CN113003940A - Low-melting-point low-expansion-coefficient glass powder and preparation method thereof - Google Patents
Low-melting-point low-expansion-coefficient glass powder and preparation method thereof Download PDFInfo
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- CN113003940A CN113003940A CN202110442414.XA CN202110442414A CN113003940A CN 113003940 A CN113003940 A CN 113003940A CN 202110442414 A CN202110442414 A CN 202110442414A CN 113003940 A CN113003940 A CN 113003940A
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- 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
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- 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
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Abstract
The invention discloses a low-melting-point low-expansion-coefficient glass powder and a preparation method thereof, wherein the glass powder comprises the following raw materials in parts by weight: 40-60 parts of oxalic acid, 20-30 parts of stannous chloride, 25-30 parts of zinc chloride, 0.5-2 parts of lithium chloride, 0.5-1 part of cuprous chloride, 1-3 parts of ferric trichloride, 2-6 parts of aluminum chloride, 1-5 parts of zinc chloride, 0.5-2 parts of barium chloride, 1-1.5 parts of titanium tetrachloride and 6-8 parts of ammonium dihydrogen phosphate. The glass powder disclosed by the invention does not contain lead, mercury, chromium and cadmium substances, has the fire resistance temperature of 200-600 ℃, has a lower expansion coefficient, the transition temperature of 200 +/-3 ℃, the softening temperature of 230 +/-DEG C, the average linear expansion coefficient of 75 +/-3 multiplied by 10 < -7 >/DEG C at 20-600 ℃, is stable in 5% hydrochloric acid and sulfuric acid and is not corroded, and is mainly used for welding metals and metal products thereof in an acid environment.
Description
Technical Field
The invention belongs to the technical field of glass powder preparation, and particularly relates to low-melting-point and low-expansion-coefficient glass powder and a preparation method thereof.
Background
With the development of the electronic industry, multilayer chip components characterized by small size, high reliability, excellent electrical performance and capability of realizing chip surface assembly are widely applied in the fields of communication, computers and peripheral products, consumer electronics, office automation, automotive electronics and the like.
The multi-layer chip component generally comprises a substrate, a metal membrane electrode, a terminal electrode and the like, wherein the terminal electrode is the key for realizing chip surface assembly. The terminal electrode is generally composed of a silver electrode and an electroplated layer. The end-coated silver paste for forming the silver electrode consists of silver powder, glass powder, additives and an organic carrier. The end coating silver paste is attached to the end of the chip component through sintering to form a silver electrode, and the silver electrode is electroplated to form the end electrode. During sintering, the glass powder in the end-coated silver paste enables the silver electrode to be firmly attached to the substrate through wetting, permeation and other actions, and the key point that the silver electrode can form strong attachment at the end of the chip component is. Meanwhile, in order to plate a protective layer such as nickel, tin, etc. on the silver electrode, the glass frit needs to have good acid resistance after sintering so as to resist the corrosion of the silver electrode by the acid plating solution.
At present, most of end-coating silver paste sold in the market adopts glass powder with poor acid resistance, the problems of silver electrode adhesion reduction, cracking, falling and the like can occur after electroplating in acid electroplating solution, the welding resistance, the weldability, the adhesion of a plating layer are reduced after electroplating, and the ageing resistance and the electrical property of components are deteriorated.
Disclosure of Invention
The invention aims to provide the glass powder with good acid resistance, stable chemical property, low melting point and low expansion coefficient.
The invention relates to a low-melting-point low-expansion-coefficient glass powder which comprises the following raw materials in parts by weight:
40-60 parts of oxalic acid, 20-30 parts of stannous chloride, 25-30 parts of zinc chloride, 0.5-2 parts of lithium chloride, 0.5-1 part of cuprous chloride, 1-3 parts of ferric trichloride, 2-6 parts of aluminum chloride, 1-5 parts of zinc chloride, 0.5-2 parts of barium chloride, 1-1.5 parts of titanium tetrachloride and 6-8 parts of ammonium dihydrogen phosphate.
