O30.2 to 3 percent of CeO2。
6. A lead-free low-melting-point sealing glass doped with a fusible metal alloy as claimed in any one of claims 1 to 5, wherein the low-expansion filler is at least one selected from the group consisting of aluminum titanate, eucryptite, cordierite, zircon, bismuth niobate, zinc silicate and quartz glass, and has an expansion coefficient in the range of (-110 to 60) x 10-7/℃。
7. The lead-free low-melting-point sealing glass doped with the fusible metal alloy as claimed in claim 6, wherein the fusible metal alloy is a bismuth-tin metal alloy.
8. The lead-free low-melting-point sealing glass doped with the fusible metal alloy as claimed in claim 7, wherein the bismuth-tin metal alloy is 20 to 80 mass% of bismuth, and the tin is 80 to 20 mass%.
9. A method for producing a lead-free low-melting-point sealing glass doped with a fusible metal alloy as claimed in any one of claims 1 to 8, comprising the steps of:
the method comprises the following steps: weighing raw materials according to the weight percentage of the components, and fully mixing to obtain a batch material, wherein the raw materials are oxides or corresponding compounds;
step two: heating a silicon-molybdenum rod electric furnace to 900-1100 ℃ in advance;
step three: putting the batch mixture in the step one into a corundum crucible, and then putting the corundum crucible into a resistance furnace with the furnace temperature of 200-250 ℃ for preheating;
step four: putting the batch preheated in the third step into a silicon-molybdenum rod electric furnace for glass melting for 1-3 hours;
step five: pouring the molten glass into a tablet press to be pressed into thin glass sheets, and cooling and storing the thin glass sheets;
step six: putting the flaky glass prepared in the step five into a ball milling tank for ball milling;
step seven: sieving and storing the glass powder subjected to ball milling in the step six by using a required screen to obtain lead-free basic glass powder;
step eight: the lead-free base glass powder, the low-expansion filler powder and the bismuth-tin metal alloy powder are respectively and independently screened, a screen mesh with 200-240 meshes is used for screening, the powder passing through the screen mesh is fully homogenized and mixed in a high-speed mixer according to the proportion and the mixing time is 80-90 minutes at 80-95 revolutions per minute, and the homogenized and mixed powder is the lead-free low-melting-point sealing glass complex doped with the fusible metal alloy.
10. The method of claim 9, wherein the preheating time is 30 to 60 minutes.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210196815.6A CN114477768A (en) | 2022-03-01 | 2022-03-01 | Lead-free low-melting-point sealing glass doped with fusible metal alloy and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210196815.6A CN114477768A (en) | 2022-03-01 | 2022-03-01 | Lead-free low-melting-point sealing glass doped with fusible metal alloy and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN114477768A true CN114477768A (en) | 2022-05-13 |
Family
ID=81484997
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210196815.6A Pending CN114477768A (en) | 2022-03-01 | 2022-03-01 | Lead-free low-melting-point sealing glass doped with fusible metal alloy and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114477768A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115572072A (en) * | 2022-10-08 | 2023-01-06 | 中建材玻璃新材料研究院集团有限公司 | Sealing glass powder and preparation method thereof |
| CN115925436A (en) * | 2022-12-26 | 2023-04-07 | 哈尔滨工业大学 | Method for connecting ferrite and microwave dielectric ceramic by using low-melting-point glass soldering paste |
| CN116253511A (en) * | 2023-02-23 | 2023-06-13 | 上海太洋科技有限公司 | Phosphate glass with high hardness, high Young modulus and high refractive index and preparation method thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003095697A (en) * | 2001-09-18 | 2003-04-03 | Nihon Yamamura Glass Co Ltd | Sealing composition |
| CN1772676A (en) * | 2004-11-12 | 2006-05-17 | 旭技术玻璃株式会社 | Low melting glass, sealing composition and sealing paste |
| 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 |
| WO2012001824A1 (en) * | 2010-07-02 | 2012-01-05 | 有限会社ソフィアプロダクト | Bonding material |
| JP2013136470A (en) * | 2011-12-28 | 2013-07-11 | Asahi Glass Co Ltd | Sealing composition, method for producing sealing composition and sealed structure |
| CN107010837A (en) * | 2017-04-06 | 2017-08-04 | 蚌埠玻璃工业设计研究院 | A kind of rare earth doped element leadless and low-melting point sealing glass powder and its manufacture method |
