CN115893853A - Lead-free glass powder for resistance paste and preparation method thereof - Google Patents
Lead-free glass powder for resistance paste and preparation method thereof Download PDFInfo
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- CN115893853A CN115893853A CN202310022534.3A CN202310022534A CN115893853A CN 115893853 A CN115893853 A CN 115893853A CN 202310022534 A CN202310022534 A CN 202310022534A CN 115893853 A CN115893853 A CN 115893853A
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Abstract
The invention discloses lead-free glass powder for resistance paste, which comprises the following raw materials in parts by weight: 20 to 80 parts of Bi 2 O 3 10 to 30 parts of B 2 O 3 10 to 30 parts of Ln 2 O 3 3 to 7 parts of Ce0 2 5 to 9 parts of Pr 6 O 11 1 to 3 parts of CdO; the invention also discloses a preparation method of the lead-free glass powder for the resistance paste, and the prepared lead-free glass powder for the resistance paste can realize the condition of regulating and controlling the vitrification temperature in a large rangeThe thermal expansion coefficient is kept low.
Description
Technical Field
The invention relates to the field of lead-free glass powder, in particular to lead-free glass powder for resistance paste and a preparation method thereof.
Background
With the rapid updating of electronic components since the 21 st century, the status and demand of resistor paste have increased.
The resistance paste mainly comprises a conductive functional phase, a glass bonding phase, an organic carrier and a modifier. The ruthenium-based resistor paste is a thick-film resistor paste widely used in the electronic industry, and mainly comprises ruthenate and derivatives thereof, and ruthenium dioxide (RuO) 2 ) Silver-palladium alloy (Ag-Pd), etc. as its conductive phase. The ruthenium oxide conductive phase and the glass phase are dispersed in an organic medium to form the strain characteristic of the resistance paste, and the grain diameter of the conductive phase and the glass phase is also one of the key factors influencing the electrical characteristic of the resistance.
The traditional resistance paste glass bonding phase and the conductive functional phase contain a large amount of lead elements, the content of the lead elements is usually between 20% and 60%, the lead oxide is very stable in chemical property, and the glass prepared by taking the lead oxide as a main component has the characteristics of low glass transition temperature, good adaptability with a ceramic substrate and the like. However, lead belongs to one of three heavy metal pollutants, and is a heavy metal element seriously harming human health. With the gradual increase of the national requirements for environmental protection, the demand of the lead-free resistance paste is urgent, and the difficulty of preparing the lead-free resistance paste is concentrated on the preparation of the lead-free glass.
In the resistor paste, the glass binder phase plays a crucial role. The glass transition temperature of the glass binder phase represents the temperature at which it begins to flow during sintering of the slurry. The glass transition temperature is mainly determined by the stability and compactness of the glass micro-network structure, and when the glass network has high stability and compactness, the glass network can obtain higher glass transition temperature. But the relationship between the coefficient of thermal expansion of the glass and the microstructure is opposite. Therefore, maintaining a low coefficient of thermal expansion over a wide range of glass transition temperature control is a difficulty in the bonding of lead-free glass to a corresponding resistor paste.
Disclosure of Invention
The invention aims to provide lead-free glass powder for resistance paste.
The invention also discloses a preparation method of the lead-free glass powder for the resistance paste.
The innovation point of the invention is that Bi in the invention 2 O 3 And B 2 O 3 The mass ratio is between 0.67 and 8, the glass forming performance of the glass is ensured, and Bi is changed 2 O 3 And B 2 O 3 The mass ratio of the glass transition temperature to the glass transition temperature is adjusted and controlled; introduction of oxides of lanthanides in presence of Bi 2 O 3 And B 2 O 3 In the formed glass network, the glass network is more compact, so that the thermal expansion coefficient of the glass is improved; thereby realizing that the thermal expansion coefficient is kept low under the condition of regulating and controlling the glass transition temperature in a large range.
In order to achieve the purpose, the technical scheme of the invention is as follows:
the lead-free glass powder for the resistance paste comprises the following raw materials in parts by weight: 20 to 80 parts of Bi 2 O 3 10 to 30 parts of B 2 O 3 10 to 30 parts of Ln 2 O 3 3 to 7 parts of Ce0 2 5 to 9 parts of Pr 6 O 11 And 1 to 3 parts of CdO.
