CN109192396A - A kind of preparation method of anti-oxidative conductive silver paste thick-film material - Google Patents
A kind of preparation method of anti-oxidative conductive silver paste thick-film material Download PDFInfo
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- CN109192396A CN109192396A CN201811135154.6A CN201811135154A CN109192396A CN 109192396 A CN109192396 A CN 109192396A CN 201811135154 A CN201811135154 A CN 201811135154A CN 109192396 A CN109192396 A CN 109192396A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/14—Conductive material dispersed in non-conductive inorganic material
- H01B1/16—Conductive material dispersed in non-conductive inorganic material the conductive material comprising metals or alloys
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/20—Conductive material dispersed in non-conductive organic material
- H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
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Abstract
The present invention relates to a kind of preparation methods of anti-oxidative conductive silver paste thick-film material, belong to circuit material technical field.Technical solution of the present invention uses pure zirconium chloride for zirconium source, ethyl orthosilicate is silicon source, dehydrated alcohol is solvent, lithium fluoride is mineralizer, prepare precursor sol and coating modification silver powder particles, and grout material is prepared by modified silver powder, due to being the contact condition of dispersion between the metallic particles in preset slurry thick film, after dry or solidification sintering, the conductive alternate film layer for being bound to each other to form some strength of Argent grain, the film layer of such compact texture, be effectively improved material thick-film material clad structure and anti-oxidant modified performance, while part adhesive mutually passes through Argent grain gap and penetrates into substrate surface, conductive layer crystal boundary is glued together with substrate, increase adhesive force, further increase the compact structure of material, to be effectively improved the antioxygenic property of material.
Description
Technical field
The present invention relates to a kind of preparation methods of anti-oxidative conductive silver paste thick-film material, belong to circuit material technology neck
Domain.
Background technique
Electric slurry (also known as thick film ink) is compared to other traditional circuit equipment with high-effect, the feature of environmental protection is good, energy saving
The features such as emission reduction, low cost, once it was widely used in solar battery, sensing element, resistor network, space flight and aviation, display
Deng preparation field.The major function of conduction electrons slurry is mutually the metal powders such as gold, silver, copper, its main feature is that the quality of production it is high,
Utilization benefit is high, technologically advanced, applicable scale is big.Since later 1980s, the research of conductive silver electronic paste
Fast development, silver-colored sintering technology are wanted in material composition, manufacturing condition, supply chain management, processing conditions, technical performance and client
Aspect is asked constantly to develop and get a promotion.Silver paste sintering technology changes material prescription, complicated patent environment in addition to needing to overcome
Outside the health problem of condition, the feasibility of production and detection device and Ag nanoparticle, it is also necessary to silver-colored migration is prevented, in electronics
The antioxygenic property of conductive silver paste thick film is improved in the use process of component.
Recently as the high speed development of electronics and information industry, so that electronic component increasingly tends to micromation, soft
Propertyization development, many scientific research institutions conduct in-depth research the development and application of conductive silver paste.But argentiferous electronics
Component aoxidizes the problems such as blackening, not only influences its Long-Term Properties, but also damage surface aesthetic degree.It is how more efficient
Ground improves this drawback, is the key point in existing thick-film material preparation process.
Summary of the invention
The technical problems to be solved by the invention: it for the bad problem of existing conductive silver paste material against oxidative performance, mentions
A kind of preparation method of anti-oxidative conductive silver paste thick-film material is supplied.
In order to solve the above technical problems, the technical solution adopted by the present invention is that:
(1) according to parts by weight, weigh respectively 45~50 parts of dehydrated alcohols, 2~3 parts of zirconium chlorides, 1~2 part of lithium fluoride and 6~
8 parts of ethyl orthosilicates are placed in a beaker, and are stirred and are transferred in conical flask, are stirred and oil bath heating, standing are cold
But to room temperature, mixed liquor is obtained；
(2) 1:50 in mass ratio, tetrabutylammonium bromide is added in mixed liquor, is stirred and oil bath heating, standing cool down
To room temperature, modification sol liquid is obtained；
(3) 200 mesh silver powder are added in modification sol liquid by 1:1 in mass ratio, are stirred and grinding distribution, collection disperse
Slurries and drying are collected in dry particle juxtaposition Muffle furnace, heating heating, heat preservation calcining, and standing is cooled to room temperature and grinds point
It dissipates, crosses 500 meshes, obtain modified coated silver；
(4) according to parts by weight, respectively weigh 25~30 parts of modified coated silvers, 10~15 parts of glass powders, 3~5 parts of tin oxide,
3~5 parts of Indium Tris acetylacetonates, 25~30 parts of acetone are placed in mortar, and grinding distribution simultaneously collects dispersion slurries, and dispersion slurries are stood
Deaeration is simultaneously screen printed onto clean ceramic base plate surface by hand, stands, is dry, heating heating, heat preservation calcining, and standing is cooled to
Room temperature, take off film can be prepared into anti-oxidative conductive silver paste thick-film material.
