CN113024124A - Glass powder and preparation method thereof - Google Patents
Glass powder and preparation method thereof Download PDFInfo
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- CN113024124A CN113024124A CN202010908116.0A CN202010908116A CN113024124A CN 113024124 A CN113024124 A CN 113024124A CN 202010908116 A CN202010908116 A CN 202010908116A CN 113024124 A CN113024124 A CN 113024124A
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- 239000011521 glass Substances 0.000 title claims abstract description 201
- 239000000843 powder Substances 0.000 title claims abstract description 94
- 238000002360 preparation method Methods 0.000 title claims description 16
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 42
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 39
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000002994 raw material Substances 0.000 claims abstract description 31
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 23
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 23
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 23
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 23
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 23
- 238000002844 melting Methods 0.000 claims abstract description 22
- 230000008018 melting Effects 0.000 claims abstract description 22
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims abstract description 21
- FUJCRWPEOMXPAD-UHFFFAOYSA-N Li2O Inorganic materials [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 claims abstract description 20
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910052593 corundum Inorganic materials 0.000 claims abstract description 20
- XUCJHNOBJLKZNU-UHFFFAOYSA-M dilithium;hydroxide Chemical compound [Li+].[Li+].[OH-] XUCJHNOBJLKZNU-UHFFFAOYSA-M 0.000 claims abstract description 20
- 229910001845 yogo sapphire Inorganic materials 0.000 claims abstract description 20
- 239000002245 particle Substances 0.000 claims description 52
- 238000000498 ball milling Methods 0.000 claims description 27
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 23
- 229910052726 zirconium Inorganic materials 0.000 claims description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- 238000010791 quenching Methods 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 18
- 230000000171 quenching effect Effects 0.000 claims description 18
- 238000000227 grinding Methods 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 11
- 239000006060 molten glass Substances 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 10
- 230000008569 process Effects 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 238000007873 sieving Methods 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 238000010309 melting process Methods 0.000 claims 1
- 238000005245 sintering Methods 0.000 abstract description 20
- 239000005394 sealing glass Substances 0.000 abstract description 17
- 239000000126 substance Substances 0.000 abstract description 13
- 230000009471 action Effects 0.000 abstract description 5
- 239000000463 material Substances 0.000 abstract description 4
- 238000010438 heat treatment Methods 0.000 description 12
- 239000000047 product Substances 0.000 description 10
- 230000000694 effects Effects 0.000 description 8
- 238000007789 sealing Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 229910001385 heavy metal Inorganic materials 0.000 description 7
- 238000012360 testing method Methods 0.000 description 6
- 239000012856 weighed raw material Substances 0.000 description 6
- 238000005303 weighing Methods 0.000 description 6
- 238000004383 yellowing Methods 0.000 description 6
- 238000012216 screening Methods 0.000 description 5
- 229910052787 antimony Inorganic materials 0.000 description 4
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 4
- 229910052793 cadmium Inorganic materials 0.000 description 4
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 4
- 238000010276 construction Methods 0.000 description 4
- 230000006378 damage Effects 0.000 description 4
- 229910010293 ceramic material Inorganic materials 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 239000006184 cosolvent Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 210000001808 exosome Anatomy 0.000 description 2
- 239000000156 glass melt Substances 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- 230000005764 inhibitory process Effects 0.000 description 2
- 238000011031 large-scale manufacturing process Methods 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000011819 refractory material Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 239000013589 supplement Substances 0.000 description 2
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- OBNDGIHQAIXEAO-UHFFFAOYSA-N [O].[Si] Chemical group [O].[Si] OBNDGIHQAIXEAO-UHFFFAOYSA-N 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000003796 beauty Effects 0.000 description 1
- 238000005352 clarification Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000000113 differential scanning calorimetry Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 230000014509 gene expression Effects 0.000 description 1
- 238000007496 glass forming Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 150000002632 lipids Chemical class 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000002834 transmittance 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
- C03C12/00—Powdered glass; Bead compositions
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/062—Glass compositions containing silica with less than 40% silica by weight
- C03C3/064—Glass compositions containing silica with less than 40% silica by weight containing boron
- C03C3/066—Glass compositions containing silica with less than 40% silica by weight containing boron containing zinc
Abstract
The application belongs to the technical field of materials, and particularly relates to glass powder, which comprises the following raw material components in percentage by mass based on the total mass of the glass powder being 100 percent: b is2O3 18～30％，SiO2 20～35％，ZnO 15～30％，Na2O and K2The total mass percentage of O is 2-12%, ZrO2 1～8％，TiO2 5～10％，Li2O 0.1～1.5％，F2 0～1％、BaO 2～8％，CaO 0～2％，Al2O30.5 to 1 percent. The glass powder provided by the application has the characteristics of good chemical stability, low melting point and the like through mutual combined action of the components in the raw material formula, can be used as sealing glass and sintering aid, and meets various requirements of various industries on the types and performances of the sealing glass and the sintering aid.