-
2022
- 2022-03-01 CN CN202210196815.6A patent/CN114477768A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003095697A (en) * | 2001-09-18 | 2003-04-03 | Nihon Yamamura Glass Co Ltd | Sealing composition |
| CN1772676A (en) * | 2004-11-12 | 2006-05-17 | 旭技术玻璃株式会社 | Low melting glass, sealing composition and sealing paste |
| 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 |
| WO2012001824A1 (en) * | 2010-07-02 | 2012-01-05 | 有限会社ソフィアプロダクト | Bonding material |
| CN103025676A (en) * | 2010-07-02 | 2013-04-03 | 有限会社苏菲亚制造 | Bonding material |
| JP2013136470A (en) * | 2011-12-28 | 2013-07-11 | Asahi Glass Co Ltd | Sealing composition, method for producing sealing composition and sealed structure |
| CN107010837A (en) * | 2017-04-06 | 2017-08-04 | 蚌埠玻璃工业设计研究院 | A kind of rare earth doped element leadless and low-melting point sealing glass powder and its manufacture method |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115572072A (en) * | 2022-10-08 | 2023-01-06 | 中建材玻璃新材料研究院集团有限公司 | Sealing glass powder and preparation method thereof |
| CN115925436A (en) * | 2022-12-26 | 2023-04-07 | 哈尔滨工业大学 | Method for connecting ferrite and microwave dielectric ceramic by using low-melting-point glass soldering paste |
| CN115925436B (en) * | 2022-12-26 | 2023-09-22 | 哈尔滨工业大学 | Method for connecting ferrite and microwave dielectric ceramic by using low-melting glass soldering paste |
| CN116253511A (en) * | 2023-02-23 | 2023-06-13 | 上海太洋科技有限公司 | Phosphate glass with high hardness, high Young modulus and high refractive index and preparation method thereof |
| CN116253511B (en) * | 2023-02-23 | 2023-09-22 | 上海太洋科技有限公司 | Phosphate glass with high hardness, high Young modulus and high refractive index and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN114477768A (en) | Lead-free low-melting-point sealing glass doped with fusible metal alloy and preparation method thereof | |
| CN101376561B (en) | Low-melting point lead-less glasses powder for frit slurry, and preparation and use thereof | |
| CN104066696B (en) | A kind of vanadium base melted glass with and preparation method thereof | |
| CN101723589B (en) | Lead-free glass powder with low melting point for sealing PDP and preparation method thereof | |
| CN102701593B (en) | Low-melting point glass powder and manufacturing method thereof | |
| JP2003095697A (en) | Sealing composition | |
| CN101597136A (en) | A kind of lead-free low-melting sealing glass and preparation method thereof | |
| US20120308747A1 (en) | Coefficient of thermal expansion filler for vanadium-based frit materials and/or methods of making and/or using the same | |
| CN101113073A (en) | Leadless low-melting glass powder for seal with metal or alloy and preparation method thereof | |
| CN102001833A (en) | Unleaded glass powder used for electronic paste and preparation method thereof | |
| CN100345786C (en) | Low melting point, low expanding coefficient solder glass seal powder and its preparing method | |
| CN104379523A (en) | Coefficient of thermal expansion filler for vanadium-based frit materials and/or methods of making and/or using the same | |
| CN110217993B (en) | Environment-friendly low-temperature sealing glass and preparation method thereof | |
| JP3339647B2 (en) | Lead-free low melting glass and sealing glass composition | |
| JP4826137B2 (en) | Bismuth-based lead-free glass composition | |
| CN101602573A (en) | A kind of bismuthate lead-free sealing glass material with low melting point and preparation method thereof | |
| CN112969668A (en) | Low temperature fired lead-free glass frit and paste and vacuum glass assembly using the same | |
| CN114590999B (en) | Low-melting-point lead-free glass powder and preparation method thereof | |
| JP4874492B2 (en) | Glass composition and glass-forming material containing the composition | |
| CN102211870A (en) | Leadless low melting point phosphate glass | |
| JP4766444B2 (en) | Bismuth-based lead-free sealing material | |
| CN104891803A (en) | Bi system lead-free low-melting glass powder for conductive paste and preparation method thereof | |
| CN102050577A (en) | Special environment-friendly seal glass | |
| CN103951189B (en) | A kind of barium crown sealed glass powder and preparation method thereof | |
| CN112551902A (en) | Low-melting-point glass powder containing alkaline earth metal and preparation method and application thereof |
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 | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20220513 |