Oil bath heating temperature described in step (1) is 100~110 DEG C.
Heating described in step (3), which is heated to be, is warming up to 750~800 DEG C by 1 DEG C/min.
Heat preservation calcination temperature described in step (4) is 600~650 DEG C.
The present invention is compared with other methods, and advantageous effects are:
Technical solution of the present invention uses pure zirconium chloride for zirconium source, and ethyl orthosilicate is silicon source, and dehydrated alcohol is solvent, lithium fluoride
For mineralizer, precursor sol and coating modification silver powder particles are prepared, and grout material is prepared by modified silver powder, due to preset
It is the contact condition of dispersion between metallic particles in slurry thick film, after dry or solidification sintering, on the one hand makes slurry film layer
Electric conductivity reinforce, on the other hand but also film layer and the bond strength of ceramic substrate enhance, organic binder dry or
It is heat-treated volatilization early period to decompose, high temperature sintering makes the netted knot in infiltration metallic particles gap after glass binder and oxide fusion
In structure, the reticular structure of metallic is mutually filled in glassy bond, makes Argent grain conduction is alternate to be bound to each other to form some strength
Film layer, the film layer of such compact texture, be effectively improved material thick-film material clad structure and anti-oxidant modified performance, together
When part adhesive mutually pass through Argent grain gap and penetrate into substrate surface, conductive layer crystal boundary is glued together with substrate, increases attachment
Power, further increases the compact structure of material, to be effectively improved the antioxygenic property of material.
Specific embodiment
According to parts by weight, 45~50 parts of dehydrated alcohols, 2~3 parts of zirconium chlorides, 1~2 part of lithium fluoride and 6 are weighed respectively
~8 parts of ethyl orthosilicates are placed in a beaker, and are stirred and are transferred in conical flask, are stirred and are placed in 100~110 DEG C
3~5h of lower oil bath heating, standing are cooled to room temperature, and obtain mixed liquor and in mass ratio 1:50, tetrabutylammonium bromide are added to mixed
It closes in liquid, is stirred to be placed at 100~110 DEG C and reacts 10~12h, standing is cooled to room temperature, and obtains modification sol liquid；By matter
200 mesh silver powder are added in modification sol liquid by amount than 1:1, are stirred and grinding distribution, collection dispersion slurries are placed in 45
Dry 3~5h at~50 DEG C collects dry particle and is placed in 500~550 DEG C of Muffle furnaces, 750 are warming up to by 1 DEG C/min~
800 DEG C, after 2~3h is calcined in heat preservation, standing is cooled to room temperature and grinding distribution, crosses 500 meshes, obtains modified coated silver；By weight
Number meter is measured, weighs 25~30 parts of modified coated silvers, 10~15 parts of glass powders, 3~5 parts of tin oxide, 3~5 parts of acetyl respectively
Acetone indium, 25~30 parts of acetone are placed in mortar, and grinding distribution simultaneously collects dispersion slurries, by dispersion slurries standing and defoaming and use hand
Work is screen printed onto clean ceramic base plate surface, after standing 25~30min, then dry 25~30min at 85~90 DEG C, then
Dry 3~5min in 500 DEG C of Muffle furnaces again, then 600~650 DEG C are warming up to by 3 DEG C/min, heat preservation 2~3h of calcining is stood cold
But to room temperature, take off film can be prepared into anti-oxidative conductive silver paste thick-film material.
Example 1
According to parts by weight, 45 parts of dehydrated alcohols, 2 parts of zirconium chlorides, 1 part of lithium fluoride and 6 parts of ethyl orthosilicates are weighed respectively to set
It in beaker, is stirred and is transferred in conical flask, be stirred and be placed in oil bath heating 3h at 100 DEG C, stand cooling
To room temperature, mixed liquor and in mass ratio 1:50 are obtained, tetrabutylammonium bromide is added in mixed liquor, is stirred and is placed in 100
10h is reacted at DEG C, standing is cooled to room temperature, and obtains modification sol liquid；200 mesh silver powder are added to modification sol by 1:1 in mass ratio
In liquid, it is stirred and grinding distribution, collection dispersion slurries is placed at 45 DEG C dry 3h, collects dry particle and be placed in 500
In DEG C Muffle furnace, 750 DEG C are warming up to by 1 DEG C/min, after heat preservation calcining 2h, standing is cooled to room temperature and grinding distribution, crosses 500 mesh
Sieve, obtains modified coated silver；According to parts by weight, respectively weigh 25 parts of modified coated silvers, 10 parts of glass powders, 3 parts of tin oxide,
3 parts of Indium Tris acetylacetonates, 25 parts of acetone are placed in mortar, and grinding distribution simultaneously collects dispersion slurries, simultaneously by dispersion slurries standing and defoaming
It is screen printed onto clean ceramic base plate surface by hand, after standing 25min, then the dry 25min at 85 DEG C, then again 500
Dry 3min in DEG C Muffle furnace, then 600 DEG C are warming up to by 3 DEG C/min, 2h is calcined in heat preservation, and standing is cooled to room temperature, and takes off film
Be prepared into anti-oxidative conductive silver paste thick-film material.