Description
Technical Field
The application belongs to the technical field of materials, and particularly relates to glass powder and a preparation method of the glass powder.
Background
At present, sealing glass is widely applied to sealing of integrated circuits, semiconductor devices and the like in electronic products, and the demand of the sealing glass is increasing along with the popularization of various electronic products. For a long time, the inorganic sealing glass adopted in industrial production has the advantages of simple preparation process, high temperature resistance, high strength, corrosion resistance and the like. However, the components of the adopted sealing glass often contain heavy metal elements such as lead, cadmium, antimony and the like, which causes great pollution to the surrounding environment and also causes great harm to the health of human bodies.
In the face of new generation people who continuously enhance the environmental protection consciousness, how to reduce or even stop the heavy metal elements such as lead, cadmium, antimony and the like in the sealed glass becomes the key point of the prior research of people. In addition, most ceramic materials have the problems of high sintering temperature, high energy consumption and the like. The proportion of energy consumption in the production cost of the ceramic material is relatively high, the forming temperature required by sintering of the ceramic material is reduced, and the energy consumption of enterprises in the production process can be effectively reduced. The novel sintering aid can effectively reduce the sintering temperature of the ceramic product, thereby reducing the production cost of enterprises and improving certain properties of the ceramic product. Therefore, the development of new glass system adjuvants has also become a primary task in the current research phase. Common vanadate system glass, phosphate system glass, bismuthate system glass and boron and silicate system glass can be used as sealing glass and sintering aid. However, each system glass has certain defects and shortcomings, such as: the problems of raw material sources and production cost exist in vanadate system glass and bismuthate system glass; phosphate system glasses suffer from chemical stability problems, etc.
Disclosure of Invention
The application aims to provide glass powder and a preparation method thereof, and aims to solve the problems that the existing glass powder contains heavy metal, is large in environmental pollution, poor in chemical stability, high in softening temperature and high in raw material cost to a certain extent.
In order to achieve the purpose of the application, the technical scheme adopted by the application is as follows:
in a first aspect, the present application provides a glass frit, which is characterized by comprising, by mass, 100% of the total mass of the glass frit: b is2O3 18～30％，SiO2 20～35％，ZnO 15～30％，Na2O and K2The total mass percentage of O is 2-12%, ZrO2 1～8％，TiO2 5～10％，Li2O 0.1～1.5％，F2 0～1％、BaO 2～8％，CaO 0～2％，Al2O30.5 to 1 percent. In a second aspect, the present application provides a method for preparing glass frit, comprising the steps of:
obtaining raw material components in the glass powder;
mixing the raw material components in the glass powder, and then sequentially carrying out melting treatment, quenching treatment, grinding treatment and drying treatment to obtain the glass powder.
The glass powder provided by the first aspect of the application has the characteristics of good chemical stability, low melting point and the like under the combined action of the raw material components. The sealing glass can be used as sealing glass and sintering aids, can supplement the types of the sintering aids, overcomes the defects of higher sintering temperature and sealing temperature of borosilicate series sealing glass to a certain extent, and meets the requirements of various industries on the types and performances of the sealing glass and the sintering aids and the like.
According to the preparation method of the glass powder provided by the second aspect of the application, after the raw material components in the glass powder are uniformly mixed, the components are melted and mixed into an organic whole through melting treatment, then the glass melt is quenched into glass particles through quenching treatment, and then the particle size of the glass particles is reduced through grinding treatment, so that the glass powder with uniform particle size is obtained, and the subsequent construction and application are facilitated. The preparation method of the glass powder provided by the embodiment of the application is simple in process and suitable for industrial large-scale production and application.