The invention relates to a preparation method of low-melting-point low-expansion-coefficient glass powder, which comprises the following steps:
(1) taking 40-60 parts of oxalic acid, 20-30 parts of stannous chloride, 25-30 parts of zinc chloride, 0.5-2 parts of lithium chloride, 0.5-1 part of cuprous chloride, 1-3 parts of ferric chloride, 2-6 parts of aluminum chloride, 1-5 parts of zinc chloride, 0.5-2 parts of barium chloride, 1-1.5 parts of titanium tetrachloride and 7 parts of ammonium dihydrogen phosphate according to parts by weight;
(2) preparing oxalic acid solution, namely preparing oxalic acid into aqueous solution with the molar concentration of 0.8-2 at the temperature of 60-100 ℃ for later use;
(3) adding 100 parts of water into stannous chloride, zinc chloride, lithium chloride, cuprous chloride, ferric trichloride, aluminum chloride, zinc chloride, barium chloride and titanium tetrachloride to prepare a mixture aqueous solution;
(4) adding the mixture water solution into oxalic acid solution at 60-100 ℃ at the flow rate of 80-120 ml/min for reaction, keeping the temperature for reaction for 25 min after the material is added, filtering, and taking the precipitate;
(5) drying the precipitate in an oven at the temperature of 105-115 ℃ for 23-25 hours to obtain an oxalate complex;
(6) adding 3 parts of oxalate complex into 7 parts of ammonium dihydrogen phosphate, uniformly mixing, melting in a high-temperature furnace at the temperature of 1000-1100 ℃, and preserving heat for 18-22 minutes;
(7) pouring the melted liquid into water, quickly cooling to form homogeneous glass particles in the water, and crushing to obtain the glass particles.
Compared with the prior art, the invention has obvious beneficial effects, and the oxalic acid effectively protects stannous chloride and cuprous chloride ions from changing valence until stable homogeneous vitreous body particles with stannous and cuprous ion structures are formed. The glass powder disclosed by the invention does not contain lead, mercury, chromium and cadmium substances, has the fire resistance temperature of 200-600 ℃, has a lower expansion coefficient, the transition temperature of 200 +/-3 ℃, the softening temperature of 230 +/-DEG C, the average linear expansion coefficient of 75 +/-3 multiplied by 10 < -7 >/DEG C at 20-600 ℃, is stable in 5% hydrochloric acid and sulfuric acid and is not corroded, and is mainly used for welding metals and metal products thereof in an acid environment.
Detailed Description
Example 1
A preparation method of low-melting-point and low-expansion-coefficient glass powder comprises the following steps:
(1) weighing 40 kg of oxalic acid, 30 kg of stannous chloride, 25 kg of zinc chloride, 2 kg of lithium chloride, 0.5 kg of cuprous chloride, 3 kg of ferric trichloride, 2 kg of aluminum chloride, 5 kg of zinc chloride, 0.5 kg of barium chloride, 1.5 kg of titanium tetrachloride and 7 kg of ammonium dihydrogen phosphate;
(2) preparing oxalic acid solution, namely preparing oxalic acid into aqueous solution with the concentration of 2 mol at the temperature of 60 ℃ for later use;
(3) adding 100 kilograms of water into stannous chloride, zinc chloride, lithium chloride, cuprous chloride, ferric trichloride, aluminum chloride, zinc chloride, barium chloride and titanium tetrachloride to prepare a mixture aqueous solution;
(4) adding the mixture water solution into oxalic acid solution at 100 ℃ at the flow rate of 80 ml/min for reaction, keeping the temperature for reaction for 25 min after the material is added, filtering, and taking the precipitate;
(5) drying the precipitate in an oven at 105 ℃ for 25 hours to obtain an oxalate complex;
(6) adding 7 kg of ammonium dihydrogen phosphate into 3 kg of oxalate complex, uniformly mixing, melting in a high-temperature furnace at 1000 ℃, and keeping the temperature for 22 minutes;
(7) pouring the melted liquid into water, quickly cooling to form homogeneous glass particles in the water, and crushing to obtain the glass particles.
