CN114249529B - Lithium aluminum silicon filler composition, lithium aluminum silicon filler and preparation method thereof, glass sealing material and application thereof - Google Patents
Lithium aluminum silicon filler composition, lithium aluminum silicon filler and preparation method thereof, glass sealing material and application thereof Download PDFInfo
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- CN114249529B CN114249529B CN202111476493.2A CN202111476493A CN114249529B CN 114249529 B CN114249529 B CN 114249529B CN 202111476493 A CN202111476493 A CN 202111476493A CN 114249529 B CN114249529 B CN 114249529B
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- 239000000945 filler Substances 0.000 title claims abstract description 143
- -1 Lithium aluminum silicon Chemical compound 0.000 title claims abstract description 94
- 239000011521 glass Substances 0.000 title claims abstract description 77
- 239000003566 sealing material Substances 0.000 title claims abstract description 72
- 239000000203 mixture Substances 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- NKZSPGSOXYXWQA-UHFFFAOYSA-N dioxido(oxo)titanium;lead(2+) Chemical compound [Pb+2].[O-][Ti]([O-])=O NKZSPGSOXYXWQA-UHFFFAOYSA-N 0.000 claims abstract description 41
- 229910004298 SiO 2 Inorganic materials 0.000 claims abstract description 21
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims abstract description 19
- FCSYVLNEFRBFMA-UHFFFAOYSA-N [B].[Pb] Chemical compound [B].[Pb] FCSYVLNEFRBFMA-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000005355 lead glass Substances 0.000 claims abstract description 15
- 239000000843 powder Substances 0.000 claims abstract description 12
- 238000010304 firing Methods 0.000 claims description 23
- 239000000463 material Substances 0.000 claims description 17
- 238000000498 ball milling Methods 0.000 claims description 15
- 238000007789 sealing Methods 0.000 claims description 13
- 239000002245 particle Substances 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 10
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 18
- 229910001947 lithium oxide Inorganic materials 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 12
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 8
- 239000000919 ceramic Substances 0.000 description 8
- 238000005245 sintering Methods 0.000 description 8
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 7
- 229910000679 solder Inorganic materials 0.000 description 7
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 6
- 239000005394 sealing glass Substances 0.000 description 6
- 230000009286 beneficial effect Effects 0.000 description 5
- 229910052573 porcelain Inorganic materials 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 238000007873 sieving Methods 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 229910000019 calcium carbonate Inorganic materials 0.000 description 4
- 238000005336 cracking Methods 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 230000001105 regulatory effect Effects 0.000 description 4
- 238000012216 screening Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 239000011787 zinc oxide Substances 0.000 description 3
- 229910010413 TiO 2 Inorganic materials 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- GNMQOUGYKPVJRR-UHFFFAOYSA-N nickel(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Ni+3].[Ni+3] GNMQOUGYKPVJRR-UHFFFAOYSA-N 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- KXLUWEYBZBGJRZ-POEOZHCLSA-N Canin Chemical compound O([C@H]12)[C@]1([C@](CC[C@H]1C(=C)C(=O)O[C@@H]11)(C)O)[C@@H]1[C@@]1(C)[C@@H]2O1 KXLUWEYBZBGJRZ-POEOZHCLSA-N 0.000 description 1
- GPFVKTQSZOQXLY-UHFFFAOYSA-N Chrysartemin A Natural products CC1(O)C2OC2C34OC3(C)CC5C(CC14)OC(=O)C5=C GPFVKTQSZOQXLY-UHFFFAOYSA-N 0.000 description 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- 238000010420 art technique Methods 0.000 description 1
- 229910002056 binary alloy 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
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing 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
- C03C1/00—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels
-
- 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
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F24—HEATING; RANGES; VENTILATING
- F24S—SOLAR HEAT COLLECTORS; SOLAR HEAT SYSTEMS
- F24S80/00—Details, accessories or component parts of solar heat collectors not provided for in groups F24S10/00-F24S70/00
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F24—HEATING; RANGES; VENTILATING
- F24S—SOLAR HEAT COLLECTORS; SOLAR HEAT SYSTEMS
- F24S80/00—Details, accessories or component parts of solar heat collectors not provided for in groups F24S10/00-F24S70/00
- F24S2080/01—Selection of particular materials
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/40—Solar thermal energy, e.g. solar towers
Abstract
The application provides a lithium aluminum silicon filler composition, a lithium aluminum silicon filler, a preparation method of the lithium aluminum silicon filler, a glass sealing material and application of the glass sealing material, and belongs to the field of sealing materials. The lithium aluminum silicon filler comprises 10 to 15 mass percent of LiO 2 37% -50% of Al 2 O 3 35% -48% of SiO 2 The method comprises the steps of carrying out a first treatment on the surface of the The expansion coefficient of the lithium aluminum silicon filler is-80 multiplied by 10 ‑7 /℃～50×10 ‑7 a/DEG C; the lithium aluminum silicon-based filler may be free of lead. The glass sealing material comprises boron lead glass powder, lead titanate filler and lithium aluminum silicon filler according to the second aspect; the use of the lithium aluminum silicon filler in the glass sealing material can reduce the amount of lead titanate filler and can reduce the expansion coefficient and density.