Detailed Description
In order to make the technical problems, technical solutions and advantageous effects to be solved by the present application more clearly apparent, the present application is further described in detail below with reference to the embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the present application and are not intended to limit the present application.
In the present invention, the term "and/or" describes the association relationship of the associated objects, and means that there may be three relationships, for example, a and/or B, which may mean: a is present alone, A and B are present simultaneously, and B is present alone. Wherein A and B can be singular or plural. The character "/" generally indicates that the former and latter associated objects are in an "or" relationship.
In the present invention, "at least one" means one or more, "a plurality" means two or more. "at least one of the following" or similar expressions refer to any combination of these items, including any combination of the singular or plural items. For example, "at least one (one) of a, b, or c," or "at least one (one) of a, b, and c," may each represent: a, b, c, a-b (i.e., a and b), a-c, b-c, or a-b-c, wherein a, b, and c may be single or plural, respectively.
It should be understood that, in various embodiments of the present invention, the sequence numbers of the above-mentioned processes do not mean the execution sequence, some or all of the steps may be executed in parallel or executed sequentially, and the execution sequence of each process should be determined by its function and inherent logic, and should not constitute any limitation to the implementation process of the embodiments of the present invention.
The terminology used in the embodiments of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used in the examples of the invention and the appended claims, the singular forms "a," "an," and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise.
The weight of the related components mentioned in the description of the embodiments of the present invention may not only refer to the specific content of each component, but also represent the proportional relationship of the weight among the components, and therefore, the content of the related components is scaled up or down within the scope disclosed in the description of the embodiments of the present invention as long as it is in accordance with the description of the embodiments of the present invention. Specifically, the mass in the description of the embodiments of the present invention may be a mass unit known in the chemical industry field such as μ g, mg, g, kg, etc.
The terms "first" and "second" are used for descriptive purposes only and are used for distinguishing purposes such as substances from one another, and are not to be construed as indicating or implying relative importance or implying any number of technical features indicated. For example, a first XX may also be referred to as a second XX, and similarly, a second XX may also be referred to as a first XX, without departing from the scope of embodiments of the invention. Thus, a feature defined as "first" or "second" may explicitly or implicitly include one or more of that feature.
The first aspect of the embodiments of the present application provides a glass frit, which comprises, by mass, 100% of the total mass of the glass fritRaw material components by weight: b is2O3 18～30％，SiO2 20～35％，ZnO 15～30％，Na2O and K2The total mass percentage of O is 2-12%, ZrO2 1～8％，TiO2 5～10％，Li2O 0.1～1.5％，F2 0～1％、BaO 2～8％，CaO 0～2％，Al2O3 0.5～1％。
The glass powder provided by the first aspect of the application belongs to B2O3-SiO2-ZnO borosilicate series glass, which can be used as sealing glass and sintering aid, B in the glass powder2O3、SiO2The ZnO and other raw material components have wide sources, and the production cost can be effectively reduced; and the glass is nontoxic and harmless, does not contain heavy metals such as lead, cadmium, antimony and the like, avoids the harm of heavy metal glass to the environment and the human health, and has high safety. In the raw material formula B of the glass powder passing in the embodiment of the application2O3 18～30％，SiO2 20～35％，ZnO 15～30％，Na2O and K2The total mass percentage of O is 2-12%, ZrO2 1～8％，TiO2 5～10％，Li2O 0.1～1.5％，F2 0～1％、BaO 2～8％，CaO 0～2％，Al2O3The mutual combined action of 0.5-1% of the components makes the glass powder have the characteristics of good chemical stability, low melting point and the like, can supplement the types of sintering aids, makes up the defects of higher sintering temperature and higher sealing temperature of borosilicate series sealing glass to a certain extent, and meets the requirements of various industries on the types and the performances of the sealing glass and the sintering aids and the like.
In the glass powder provided by the embodiment of the application, SiO2Is an important glass forming material, and the structural units of silicon-oxygen tetrahedron form an irregular continuous network to form a framework of the glass. SiO in glass powder2Preferably, the content of (A) is 20 to 35%, if SiO2The content is higher than 35%, the melting temperature of the glass powder is higher, and the fluidity is poor; if SiO2The content of less than 20% results in poor acid resistance after glass frit molding and a high expansion coefficient.