A preparation method of lead-free glass powder for resistance paste comprises the following steps:
(1) Weighing and mixing the raw materials according to the formula, and uniformly stirring the raw materials after mixing to obtain a mixture;
(2) Heating and melting the mixture to obtain high-temperature molten glass liquid;
(3) Slowly pouring the high-temperature molten glass liquid into deionized water for water quenching and quenching, and drying after water quenching and quenching to obtain glass particles;
(4) Grinding the glass particles to obtain glass powder, then carrying out ball milling on the glass powder to obtain glass slurry, and adding deionized water during ball milling;
(5) And filtering the glass slurry to obtain wet glass powder, drying the wet glass powder, and sieving the dried wet glass powder to obtain a finished product.
Further, in the step (2), the mixture is heated and melted, namely the mixture is put into an alumina crucible and then is put into a high-temperature box-type furnace to be heated from room temperature to 900-1200 ℃ at the heating rate of 10 ℃/min; and the temperature is kept for 1h at the temperature, thereby obtaining high-temperature molten glass.
Further, the grinding in the step (4) is carried out in an agate mortar.
Further, ball milling is carried out by adopting an agate ball in the step (4), the ball milling time is 24 to 30 hours, and the rotating speed is 350 to 450rpm; glass powder: the volume ratio of the agate balls to the deionized water is 1.
Further, the particle size of the glass powder is 0.5 to 1.5 μm.
The invention has the beneficial effects that:
1. bi in the invention 2 O 3 And B 2 O 3 The mass ratio is between 0.67 and 8, the glass forming performance of the glass is ensured, and Bi is changed 2 O 3 And B 2 O 3 The glass transition temperature is regulated and controlled by the mass ratio of the glass transition temperature to the glass transition temperature. Pure Bi 2 O 3 It cannot be formed into glass alone, but it can be formed into glass forming body B 2 O 3 Thereby forming a glass in a wider composition interval. Due to B 2 O 3 The interlayer connection is intermolecular force, so that the introduction of boron oxide into the bismuth-based glass does not cause an excessively high glass transition temperature, and in Bi 2 O 3 And B 2 O 3 In the glass network formed, there is mainly BiO 6 ，BO 3 ,BO 4 Three network architectures. BO 4 Structural contrast to BO 3 The structure has higher density and compactness, bi 2 O 3 And B 2 O 3 The increase in mass ratio promotes BO 3 Structural direction BO 4 The transformation of the structure and thus the glass transition temperature of the glass.
However, since the bond length of Bi-O bond is long and the bond strength is small, this results in BiO 6 The problem of large thermal expansion coefficient of the glass formed by the network exists, in the application of the resistance paste, the crack appears after the paste is solidified because the thermal expansion coefficient is larger than that of the ceramic substrate, and the performance of the resistance paste is poorAnd (4) impression.
Introducing a lanthanide metal oxide to be present in Bi 2 O 3 And B 2 O 3 In the formed glass network, the glass network is more compact, thereby improving the thermal expansion coefficient of the glass. Ln 2 O 3 Plays the most critical role in stabilizing the glass network, so a higher proportion of Ln is introduced 2 O 3 Reacting it with Bi 2 O 3 B 2 O 3 Together constitute the main forming part of the glass, and successfully solve the problem of large thermal expansion coefficient of the bi-based glass.
Drawings
FIG. 1 is an XRD test chart of examples 1 to 5.
Detailed Description
The technical solution in the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings.
Example 1: the lead-free glass powder for the resistance paste comprises the following raw materials in parts by weight: 20 parts of Bi 2 O 3 30 parts of B 2 O 3 10 parts of Ln 2 O 3 3 parts of Ce0 2 5 parts of Pr 6 O 11 And 1 part of CdO.
Example 2: the lead-free glass powder for the resistance paste comprises the following raw materials in parts by weight: 40 parts of Bi 2 O 3 25 parts of B 2 O 3 10 parts of Ln 2 O 3 3 parts of Ce0 2 5 parts of Pr 6 O 11 And 1 part of CdO.
Example 3: the lead-free glass powder for the resistance paste comprises the following raw materials in parts by weight: 60 parts of Bi 2 O 3 20 parts of B 2 O 3 10 parts of Ln 2 O 3 3 parts of Ce0 2 5 parts of Pr 6 O 11 And 1 part of CdO.
Example 4: the lead-free glass powder for the resistance paste comprises the following raw materials in parts by weight: 65 parts of Bi 2 O 3 15 parts of B 2 O 3 20 parts of Ln 2 O 3 5 parts of Ce0 2 7 parts of Pr 6 O 11 And 2 parts of CdO.
Example 5: the lead-free glass powder for the resistance paste comprises the following raw materials in parts by weight: 80 parts of Bi 2 O 3 10 parts of B 2 O 3 30 parts of Ln 2 O 3 7 parts of Ce0 2 9 parts of Pr 6 O 11 And 3 parts of CdO.