Description
Technical Field
The application relates to the field of sealing materials, in particular to a lithium aluminum silicon filler composition, a lithium aluminum silicon filler, a preparation method of the lithium aluminum silicon filler, a glass sealing material and application of the glass sealing material.
Background
The sealing glass is an interlayer glass for sealing glass, ceramic, metal, composite material, etc. to each other, and when in use, it is necessary to select a sealing glass having an appropriate softening temperature and expansion coefficient. High lead sealing glasses that can be used at relatively low temperatures are known as solder glasses; the stable solder glass is mainly a boron-lead binary system, and a few secondary components such as silicon dioxide, barium oxide, zinc oxide, aluminum oxide, copper oxide and the like are often added to increase the stability and reduce the expansion coefficient.
At present, in sealing a device with a low expansion coefficient, lead titanate filler is generally used for solder glass to reduce the expansion coefficient of a glass sealing material, so that the glass sealing material is matched with the device, and adverse phenomena such as cracking and the like after sealing caused by unmatched expansion coefficients are effectively prevented.
Among them, lead titanate filler can reduce the expansion coefficient of solder glass to some extent, but the filler component contains lead, and even in the case of high usage, the solder glass still has a higher expansion coefficient, and the solder glass has a higher density, resulting in higher cost.
Disclosure of Invention
The invention aims to provide a lithium aluminum silicon filler composition, a lithium aluminum silicon filler and a preparation method thereof, a glass sealing material and application thereof, wherein the lithium aluminum silicon filler can be free of lead; the use of the lithium aluminum silicon filler in the glass sealing material can reduce the use amount of lead titanate filler and effectively reduce the expansion coefficient and density.
Embodiments of the present application are implemented as follows:
in a first aspect, the present application provides a lithium aluminum silicon-based filler composition comprising LiO 2 Source, al 2 O 3 Source and SiO 2 A source; in LiO 2 LiO provided by source 2 、Al 2 O 3 Source provided Al 2 O 3 SiO 2 Source provided SiO 2 The sum of the mass percentages of (2) is 100%, liO 2 Is 10 to 15 percent of the mass percentage of Al 2 O 3 37-50% of SiO 2 The mass percentage of (2) is 35-48%.
In a second aspect, the application provides a lithium aluminum silicon filler, which comprises 10 to 15 mass percent of LiO 2 37% -50% of Al 2 O 3 35% -48% of SiO 2 The method comprises the steps of carrying out a first treatment on the surface of the The expansion coefficient of the lithium aluminum silicon filler is-80 multiplied by 10 -7 /℃～50×10 -7 /℃。
In a third aspect, the present application provides a method for preparing the lithium aluminum silicon filler according to the second aspect, comprising: preparing the lithium aluminum silicon filler composition according to the first aspect, and subjecting the lithium aluminum silicon filler composition to a firing treatment.
In a fourth aspect, the present application provides a glass sealing material comprising boron lead glass frit, lead titanate filler, and a lithium aluminum silicon-based filler as in the second aspect.