In the glass powder provided by the embodiment of the application, B2O3Also is an oxide of the glass, can improve the thermal stability of the glass, reduce the viscosity of the glass at high temperature and play a role in fluxing. B in glass powder2O3The content of (A) is preferably 18-30%, and if the content is less than 18%, the glass is turbid during melting, and has poor purity and light transmittance; if the content is more than 30%, the expansion coefficient of the glass increases, and abnormal boron phenomenon occurs, and the acid resistance is lowered.
In the glass powder provided by the embodiment of the application, ZnO is used as a network exosome oxide and mainly plays a role in reducing the softening point of the glass powder in glass, and the optimal content is 15-30%. If the content is less than 15%, the adjusting effect on the melting temperature of the glass powder is not obvious; if the content is more than 30%, the glass tends to be crystallized.
In the glass powder provided by the embodiment of the application, Na2O，K2O is a cosolvent, so that the viscosity of the glass can be reduced, the glass is easy to melt, the total content is 2-12%, and the thermal stability, the chemical stability and the mechanical strength are easy to reduce if the content is too high; if the content is too low, the effect of adjusting the melt viscosity, the melting temperature, etc. of the glass powder is not good. Li2O is also a network exosome and can replace Na2O or K2O reduces the glass expansion coefficient, reduces the crystallization tendency, and lowers the melting temperature of the glass. Generally, the addition of 0.1 to 1.5% is preferred, and the tendency to crystallize is increased by introducing too much.
In the glass powder provided by the embodiment of the application, Al2O3The crystallization tendency of the glass can be reduced, the chemical stability of the glass is improved, the corrosion of the glass to refractory materials is reduced, the content is preferably 0.5-1%, and if the content is too high, the phenomena of too high viscosity and poor liquidity of the glass are easily caused; if the content is too low, the glass powder has poor adjusting effects on the chemical stability, weather resistance and the like of the glass powder, and the overall performance of the glass powder is reduced.
In the glass powder provided by the embodiment of the application, TiO2The refractive index and the chemical stability of the glass can be improved, and the content is preferably 5-10%.
In the glass powder provided by the embodiment of the application, ZrO2The glass mainly plays a role in improving the hardness of glass and reducing the thermal expansion coefficient of the glass in the glass system, the content is preferably 1-8%, if the content is lower than 1%, the effects of reducing the thermal expansion coefficient of the glass and improving the hardness of the glass are small, and if the content is higher than 8%, the viscosity of the glass is too high, the wettability of the glass and metal is poor, and the sealing effect is influenced.
In the glass powder provided by the embodiment of the application, BaO and CaO respectively account for 2-8% and 0-2%, the chemical resistance of glass can be improved, and when the content is excessive, the corrosion to refractory materials is easily caused.
In the glass powder provided by the embodiment of the application, the content of F is 0-1%2Is an auxiliary raw material, accelerates the clarification of the glass, and is a cosolvent, so that the melting speed of the glass can be improved.
In some embodiments, the glass frit has an average particle size of no greater than 2 microns, and the small and uniform size of the glass frit facilitates its use as a sealing glass or sintering aid and provides a formed glass with better flatness and finish. In some embodiments, the glass frit has an average particle size of 0.1 microns, 0.5 microns, 0.8 microns, 1 micron, 1.2 microns, 1.5 microns, 1.8 microns, 2 microns, or the like.
In some embodiments, the glass powder of the embodiments of the present application has a lower softening temperature, which is not higher than 536 ℃, through the combined action of the raw material components, and is more favorable for the use of the glass powder as sealing glass or sintering aid. The glass powder can be used at low temperature, particularly for sealing of some electronic products, the substrate can be damaged when the temperature is too high, and the lower the sealing temperature is, the better the performance is ensured.