Example 2
A preparation method of low-melting-point and low-expansion-coefficient glass powder comprises the following steps:
(1) weighing 50 kg of oxalic acid, 25 kg of stannous chloride, 27.5 kg of zinc chloride, 1.25 kg of lithium chloride, 0.75 kg of cuprous chloride, 2 kg of ferric trichloride, 4 kg of aluminum chloride, 3 kg of zinc chloride, 1.25 kg of barium chloride, 1.25 kg of titanium tetrachloride and 7 kg of ammonium dihydrogen phosphate;
(2) preparing oxalic acid solution, namely preparing oxalic acid into aqueous solution with the molar concentration of 1.4 at the temperature of 80 ℃ for later use;
(3) adding 100 kilograms of water into stannous chloride, zinc chloride, lithium chloride, cuprous chloride, ferric trichloride, aluminum chloride, zinc chloride, barium chloride and titanium tetrachloride to prepare a mixture aqueous solution;
(4) adding the mixture water solution into an oxalic acid solution at the temperature of 80 ℃ at the flow rate of 100 ml/min for reaction, keeping the temperature for reaction for 25 min after the material is added, filtering, and taking a precipitate;
(5) drying the precipitate in a drying oven at 110 ℃ for 24 hours to obtain an oxalate complex;
(6) adding 7 kg of ammonium dihydrogen phosphate into 3 kg of oxalate complex, uniformly mixing, melting in a high-temperature furnace at 1050 ℃, and keeping the temperature for 20 minutes;
(7) pouring the melted liquid into water, quickly cooling to form homogeneous glass particles in the water, and crushing to obtain the glass particles.
Example 3
A preparation method of low-melting-point and low-expansion-coefficient glass powder comprises the following steps:
(1) weighing 60 kg of oxalic acid, 20 kg of stannous chloride, 30 kg of zinc chloride, 0.5 kg of lithium chloride, 1 kg of cuprous chloride, 1 kg of ferric trichloride, 6 kg of aluminum chloride, 1 kg of zinc chloride, 2 kg of barium chloride, 1 kg of titanium tetrachloride and 7 kg of ammonium dihydrogen phosphate;
(2) preparing oxalic acid solution, namely preparing oxalic acid into 0.8 molar concentration aqueous solution at 100 ℃ for later use;
(3) adding 100 kilograms of water into stannous chloride, zinc chloride, lithium chloride, cuprous chloride, ferric trichloride, aluminum chloride, zinc chloride, barium chloride and titanium tetrachloride to prepare a mixture aqueous solution;
(4) adding the mixture water solution into an oxalic acid solution at 60 ℃ at the flow rate of 120 ml/min for reaction, keeping the temperature for reaction for 25 min after the material is added, filtering, and taking a precipitate;
(5) drying the precipitate in an oven at 115 ℃ for 23 hours to obtain an oxalate complex;
(6) adding 7 kg of ammonium dihydrogen phosphate into 3 kg of oxalate complex, uniformly mixing, melting in a high-temperature furnace at 1100 ℃, and keeping the temperature for 18 minutes;
(7) pouring the melted liquid into water, quickly cooling to form homogeneous glass particles in the water, and crushing to obtain the glass particles.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention in any way, and any simple modification, equivalent change and modification made to the above embodiment according to the technical spirit of the present invention are within the scope of the present invention without departing from the technical spirit of the present invention.
Claims (2)
1. The glass powder with low melting point and low expansion coefficient comprises the following raw materials in parts by weight:
40-60 parts of oxalic acid, 20-30 parts of stannous chloride, 25-30 parts of zinc chloride, 0.5-2 parts of lithium chloride, 0.5-1 part of cuprous chloride, 1-3 parts of ferric trichloride, 2-6 parts of aluminum chloride, 1-5 parts of zinc chloride, 0.5-2 parts of barium chloride, 1-1.5 parts of titanium tetrachloride and 6-8 parts of ammonium dihydrogen phosphate.