In a fifth aspect, the present application provides an application of the glass sealing material according to the fourth aspect in sealing a lightning arrester valve plate or a solar heat collecting tube.
The lithium aluminum silicon filler composition, the lithium aluminum silicon filler and the preparation method thereof, the glass sealing material and the application thereof provided by the application have the beneficial effects that:
the lithium aluminum silicon filler composition and the lithium aluminum silicon filler can be lead-free and have better environmental protection; wherein the LiO is contained in a specific ratio 2 、Al 2 O 3 And SiO 2 Can be fired to obtain specific crystal phase, so that the lithium aluminum silicon filler has low expansion coefficient (-80×10) -7 /℃～50×10 -7 The expansion coefficient of the glass sealing material can be effectively reduced; at the same time, can effectively reduce the glassDensity of the sealing material.
In the glass sealing material, the lithium aluminum silicon filler is matched with the lead titanate filler, so that the expansion coefficient is reduced better than that of the lead titanate filler alone, the consumption of the lead titanate filler can be reduced, the expansion coefficient of the glass sealing material is ensured to be reduced better, and the glass sealing material can achieve lower expansion coefficient (50 multiplied by 10) -7 /℃～62×10 -7 /(deg.C.); the use of the lithium aluminum silicon filler can also effectively reduce the density of the glass sealing material, thereby being beneficial to reducing the cost.
The glass sealing material can achieve a lower expansion coefficient, can be well matched with a lightning arrester valve plate with a low expansion coefficient and a solar heat collecting tube, and effectively prevents bad phenomena such as cracking after sealing caused by unmatched expansion coefficients.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings that are needed in the embodiments will be briefly described below, it being understood that the following drawings only illustrate some embodiments of the present application and therefore should not be considered limiting the scope, and that other related drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
Fig. 1 is a process flow chart of a preparation process of a lithium aluminum silicon filler provided in an embodiment of the present application;
FIG. 2 is a graph showing sintering temperatures of lithium aluminum silicon based fillers provided in the examples of the present application;
FIG. 3 is a diagram showing a sintered glass sealing material according to an embodiment of the present application;
fig. 4 is a pattern diagram of the glass sealing material of the comparative example of the present application after sintering.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present application more clear, the technical solutions in the embodiments of the present application will be clearly and completely described below. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
In the description of the present application, the range of "numerical value a to numerical value b" includes both the end values "a" and "b".
In addition, "and/or" in this application, such as "feature 1 and/or feature 2", each refer to "feature 1" alone, and "feature 2" alone, and "feature 1" plus "feature 2" alone, in these three cases.
The lithium aluminum silicon filler composition, the lithium aluminum silicon filler, the preparation method thereof, the glass sealing material and the application thereof in the embodiment of the application are specifically described below.
In a first aspect, the present application provides a lithium aluminum silicon-based filler composition comprising LiO 2 Source, al 2 O 3 Source and SiO 2 A source.
In LiO 2 LiO provided by source 2 、Al 2 O 3 Source provided Al 2 O 3 SiO 2 Source provided SiO 2 The sum of the mass percentages of (2) is 100%, liO 2 10% to 15% by mass, such as, but not limited to, any one point value or range value between any two of 10%, 11%, 12%, 13%, 14% and 15%; al (Al) 2 O 3 37% to 50% by mass, such as, but not limited to, any one point value or a range value between any two of 37%, 40%, 42%, 43%, 45%, 47% and 50%; siO (SiO) 2 For example, but not limited to, 35% to 48% by mass, such as any one point value or a range value between any two of 35%, 38%, 40%, 42%, 45%, 46% and 48%.
In the present application, liO 2 The source means that LiO can be provided 2 Can be a component capable of producing LiO by a synthetic reaction 2 Is a substance of (a); it may be LiO 2 Itself, the method comprises the steps of; it is also possible to obtain LiO by decomposition or physical reaction 2 Substances of (2), e.g. Li 2 CO 3 。Al 2 O 3 Source and SiO 2 Source canIn the same manner, the explanation will not be repeated.