In some specific embodiments, the glass powder comprises the following raw material components by mass percent, based on 100% of the total mass of the glass powder: b is2O3 27％、SiO2 25％、ZnO 23％、Na2O 3％、K2O 4％、ZrO2 8％、TiO2 5％、Li2O 1％、BaO 3.5％、Al2O3 0.5％。
In other specific embodiments, the composition comprises the following raw material components in percentage by mass: b is2O3 25％、SiO2 30％、ZnO 23％、Na2O 0.6％、K2O 2.8％、ZrO2 3％、TiO2 7％、Li2O 0.6％、F2 0.5％、BaO 6％、CaO 1％、Al2O3 0.5％。
In other specific embodiments, the composition comprises the following raw material components in percentage by mass: b is2O3 24％、SiO2 30％、ZnO 20％、Na2O 2％、K2O 4.5％、ZrO2 4％、TiO2 6％、Li2O 1％、F2 1％、BaO 4.5％、CaO 2.0％、Al2O3 1％。
In other specific embodiments, the composition comprises the following raw material components in percentage by mass: b is2O3 20％、SiO2 30％、ZnO 17％、Na2O 7％、K2O 5％、ZrO2 3.2％、TiO2 8％、Li2O 1％、BaO 7％、CaO 1％、Al2O30.8％。
The glass powder provided by the embodiment of the application can be prepared by the following method of the embodiment.
A second aspect of the embodiments of the present application provides a method for preparing glass frit, including the following steps:
obtaining raw material components in the glass powder of the embodiment;
mixing the raw material components in the glass powder, sequentially carrying out melting treatment, quenching treatment and grinding treatment, and drying to obtain the glass powder.
According to the preparation method of the glass powder provided by the second aspect of the application, after the raw material components in the glass powder are uniformly mixed, the components are melted and mixed into an organic whole through melting treatment, then the glass melt is quenched into glass particles through quenching treatment, the particle size of the glass particles is reduced through grinding treatment, the glass powder with uniform particle size is obtained after drying, and the subsequent construction and application are facilitated. The preparation method of the glass powder provided by the embodiment of the application is simple in process and suitable for industrial large-scale production and application.
In some embodiments, the raw material components in the glass powder are mixed uniformly, and then are melted and mixed for 30-90 min at 1100-1300 ℃ to fully react the raw material components. In some embodiments, the melting temperature may be 1100 ℃ to 1200 ℃ to 1300 ℃.
In some embodiments, the step of quenching comprises: and quenching the molten glass after the melting treatment by using water as a quenching agent to water-quench the molten glass into glass particles. In some embodiments, the molten glass is poured directly into water and water quenched into glass particles.
In some embodiments, the step of grinding comprises: under the condition that the mass ratio of the glass particles to water to the large zirconium balls to the small zirconium balls is 1:1 (2-4) to (2-5), ball milling treatment is carried out on the glass particles for 3-4.5 hours at the rotating speed of 200-350 r/min, and the particle size of the glass particles is smaller and uniform through ball milling treatment, so that the subsequent melting application is facilitated. In some embodiments, the step of ball milling comprises: under the condition that the mass ratio of the glass particles to water to the large zirconium balls to the small zirconium balls is 1:1 (2-4) to (2-5), ball milling treatment is carried out on the glass particles for 2-3 hours at the rotating speed of 200-300 r/min, then ball milling treatment is carried out for 1-2 hours at the rotating speed of 300-350 r/min, and the particle size of the glass particles can be better refined through ball milling in stages. In some embodiments, the step of ball milling comprises: under the condition that the mass ratio of the glass particles to water to the large zirconium balls to the small zirconium balls is 1:1:3:3, the glass particles are subjected to ball milling treatment for 2-3 hours at the rotating speed of 250r/min, then are subjected to ball milling treatment for 1-2 hours at the rotating speed of 320r/min, and the particle size of the glass particles can be better refined through staged ball milling.
In some embodiments, after the grinding process, the method further comprises the steps of: the product after grinding treatment is sieved, the particle size of the collected glass powder is small and uniform, and the melting softening temperature and the melting softening speed of the small-particle-size and uniform glass powder are the same during construction and application, so that the construction and application are facilitated; meanwhile, the problem of insufficient melting and softening caused by large particle size difference in application of the glass powder can be avoided, and the formed glass has better flatness and smoothness. And the glass powder particles with larger particle size after sieving can be ground again or recycled to the next batch of products to be ground together with the next batch of products. In some embodiments, the glass powder after grinding and sieving treatment has a particle size of not more than 2 microns, and the glass powder with small and uniform particle size is more convenient to use as sealing glass or sintering aid.