Comparative example 1: the lead-free glass powder for the resistance paste comprises the following raw materials in parts by weight: 20 parts of Bi 2 O 3 30 parts of B 2 O 3 5 parts of Ln 2 O 3 3 parts of Ce0 2 5 parts of Pr 6 O 11 And 1 part of CdO.
Comparative example 2: the lead-free glass powder for the resistance paste comprises the following raw materials in parts by weight: 90 parts of Bi 2 O 3 5 parts of B 2 O 3 20 parts of Ln 2 O 3 5 parts of Ce0 2 7 parts of Pr 6 O 11 And 2 parts of CdO.
Example 6: a preparation method of lead-free glass powder for resistance paste comprises the following steps: weighing and mixing the raw materials according to the formula of the embodiment 1, and uniformly stirring the raw materials after mixing to obtain a mixture; putting the mixture into an alumina crucible, and then putting the alumina crucible into a high-temperature box-type furnace to heat the mixture from room temperature to 900 ℃ at the heating rate of 10 ℃/min; and the temperature is kept for 1h at the temperature, thereby obtaining high-temperature molten glass. Obtaining high-temperature molten glass; slowly pouring the high-temperature molten glass liquid into deionized water for water quenching and quenching, and drying after water quenching and quenching to obtain glass particles; grinding the glass particles to obtain glass powder, wherein the particle size of the glass powder is 0.5 to 1.5 mu m. The grinding was carried out in an agate mortar. Then ball milling the glass powder to obtain glass slurry, and adding deionized water during ball milling; the ball milling is carried out by agate balls, the ball milling time is 24 hours, and the rotating speed is 350rpm; glass powder: the volume ratio of the agate balls to the deionized water is 1. And filtering the glass slurry to obtain wet glass powder, drying the wet glass powder, and sieving the dried wet glass powder to obtain a finished product.
Example 7: a preparation method of lead-free glass powder for resistance paste comprises the following steps: weighing and mixing the raw materials according to the formula of the embodiment 2, and uniformly stirring the raw materials after mixing to obtain a mixture; putting the mixture into an alumina crucible, and then putting the alumina crucible into a high-temperature box-type furnace to heat the mixture from room temperature to 1000 ℃ at the heating rate of 10 ℃/min; and the temperature is kept for 1h at the temperature, thereby obtaining high-temperature molten glass. Obtaining high-temperature molten glass liquid; slowly pouring the high-temperature molten glass liquid into deionized water for water quenching and quenching, and drying after water quenching and quenching to obtain glass particles; grinding the glass particles to obtain glass powder, wherein the particle size of the glass powder is 0.5 to 1.5 mu m. The grinding was carried out in an agate mortar. Then ball milling the glass powder to obtain glass slurry, and adding deionized water during ball milling; the ball milling is carried out by agate balls, the ball milling time is 27 hours, and the rotating speed is 400rpm; glass powder: the volume ratio of the agate balls to the deionized water is 1. And filtering the glass slurry to obtain wet glass powder, drying the wet glass powder, and sieving the dried wet glass powder to obtain a finished product.
Example 8: a preparation method of lead-free glass powder for resistance paste comprises the following steps: weighing the raw materials according to the formula of the embodiment 3, mixing, and uniformly stirring to obtain a mixture; placing the mixture into an alumina crucible, and then placing the alumina crucible into a high-temperature box type furnace to heat the mixture from room temperature to 1200 ℃ at the heating rate of 10 ℃/min; and the temperature is kept for 1h at the temperature, thereby obtaining high-temperature molten glass. Obtaining high-temperature molten glass liquid; slowly pouring the high-temperature molten glass liquid into deionized water for water quenching and quenching, and drying after water quenching and quenching to obtain glass particles; grinding the glass particles to obtain glass powder, wherein the particle size of the glass powder is 0.5 to 1.5 mu m. The grinding was carried out in an agate mortar. Then ball milling the glass powder to obtain glass slurry, and adding deionized water during ball milling; the ball milling is carried out by agate balls, the ball milling time is 30 hours, and the rotating speed is 450rpm; glass powder: the volume ratio of the agate balls to the deionized water is 1. And filtering the glass slurry to obtain wet glass powder, drying the wet glass powder, and sieving the dried wet glass powder to obtain a finished product.
And (3) performance testing:
as can be seen from the XRD test, in each of examples 1 to 5, 2 positions show a broad diffraction peak in a diffuse scattering state, and the diffraction peak shows that the example is amorphous glass with long-range disorder.