As an example, liO 2 The source is LiO 2 ，Al 2 O 3 The source is Al 2 O 3 ，SiO 2 The source is SiO 2 The method comprises the steps of carrying out a first treatment on the surface of the Further, the lithium aluminum silicon filler composition is composed of LiO 2 、Al 2 O 3 SiO 2 Composition is prepared.
In the application, the lithium aluminum silicon filler composition can be lead-free and has better environmental protection. The lithium aluminum silicon filler composition contains LiO in a specific ratio 2 、Al 2 O 3 And SiO 2 The lithium aluminum silicon filler with specific crystalline phase can be obtained by firing, so that the lithium aluminum silicon filler obtained by firing has lower expansion coefficient (-80 multiplied by 10) -7 /℃～50×10 -7 The expansion coefficient of the glass sealing material can be effectively reduced; meanwhile, the density of the glass sealing material can be effectively reduced.
In a second aspect, the present application provides a lithium aluminum silicon filler comprising 10 to 15 mass% of LiO 2 37% -50% of Al 2 O 3 35-48% SiO 2 . The lithium aluminum silicon filler can be obtained by sintering a lithium aluminum silicon filler composition according to the first aspect, wherein LiO 2 、Al 2 O 3 SiO 2 The mass percentage of the components in the lithium aluminum silicon filler composition may be the same as the mass percentage of the components in the lithium aluminum silicon filler composition.
In the present application, the expansion coefficient of the lithium aluminum silicon filler is-80×10 -7 /℃～50×10 -7 It has a lower expansion coefficient, and the use of the lithium aluminum silicon filler in combination with the lead titanate filler is preferable in terms of lowering the expansion coefficient than the use of the lead titanate filler alone. Therefore, in the sealing glass material, the lithium aluminum silicon filler can partially replace the lead titanate filler, so that the use amount of the lead titanate filler can be reduced, and the expansion coefficient of the glass sealing material can be better reduced.
In the application, the lithium aluminum silicon filler is applied to the sealing glass material, so that the density of the glass sealing material can be effectively reduced, and the cost is reduced.
In a third aspect, the present application provides a method for preparing the lithium aluminum silicon filler according to the second aspect, comprising: preparing the lithium aluminum silicon filler composition according to the first aspect, and subjecting the lithium aluminum silicon filler composition to a firing treatment.
In the method for producing a lithium aluminum silicon filler provided in the present application, other pretreatment or post-treatment steps may be added before and after the firing treatment step, as required.
As for the pretreatment step, as an example, the firing treatment step may be preceded by a ball milling treatment of the lithium aluminum silicon-based filler composition. As the granularity of the industrial grade raw materials of each component in the lithium aluminum silicon filler composition is large, the ball milling treatment is carried out in advance, which is beneficial to the uniform mixing of each component.
Optionally, in the ball milling treatment step, the ball-material ratio is (1.5-2.5): 1, or is (1.8-2.2): 1, for example, is 2:1, so that better ball milling efficiency and effect are ensured.
The particle diameter D50 of the material after ball milling is 8-10 μm or 8.5-9.5 μm, for example 9 μm; further, after the ball milling process, the material is sieved, for example, through a 200 mesh sieve and the undersize is taken. Pretreatment according to the above standard is beneficial to subsequent better firing.
As for the post-treatment step, as an example, the firing treatment step may further include pulverizing the fired material, for example, by ball milling, in a ball-to-material ratio of, for example, (0.4 to 0.6): 1, for example, 0.5:1; and then screened again, for example, through a 200 mesh screen and the undersize removed. The post-treatment is carried out according to the standard, so that the glass sealing material has proper particle size when being applied to the glass sealing material, and is convenient to mix uniformly.
As shown in fig. 1, in some exemplary embodiments, the method of preparing the lithium aluminum silicon-based filler includes:
(1) Weighing: the components in the lithium aluminum silicon filler composition are weighed according to the proportion, and the preparation of the lithium aluminum silicon filler composition is completed.
(2) Ball milling: ball milling is carried out on the lithium aluminum silicon filler composition.