The glass powder prepared by the embodiment of the application does not contain heavy metals such as lead, cadmium, antimony and the like, so that the harm caused by the heavy metals is avoided; compared with bismuthate glass, the bismuthate glass has sufficient raw material supply, and can effectively reduce the cost required by purchasing raw materials. And the prepared glass powder has the advantages of low melting point, chemical stability and the like through the combined action of the raw material components.
In order to make the above-mentioned details and operations of the present application clearly understood by those skilled in the art and to make the progress of the glass powder and the method for preparing the same apparent, the above-mentioned technical solutions are illustrated by the following examples.
Example 1
The glass powder comprises the following preparation steps:
weighing B according to the mass percent, wherein the total mass of the glass powder is 100 percent2O3 27％、SiO2 25％、ZnO 23％、Na2O 3％、K2O 4％、ZrO2 8％、TiO2 5％、Li2O 1％、BaO 3.5％、Al2O3 0.5％；
Secondly, putting the weighed raw materials into a mixer, mixing for 1h, taking out, putting into a crucible, heating to 1250 ℃ at a heating rate of 10 ℃/min, preserving heat for 1h, pouring molten glass into water, and quenching to obtain glass particles;
thirdly, according to the glass: pure water: large zirconium balls: and (3) placing the small zirconium balls into a ball milling tank according to the proportion of 1:1:3:3, carrying out ball milling at 250r/min for 3 hours and at 320r/min for 1.5 hours, taking out, drying in an oven at 110 ℃, and screening by using a 3000-mesh screen to obtain glass powder with the average particle size of 685 nm.
Example 2
The glass powder comprises the following preparation steps:
weighing B according to the mass percent, wherein the total mass of the glass powder is 100 percent2O3 25％、SiO2 30％、ZnO 23％、Na2O 0.6％、K2O 2.8％、ZrO2 3％、TiO2 7％、Li2O 0.6％、F2 0.5％、BaO 6％、CaO 1％、Al2O3 0.5％；
Secondly, putting the weighed raw materials into a mixer, mixing for 1h, taking out, putting into a crucible, heating to 1150 ℃ at a heating rate of 10 ℃/min, preserving heat for 1h, pouring molten glass into water, and quenching to obtain glass particles;
thirdly, according to the glass: pure water: large zirconium balls: and (3) placing the small zirconium balls into a ball milling tank according to the ratio of 1:1:3:3, carrying out ball milling at 250r/min for 3 hours and 320r/min for 1.5 hours, taking out, drying in an oven at 110 ℃, and screening by using a 3000-mesh screen to obtain the glass powder with the average particle size of 613 nm.
Example 3
The glass powder comprises the following preparation steps:
weighing B according to the mass percent, wherein the total mass of the glass powder is 100 percent2O3 24％、SiO2 30％、ZnO 20％、Na2O 2％、K2O 4.5％、ZrO2 4％、TiO2 6％、Li2O 1％、F2 1％、BaO 4.5％、CaO 2.0％、Al2O3 1％；
Secondly, putting the weighed raw materials into a mixer, mixing for 1h, taking out, putting into a crucible, heating to 1250 ℃ at a heating rate of 10 ℃/min, preserving heat for 1h, pouring molten glass into water, and quenching to obtain glass particles;
thirdly, according to the glass: pure water: large zirconium balls: and (3) placing the small zirconium balls into a ball milling tank according to the proportion of 1:1:3:3, carrying out ball milling at 250r/min for 3 hours and at 320r/min for 1.5 hours, taking out, drying in an oven at 110 ℃, and screening by using a 3000-mesh screen to obtain the glass powder with the average particle size of 598 nm.
Example 4
The glass powder comprises the following preparation steps:
weighing B according to the mass percent, wherein the total mass of the glass powder is 100 percent2O3 20％、SiO2 30％、ZnO 17％、Na2O 7％、K2O 5％、ZrO2 3.2％、TiO2 8％、Li2O 1％、BaO 7％、CaO 1％、Al2O3 0.8％；
Secondly, putting the weighed raw materials into a mixer, mixing for 1h, taking out, putting into a crucible, heating to 1300 ℃ at a heating rate of 10 ℃/min, preserving heat for 1h, pouring molten glass into water, and quenching to obtain glass particles;
thirdly, according to the glass: pure water: large zirconium balls: and (3) placing the small zirconium balls into a ball milling tank according to the ratio of 1:1:3:3, carrying out ball milling at 250r/min for 3 hours and at 320r/min for 1.5 hours, taking out, drying in an oven at 110 ℃, and sieving by using a 3000-mesh sieve to obtain the glass powder with the average particle size of 491 nm.