2. The method of claim 1, wherein the method comprises the steps of:
(1) taking 40-60 parts of oxalic acid, 20-30 parts of stannous chloride, 25-30 parts of zinc chloride, 0.5-2 parts of lithium chloride, 0.5-1 part of cuprous chloride, 1-3 parts of ferric chloride, 2-6 parts of aluminum chloride, 1-5 parts of zinc chloride, 0.5-2 parts of barium chloride, 1-1.5 parts of titanium tetrachloride and 7 parts of ammonium dihydrogen phosphate according to parts by weight;
(2) preparing oxalic acid solution, namely preparing oxalic acid into aqueous solution with the molar concentration of 0.8-2 at the temperature of 60-100 ℃ for later use;
(3) adding 100 parts of water into stannous chloride, zinc chloride, lithium chloride, cuprous chloride, ferric trichloride, aluminum chloride, zinc chloride, barium chloride and titanium tetrachloride to prepare a mixture aqueous solution;
(4) adding the mixture water solution into an oxalic acid solution for reaction and filtration, and taking a precipitate;
(5) drying the precipitate in an oven at the temperature of 105-115 ℃ for 23-25 hours to obtain an oxalate complex;
(6) adding 3 parts of oxalate complex into 7 parts of ammonium dihydrogen phosphate, uniformly mixing, melting in a high-temperature furnace at the temperature of 1000-1100 ℃, and preserving heat for 18-22 minutes;
(7) pouring the melted liquid into water, quickly cooling to form homogeneous glass particles in the water, and crushing to obtain the glass particles.
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| CN202110442414.XA CN113003940A (en) | 2021-04-23 | 2021-04-23 | Low-melting-point low-expansion-coefficient glass powder and preparation method thereof |
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| CN202110442414.XA CN113003940A (en) | 2021-04-23 | 2021-04-23 | Low-melting-point low-expansion-coefficient glass powder and preparation method thereof |
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11349347A (en) * | 1998-06-08 | 1999-12-21 | Asahi Glass Co Ltd | Crystalline low melting point glass composition |
| JP2000219536A (en) * | 1999-01-27 | 2000-08-08 | Asahi Glass Co Ltd | Low moisture absorbing glass frit and glass ceramics composition |
| JP2001302279A (en) * | 2000-04-21 | 2001-10-31 | Asahi Glass Co Ltd | Lead-free and low-melting point glass and glass frit |
| CN101066840A (en) * | 2006-06-22 | 2007-11-07 | 中国建筑材料科学研究总院 | No-lead RE doped sealing glass powder with low smelting point and its production process |
| CN101712533A (en) * | 2009-12-16 | 2010-05-26 | 贵阳华利美化工有限责任公司 | Lead-free glass powder for glass-ceramics adhesion, preparation method and application thereof |
| CN106430989A (en) * | 2016-09-29 | 2017-02-22 | 河南晶泰航空航天高新材料科技有限公司 | Low-melting-point glass powder, preparation method and application thereof and method of utilizing same to prepare composite glass column |
| CN107459257A (en) * | 2016-06-03 | 2017-12-12 | 南京豪祺新材料有限公司 | A kind of sealing-in Unlead low-smelting point glass and preparation method thereof |
| CN108640519A (en) * | 2018-05-31 | 2018-10-12 | 北京天力创玻璃科技开发有限公司 | Barium crown sealed glass and preparation method thereof |
-
2021
- 2021-04-23 CN CN202110442414.XA patent/CN113003940A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11349347A (en) * | 1998-06-08 | 1999-12-21 | Asahi Glass Co Ltd | Crystalline low melting point glass composition |
| JP2000219536A (en) * | 1999-01-27 | 2000-08-08 | Asahi Glass Co Ltd | Low moisture absorbing glass frit and glass ceramics composition |
| JP2001302279A (en) * | 2000-04-21 | 2001-10-31 | Asahi Glass Co Ltd | Lead-free and low-melting point glass and glass frit |
| CN101066840A (en) * | 2006-06-22 | 2007-11-07 | 中国建筑材料科学研究总院 | No-lead RE doped sealing glass powder with low smelting point and its production process |
| CN101712533A (en) * | 2009-12-16 | 2010-05-26 | 贵阳华利美化工有限责任公司 | Lead-free glass powder for glass-ceramics adhesion, preparation method and application thereof |
| CN107459257A (en) * | 2016-06-03 | 2017-12-12 | 南京豪祺新材料有限公司 | A kind of sealing-in Unlead low-smelting point glass and preparation method thereof |
| CN106430989A (en) * | 2016-09-29 | 2017-02-22 | 河南晶泰航空航天高新材料科技有限公司 | Low-melting-point glass powder, preparation method and application thereof and method of utilizing same to prepare composite glass column |
| CN108640519A (en) * | 2018-05-31 | 2018-10-12 | 北京天力创玻璃科技开发有限公司 | Barium crown sealed glass and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 王承遇、陶瑛主编: "《玻璃性质与工艺手册》", 化学工业出版社 * |
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