(3) And (3) screening: and (5) screening the ball-milled material, and taking undersize.
(4) Firing: and firing the ball-milled and sieved lithium aluminum silicon filler composition.
(5) Crushing: and crushing the fired material.
(6) And (3) screening: sieving the crushed materials, and taking undersize materials.
The inventor researches that the lithium aluminum silicon filler composition provided by the application is favorable for firing to obtain a specific crystalline phase at 1250-1400 ℃ when being fired, and ensures that the lithium aluminum silicon filler has a lower expansion coefficient. If the firing is insufficient or excessive, a specific crystal phase cannot be formed well, and the expansion coefficient of the fired lithium aluminum silicon filler is eventually high.
Based on the above findings, in order to secure a good firing effect, as an example, the firing temperature in the firing treatment step is 1250 ℃ to 1400 ℃, for example, but not limited to, any one point value or a range value between any two of 1250 ℃, 1300 ℃, 1350 ℃ and 1400 ℃.
Further, the firing time is 2h to 5h, such as, but not limited to, any one of the point values of 2h, 3h, 4h, and 5h or a range value between any two.
In a fourth aspect, the present application provides a glass sealing material comprising boron lead glass frit, lead titanate filler, and a lithium aluminum silicon-based filler as in the second aspect. The glass sealing material provided by the application can be added with other auxiliary materials, such as pigment and the like, according to the requirement.
In the application, the glass sealing material is matched with the lead titanate filler by using the lithium aluminum silicon filler, so that the expansion coefficient is reduced better than that of the lead titanate filler singly, the consumption of the lead titanate filler can be reduced, and the expansion coefficient of the glass sealing material is ensured to be reduced better; the use of the lithium aluminum silicon filler can also effectively reduce the density of the glass sealing material, thereby being beneficial to reducing the cost.
In the application, the glass sealing material is matched with the lead titanate filler by using the lithium aluminum silicon filler, and the color of the glass sealing material after being sintered with the sealing material only using the lead titanate filler is better consistent, so that the appearance of the device is better consistent when the device is sealed by using different sealing materials.
In this application, the boron lead glass powder and lead titanate filler may be formulated as desired or selected according to criteria conventional in the art.
Regarding the boron-lead glass frit, as an example, it includes, in mass percent: 55% -70% of PbO and 10% -20% of B 2 O 3 2 to 10 percent of Al 2 O 3 2 to 8 percent of SiO 2 And 5% -15% of ZnO. Further, the boron-lead glass powder comprises the following components in percentage by mass: 60 to 65 percent of PbO and 15 to 18 percent of B 2 O 3 3 to 4 percent of Al 2 O 3 5 to 6 percent of SiO 2 And 10% -12% of ZnO.
Optionally, the boron-lead glass powder also comprises Ni with the total content less than or equal to 3 percent by mass 2 O 3 、Co 2 O 3 MnO and 2 . Further, ni 2 O 3 The mass percentage of Co is 0-1 percent 2 O 3 The mass percentage of (2) is 0-1%, mnO 2 The mass percentage of (2) is 0-1%.
As regards the lead titanate filler, as an example, it comprises, in mass percent: 62-79% of PbO and 20-30% of TiO 2 1% -8% CaCO 3 . Further, the lead titanate filler comprises the following components in percentage by mass: 69-72% of PbO and 25-27% of TiO 2 3% -4% CaCO 3 。
The glass sealing material provided by the application is prepared from boron lead glass powder, lead titanate filler and lithium aluminum silicon filler according to a proper proportion, and the expansion coefficient can be less than or equal to 62 multiplied by 10 -7 Criteria of/°c; the density can also be controlled to be less than or equal to 5.5g/cm 3 Even reaching the standard of less than or equal to 5g/cm 3 Is a standard of (2). As an example, the expansion coefficient of the glass sealing material is 50X 10 -7 /℃～62×10 -7 a/DEG C; glass sealThe expansion coefficient of the material is 4.4g/cm 3 ～5.5g/cm 3 Further, it is 4.4g/cm 3 ～5g/cm 3 。
Regarding the amount of the lead titanate filler, as an example, the mass percentage of the lead titanate filler in the glass sealing material is 10% or less, alternatively 3% to 10%, for example, but not limited to, any one point value or a range value between any two of 3%, 4%, 5%, 6%, 7%, 8%, 9% and 10%.