Comparative example 1
The glass powder comprises the following preparation steps:
weighing B according to the mass percentage, wherein the total mass of the glass powder is 100 percent2O3 8％、SiO2 38％、ZnO 33％、Na2O 2％、K2O 2％、TiO2 1％、Li2O 5％、BaO 2％、CaO 2％、MgO 2％、Al2O3 5％；
Secondly, putting the weighed raw materials into a mixer, mixing for 1h, taking out, putting into a crucible, heating to 1350 ℃ at a heating rate of 10 ℃/min, preserving heat for 1h, pouring the molten glass into water, and quenching to obtain glass particles;
thirdly, according to the glass: pure water: large zirconium balls: the small zirconium balls are placed in a ball milling tank according to the proportion of 1:1:3:3, ball milling is carried out for 3 hours at the speed of 250r/min, ball milling is carried out for 1.5 hours at the speed of 320r/min, the small zirconium balls are taken out and dried in an oven at the temperature of 110 ℃, and screening is carried out by using a 3000-mesh screen, so that glass powder with the average particle size of 549nm is obtained.
Comparative example 2
The glass powder comprises the following preparation steps:
weighing B according to the mass percentage, wherein the total mass of the glass powder is 100 percent2O3 13％、SiO2 40％、ZnO 11％、Na2O 5％、K2O 4％、TiO2 2％、Li2O 10％、BaO 3％、CaO 3％、MgO 3％、Al2O3 6％；
Secondly, putting the weighed raw materials into a mixer, mixing for 1h, taking out, putting into a crucible, heating to 1350 ℃ at a heating rate of 10 ℃/min, preserving heat for 1h, pouring the molten glass into water, and quenching to obtain glass particles;
thirdly, according to the glass: pure water: large zirconium balls: and (3) placing the small zirconium balls into a ball milling tank according to the ratio of 1:1:3:3, carrying out ball milling at 250r/min for 3 hours and 320r/min for 1.5 hours, taking out, drying in an oven at 110 ℃, and screening by using a 3000-mesh screen to obtain the glass powder with the average particle size of 486 nm.
Further, in order to verify the progress of the glass frit and the method for preparing the same in the examples of the present application, the following tests were performed on the glass frits prepared in examples 1 to 4 and comparative examples 1 to 2:
1. the glass powders of examples 1 to 4 and comparative examples 1 to 2 were tested for softening point temperature using Differential Scanning Calorimetry (DSC) analysis equipment, and the results are shown in table 1 below:
2. adding the glass powder of the embodiment 1-4 into solvents such as alcohols, ethers and lipid solvents respectively to prepare slurry, printing a coating with the thickness of 20-30 μm on the surface of the glass by using a screen printer, drying at 120 ℃, and then placing the glass into a sintering furnace to sinter for 3min at 690 ℃ to obtain the formed glass. The glass prepared from the glass powder of examples 1-4 and comparative examples 1-2 was tested for yellowing resistance and adhesion, wherein the adhesion was determined by cross hatch test, classified by cross hatch test (GB/T9286-1998), and the results are shown in Table 1 below:
3. the particle sizes of the glass powders of examples 1 to 4 and comparative examples 1 to 2 were measured by an electron microscope SEM and a laser particle sizer, and the results are shown in table 1 below:
TABLE 1
Note that: x represents yellowing of the glass frit after sintering, and O represents no yellowing.
According to the test results, the glass powder prepared in the embodiments 1 to 4 has small and uniform particle size, so that the formed glass has better flatness and smoothness. The softening temperatures are 488 deg.C, 536 deg.C, 427 deg.C and 491 deg.C, respectively, and the softening temperature is low, and can be used at low temperature. Particularly, for sealing of some electronic products, the substrate can be damaged when the temperature is too high, and the lower the sealing temperature is, the better the performance is ensured. As can be seen from the yellowing inhibition test, the glass prepared in the embodiment 2-4 of the application has no yellowing, is durable and attractive, and is convenient to apply for a long time. The adhesion tests show that the glass prepared in the examples 2 and 4 has the adhesion of more than grade 1, wherein the adhesion of the examples 1 and 3 is grade 0, and the adhesion performance is excellent. The softening point temperatures of the comparative examples 1 and 2 reach 610 ℃ and 657 ℃ respectively, the softening temperature is high, and the application devices are easy to damage due to high temperature, so that the application in electronic products is not facilitated. In addition, the adhesive force is respectively 3 grades and 4 grades, and the adhesive force is poor; and the yellowing inhibition effect is poor, which affects the beauty and application effect.