From the above examples, we can find that the glass transition temperature can be regulated and controlled between 653 ℃ and 468 ℃. And the thermal expansion coefficient can be compared with that of an alumina substrate (6.9 ppm/DEG C20-300 ℃), the glass can realize very good matching, greatly enhances the bonding performance of a bonding phase, and reduces the risk of cracks in the sintering of the resistance paste.
The described embodiments are only some embodiments of the invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Claims (6)
1. The lead-free glass powder for the resistance paste is characterized by comprising the following raw materials in parts by weight: 20 to 80 parts of Bi 2 O 3 10 to 30 parts of B 2 O 3 10 to 30 parts of Ln 2 O 3 3 to 7 parts of Ce0 2 5 to 9 parts of Pr 6 O 11 And 1 to 3 parts of CdO.
2. The method for preparing the lead-free glass frit for resistor paste according to claim 1, comprising the steps of:
(1) Weighing and mixing the raw materials according to the formula, and uniformly stirring the raw materials after mixing to obtain a mixture;
(2) Heating and melting the mixture to obtain high-temperature molten glass liquid;
(3) Pouring the high-temperature molten glass liquid into deionized water for water quenching and quenching, and drying after water quenching and quenching to obtain glass particles;
(4) Grinding the glass particles to obtain glass powder, then carrying out ball milling on the glass powder to obtain glass slurry, and adding deionized water during ball milling;
(5) And filtering the glass slurry to obtain wet glass powder, drying the wet glass powder, and sieving the dried wet glass powder to obtain a finished product.
3. The preparation method of the lead-free glass powder for the resistance paste according to claim 2, wherein in the step (2), the mixture is heated and melted by putting the mixture into an alumina crucible, and then putting the alumina crucible into a high-temperature box-type furnace to be heated from room temperature to 900-1200 ℃ at a heating rate of 10 ℃/min; and the temperature was maintained at that temperature for 1 hour to obtain a high-temperature molten glass.
4. The method for preparing a lead-free glass frit for an electrical resistance paste according to claim 2, wherein the grinding in the step (4) is carried out in an agate mortar.
5. The method for preparing the lead-free glass powder for the resistance paste according to claim 2, wherein agate ball milling is adopted during ball milling in the step (4), the ball milling time is 24-30 hours, and the rotation speed is 350-450rpm; glass powder: the volume ratio of the agate balls to the deionized water is 1.
6. The method for preparing the lead-free glass powder for the resistor paste according to claim 2, wherein the particle size of the glass powder is 0.5 to 1.5 μm.
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Citations (7)
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| JP2007246311A (en) * | 2006-03-14 | 2007-09-27 | Ohara Inc | Glass composition |
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| CN101456674A (en) * | 2009-01-04 | 2009-06-17 | 武汉理工大学 | Rare-earth doped leadless and low-melting point sealing glass and its preparation method |
| JP2010018502A (en) * | 2008-07-14 | 2010-01-28 | Nippon Electric Glass Co Ltd | Bismuth-based glass composition and sealing material |
| CN103258584A (en) * | 2013-01-09 | 2013-08-21 | 深圳市创智材料科技有限公司 | Electric conductive silver paste and manufacturing method thereof |
| CN109369027A (en) * | 2018-11-13 | 2019-02-22 | 江西合创光电技术有限公司 | Add the novel environment friendly glass powder and preparation method thereof of nano-metal-oxide |
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2023
- 2023-01-08 CN CN202310022534.3A patent/CN115893853A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007246311A (en) * | 2006-03-14 | 2007-09-27 | Ohara Inc | Glass composition |
| CN101323502A (en) * | 2008-06-20 | 2008-12-17 | 中国科学院上海光学精密机械研究所 | Leadless low-melting point glasses with very high refractive index and method for making same |
| JP2010018502A (en) * | 2008-07-14 | 2010-01-28 | Nippon Electric Glass Co Ltd | Bismuth-based glass composition and sealing material |
| CN101376561A (en) * | 2008-09-28 | 2009-03-04 | 陈培 | Low-melting point lead-less glasses powder for frit slurry, and preparation and use thereof |
| CN101456674A (en) * | 2009-01-04 | 2009-06-17 | 武汉理工大学 | Rare-earth doped leadless and low-melting point sealing glass and its preparation method |
| CN103258584A (en) * | 2013-01-09 | 2013-08-21 | 深圳市创智材料科技有限公司 | Electric conductive silver paste and manufacturing method thereof |
| CN109369027A (en) * | 2018-11-13 | 2019-02-22 | 江西合创光电技术有限公司 | Add the novel environment friendly glass powder and preparation method thereof of nano-metal-oxide |
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