Regarding the amount of the lithium aluminum silicon filler, as an example, the mass percentage of the lithium aluminum silicon filler in the glass sealing material is 15% or less, alternatively 5% to 10%, for example, but not limited to, any one point value or a range value between any two of 5%, 6%, 7%, 8%, 9% and 10%.
The amounts of lead titanate filler and lithium aluminum silicon filler are regulated according to the proportion, so that the glass sealing material has a lower expansion coefficient and density which meet the above-mentioned exemplary standards, and the expansion coefficient of the glass sealing material has better matching with low expansion coefficient devices such as a lightning arrester valve plate and a solar heat collecting tube while ensuring the lower expansion coefficient and density of the glass sealing material.
The glass sealing material provided by the application is regulated and controlled according to the standard, and has better fluidity, proper softening temperature and sealing temperature. Wherein, the softening temperature can be regulated and controlled between 300 ℃ and 350 ℃, and the sealing temperature can be regulated and controlled between 500 ℃ and 550 ℃.
In the application, according to different expansion coefficients and density requirements, different types of boron lead glass powder and lead titanate filler can be matched, or the amounts of the lead titanate filler and the lithium aluminum silicon filler can be controlled according to different standards.
In a fifth aspect, the present application provides an application of the glass sealing material according to the fourth aspect in sealing a lightning arrester valve plate or a solar heat collecting tube.
The expansion coefficients of the lightning arrester valve plate and the solar heat collecting tube are low, wherein the prior art adopts solder glass to seal the lightning arrester valve plateWhen in connection, adverse phenomena such as cracking and the like usually occur after sealing due to mismatch of expansion coefficients; the expansion coefficient of solar collector tubes is typically 33×10 -7 However, prior art techniques generally use only metals for sealing.
The glass sealing material can be provided with the low expansion coefficient for matching and sealing the arrester valve plate and the solar heat collecting tube, can be used for better sealing the arrester valve plate and the solar heat collecting tube, and effectively prevents bad phenomena such as cracking after sealing caused by unmatched expansion coefficients.
The features and capabilities of the present application are described in further detail below in connection with the examples.
And (I) preparing a glass sealing material.
1.1, preparing boron-lead glass powder.
The preparation method comprises the following steps of: yellow lead (PbO) 63.35%; boric acid (B) 2 O 3 ) 16.2%; 11% of zinc oxide (ZnO); silicon dioxide (SiO) 2 ) 5.55%; alumina (Al) 2 O 3 ) 3.6%; nickel sesquioxide (Ni) 2 O 3 ) 0.15%; cobalt oxide (Co) 2 O 3 ) 0.1%; manganese dioxide (MnO) 2 )0.05％。
And (3) uniformly mixing the raw materials, loading the mixture into a ceramic small crucible, putting the ceramic small crucible into a muffle furnace, melting the ceramic small crucible for 1h at the constant temperature of 1150 ℃, taking out the ceramic small crucible, using a rolling mill to press glass liquid into sheets, performing ball milling after the glass sheets are cooled, and sieving the glass sheets with a 280-mesh sieve to obtain the boron-lead glass powder. The density of the boron-lead glass powder is 5.2+/-0.15 g/cm 3 。
1.2, preparing lead titanate filler.
The preparation method comprises the following steps of: 70.24% of yellow lead (PbO); titanium dioxide (TiO) 2 ) 26.22%; calcium carbonate (CaCO) 3 )3.54％。
The raw materials are uniformly mixed, the mixture is put into a ceramic sagger, the ceramic sagger is put into a pit furnace to be burned for 2 hours at the constant temperature of 1100 ℃, the lead titanate filler blocks are ball-milled after being taken out, and then the lead titanate filler is obtained by sieving the lead titanate filler blocks with 280 meshes to obtain the screen lower material. The density of the lead titanate filler is7.5±0.1g/cm 3 。
1.3, preparing the lithium aluminum silicon filler.