The above description is only exemplary of the present application and should not be taken as limiting the present application, as any modification, equivalent replacement, or improvement made within the spirit and principle of the present application should be included in the protection scope of the present application.
Claims (10)
1. The glass powder is characterized by comprising the following raw material components in percentage by mass based on 100% of the total mass of the glass powder: b is2O3 18～30％，SiO2 20～35％，ZnO 15～30％，Na2O and K2The total mass percentage of O is 2-12%, ZrO2 1～8％，TiO2 5～10％，Li2O 0.1～1.5％，F2 0～1％、BaO 2～8％，CaO 0～2％，Al2O3 0.5～1％。
2. The glass frit according to claim 1, wherein the glass frit has an average particle size of not greater than 2 μm.
3. The glass powder according to claim 1 or 2, comprising the following raw material components by mass percent, based on 100% of the total mass of the glass powder: b is2O3 27％、SiO2 25％、ZnO 23％、Na2O 3％、K2O 4％、ZrO28％、TiO2 5％、Li2O 1％、BaO 3.5％、Al2O3 0.5％；
Or the raw material composition comprises the following components in percentage by mass: b is2O3 25％、SiO2 30％、ZnO 23％、Na2O 0.6％、K2O 2.8％、ZrO2 3％、TiO2 7％、Li2O 0.6％、F2 0.5％、BaO 6％、CaO 1％、Al2O3 0.5％；
Or the raw material composition comprises the following components in percentage by mass: b is2O3 24％、SiO2 30％、ZnO 20％、Na2O 2％、K2O 4.5％、ZrO2 4％、TiO2 6％、Li2O 1％、F2 1％、BaO 4.5％、CaO 2.0％、Al2O3 1％；
Or the raw material composition comprises the following components in percentage by mass: b is2O3 20％、SiO2 30％、ZnO 17％、Na2O 7％、K2O 5％、ZrO2 3.2％、TiO2 8％、Li2O 1％、BaO 7％、CaO 1％、Al2O30.8％。
4. The glass frit according to claim 3, wherein the glass frit has a softening temperature of not higher than 536 ℃.
5. The preparation method of the glass powder is characterized by comprising the following steps:
obtaining raw material components in the glass powder according to any one of claims 1 to 4;
mixing the raw material components in the glass powder, sequentially carrying out melting treatment, quenching treatment and grinding treatment, and drying to obtain the glass powder.
6. The method of producing glass frit according to claim 5, wherein the conditions of the melting process include: and carrying out melt mixing treatment for 30-90 min at the temperature of 1100-1300 ℃.
7. The method for producing glass frit according to claim 5 or 6, wherein the quenching process comprises: and quenching the molten glass after the melting treatment by using water as a quenching agent to form glass particles by water quenching of the molten glass.
8. The method of preparing glass frit according to claim 7, wherein the grinding process comprises: under the condition that the mass ratio of the glass particles to the water to the large zirconium balls to the small zirconium balls is 1:1 (2-4) to (2-5), ball milling treatment is carried out on the glass particles at the rotating speed of 200-350 r/min for 3-4.5 hours.
9. The method of preparing glass frit according to claim 8, wherein the step of ball milling comprises: under the condition that the mass ratio of the glass particles to the water to the large zirconium balls to the small zirconium balls is 1:1 (2-4) to (2-5), ball-milling the glass particles at the rotating speed of 200-300 r/min for 2-3 hours, and then ball-milling the glass particles at the rotating speed of 300-350 r/min for 1-2 hours.
10. The method of producing glass frit according to any one of claims 5, 6, or 8 to 9, wherein after the grinding treatment, further comprising the step of: and sieving the product after grinding and drying to obtain the glass powder.
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