The preparation method comprises the following steps of: lithium oxide (LiO) 2 ) 11.4% of alumina (Al) 2 O 3 ) 42.77% and silicon oxide (SiO) 2 )45.83％。
The raw materials are put into a porcelain bottle, and alumina porcelain balls with the weight being 2 times of the total weight of the raw materials are put into the porcelain bottle for ball milling. The mixture D50 is approximately equal to 9 after ball milling, and the mixture is sieved by a 200-mesh sieve to obtain a sieve bottom. The mixture after sieving is put into a small ceramic crucible and is put into an atmosphere furnace to be fired for 4 hours, and the firing temperature curve is shown in figure 2. And taking out the agglomerated filler after firing, putting the agglomerated filler into a porcelain bottle, putting 1/2 of alumina porcelain balls in the total weight of the filler block for ball milling, and sieving the mixture by a 200-mesh sieve to obtain the lithium aluminum silicon filler.
1.4, preparing a glass sealing material.
The boron-lead glass powder, lead titanate filler and lithium aluminum silicon filler prepared by the above steps were mixed in a specific ratio, and a certain amount of black pigment was added, and the compositions of each example and comparative example are shown in table 1.
TABLE 1 glass sealing material component mass percent
And (II) testing the performance glass sealing material.
2.1, the density and expansion coefficient of the glass sealing material were measured, and the measurement results are shown in Table 2.
The method for testing the expansion coefficient comprises the following steps: and (3) placing the glass sealing material into a cylindrical or ship-shaped mold of an aluminum foil roll, repeatedly compacting, and then placing into a muffle furnace to sinter at the temperature of 460 ℃. And taking out the sample after the sintering is completed and cooled, stripping the aluminum foil, grinding the two ends of the sample, then testing by using a coefficient of expansion instrument, and reading the average coefficient of expansion at the room temperature to 250 ℃.
TABLE 2 Properties of glass sealing Material
As can be seen from table 2:
the glass sealing materials provided in examples 1 to 3 of the present application all had densities controlled at 4.4g/cm 3 ～5g/cm 3 Has a smaller density in the range of (2); the expansion coefficients are controlled to be 50 multiplied by 10 -7 /℃～62×10 -7 In the range of/. Degree.C, has a small expansion coefficient.
In comparative example 1, no lithium aluminum silicon filler was added and the amount of lead titanate filler was higher than in example 1.
In comparative example 1, since no lithium aluminum silicon filler was added, lead titanate filler was used in a large amount as much as possible, and the density and expansion coefficient were still high.
Comparative example 2 is the same in total filler as example 1, but no lithium aluminum silicon filler was added; comparative example 3 is the same in total filler as example 2, but no lithium aluminum silicon filler was added; comparative example 4 was identical in total filler amount to example 3, but no lithium aluminum silicon filler was added.
The comparison of comparative example 2 and example 1, the comparison of comparative example 3 and example 2, and the comparison of comparative example 4 and example 3 are all represented by: under the condition that the material used for the filler is unchanged, the density and the expansion coefficient are obviously increased because no lithium aluminum silicon filler is added.
2.2, sintering the glass sealing material, and observing the sintered form.
Fig. 3 is a pattern diagram of the glass sealing material of the example after sintering, and fig. 4 is a pattern diagram of the glass sealing material of the comparative example after sintering.
As can be seen from fig. 3 and 4, the glass sealing material using the lithium aluminum silicon filler and the lead titanate filler in the embodiment of the present application has better consistency of the color of the sealing material after sintering compared with the sealing material using the lead titanate filler in the comparative example.
The embodiments described above are some, but not all, of the embodiments of the present application. The detailed description of the embodiments of the present application is not intended to limit the scope of the application, as claimed, but is merely representative of selected embodiments of the application. All other embodiments, which can be made by one of ordinary skill in the art based on the embodiments herein without making any inventive effort, are intended to be within the scope of the present application.
Claims (4)
1. The glass sealing material is characterized by comprising boron-lead glass powder, lead titanate filler and lithium aluminum silicon filler; the expansion coefficient of the glass sealing material is 50 multiplied by 10 -7 /℃～62×10 -7 a/DEG C; the density of the glass sealing material is 4.4g/cm 3 ～5.5g/cm 3 ；
The boron-lead glass powder comprises 60-65% of PbO and 15-18% of B by mass percent 2 O 3 3 to 4 percent of Al 2 O 3 5 to 6 percent of SiO 2 10 to 12 percent of ZnO and 0 to 1 percent of Ni 2 O 3 0 to 1 percent of Co 2 O 3 MnO 0-1% 2 Composition;
the lead titanate filler consists of 69-72% of PbO and 25-27% of TiO by mass percent 2 3% -4% CaCO 3 Composition;
the mass percentage of the lead titanate filler is less than or equal to 10%;
the mass percentage of the lithium aluminum silicon filler is less than or equal to 15 percent;
the preparation method of the lithium aluminum silicon filler comprises the following steps: preparing a lithium aluminum silicon filler composition, and firing the lithium aluminum silicon filler composition; in the firing treatment step, the firing temperature is 1250-1400 ℃ and the firing time is 2-5 h;
the lithium aluminum silicon filler comprises 10-15% of Li by mass percent 2 O, 37-50% Al 2 O 3 35% -48% of SiO 2 Composition; the saidThe expansion coefficient of the lithium aluminum silicon filler is-80 multiplied by 10 -7 /℃～50×10 -7 /℃。
2. The glass sealing material according to claim 1, wherein the method for producing a lithium aluminum silicon filler, before the firing step, further comprises: and ball milling the lithium aluminum silicon filler composition.
3. The glass sealing material according to claim 2, wherein in the ball-milling step, the ball-to-material ratio is (1.5-2.5): 1, and the particle diameter D50 of the ball-milled material is 8 μm-10 μm.
4. Use of a glass sealing material according to any one of claims 1 to 3 for sealing a lightning arrester panel or a solar heat collecting tube.
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| US4710479A (en) * | 1986-04-16 | 1987-12-01 | Nippon Electric Glass Company, Limited | Sealing glass composition with lead calcium titanate filler |
| JPH0517149A (en) * | 1991-07-03 | 1993-01-26 | Iwaki Glass Kk | Lead titanate solid solution and sealing material using the same solid solution |
| CN1208396A (en) * | 1996-01-16 | 1999-02-17 | 康宁股份有限公司 | Athermal optical device |
| JP2001089188A (en) * | 2000-08-03 | 2001-04-03 | Nippon Electric Glass Co Ltd | Composition for low temperature sealing |
| JP2003327434A (en) * | 2002-05-13 | 2003-11-19 | Nippon Electric Glass Co Ltd | Method for manufacturing sealing material |
| CN1587147A (en) * | 2004-07-30 | 2005-03-02 | 京东方科技集团股份有限公司 | Low melting point, low expanding coefficient solder glass seal powder and its preparing method |
| CN111499207A (en) * | 2020-04-20 | 2020-08-07 | 北京北旭电子材料有限公司 | Glass powder, valve plate structure and preparation method |
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|---|---|---|---|---|
| US4710479A (en) * | 1986-04-16 | 1987-12-01 | Nippon Electric Glass Company, Limited | Sealing glass composition with lead calcium titanate filler |
| JPH0517149A (en) * | 1991-07-03 | 1993-01-26 | Iwaki Glass Kk | Lead titanate solid solution and sealing material using the same solid solution |
| CN1208396A (en) * | 1996-01-16 | 1999-02-17 | 康宁股份有限公司 | Athermal optical device |
| JP2001089188A (en) * | 2000-08-03 | 2001-04-03 | Nippon Electric Glass Co Ltd | Composition for low temperature sealing |
| JP2003327434A (en) * | 2002-05-13 | 2003-11-19 | Nippon Electric Glass Co Ltd | Method for manufacturing sealing material |
| CN1587147A (en) * | 2004-07-30 | 2005-03-02 | 京东方科技集团股份有限公司 | Low melting point, low expanding coefficient solder glass seal powder and its preparing method |
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