Example 2
According to parts by weight, 47 parts of dehydrated alcohols, 2 parts of zirconium chlorides, 1 part of lithium fluoride and 7 parts of ethyl orthosilicates are weighed respectively to set
It in beaker, is stirred and is transferred in conical flask, be stirred and be placed in oil bath heating 4h at 105 DEG C, stand cooling
To room temperature, mixed liquor and in mass ratio 1:50 are obtained, tetrabutylammonium bromide is added in mixed liquor, is stirred and is placed in 105
11h is reacted at DEG C, standing is cooled to room temperature, and obtains modification sol liquid；200 mesh silver powder are added to modification sol by 1:1 in mass ratio
In liquid, it is stirred and grinding distribution, collection dispersion slurries is placed at 47 DEG C dry 4h, collects dry particle and be placed in 525
In DEG C Muffle furnace, 775 DEG C are warming up to by 1 DEG C/min, after heat preservation calcining 2h, standing is cooled to room temperature and grinding distribution, crosses 500 mesh
Sieve, obtains modified coated silver；According to parts by weight, respectively weigh 27 parts of modified coated silvers, 12 parts of glass powders, 4 parts of tin oxide,
4 parts of Indium Tris acetylacetonates, 27 parts of acetone are placed in mortar, and grinding distribution simultaneously collects dispersion slurries, simultaneously by dispersion slurries standing and defoaming
It is screen printed onto clean ceramic base plate surface by hand, after standing 27min, then the dry 27min at 87 DEG C, then again 500
Dry 4min in DEG C Muffle furnace, then 625 DEG C are warming up to by 3 DEG C/min, 2h is calcined in heat preservation, and standing is cooled to room temperature, and takes off film
Be prepared into anti-oxidative conductive silver paste thick-film material.
Example 3
According to parts by weight, 50 parts of dehydrated alcohols, 3 parts of zirconium chlorides, 2 parts of lithium fluoride and 8 parts of ethyl orthosilicates are weighed respectively to set
It in beaker, is stirred and is transferred in conical flask, be stirred and be placed in oil bath heating 5h at 110 DEG C, stand cooling
To room temperature, mixed liquor and in mass ratio 1:50 are obtained, tetrabutylammonium bromide is added in mixed liquor, is stirred and is placed in 110
12h is reacted at DEG C, standing is cooled to room temperature, and obtains modification sol liquid；200 mesh silver powder are added to modification sol by 1:1 in mass ratio
In liquid, it is stirred and grinding distribution, collection dispersion slurries is placed at 50 DEG C dry 5h, collects dry particle and be placed in 550
In DEG C Muffle furnace, 800 DEG C are warming up to by 1 DEG C/min, after heat preservation calcining 3h, standing is cooled to room temperature and grinding distribution, crosses 500 mesh
Sieve, obtains modified coated silver；According to parts by weight, respectively weigh 30 parts of modified coated silvers, 15 parts of glass powders, 5 parts of tin oxide,
5 parts of Indium Tris acetylacetonates, 30 parts of acetone are placed in mortar, and grinding distribution simultaneously collects dispersion slurries, simultaneously by dispersion slurries standing and defoaming
It is screen printed onto clean ceramic base plate surface by hand, after standing 30min, then the dry 30min at 90 DEG C, then again 500
Dry 5min in DEG C Muffle furnace, then 650 DEG C are warming up to by 3 DEG C/min, 3h is calcined in heat preservation, and standing is cooled to room temperature, and takes off film
Be prepared into anti-oxidative conductive silver paste thick-film material.
Example 1,2,3 prepared by the present invention is tested for the property, specific test result is as follows shown in table table 1:
1 performance test table of table
As seen from the above table, thick film silver pulp material prepared by the present invention has excellent antioxygenic property.
Claims (4)
1. a kind of preparation method of anti-oxidative conductive silver paste thick-film material, it is characterised in that specific preparation step are as follows:
(1) according to parts by weight, weigh respectively 45~50 parts of dehydrated alcohols, 2~3 parts of zirconium chlorides, 1~2 part of lithium fluoride and 6~
8 parts of ethyl orthosilicates are placed in a beaker, and are stirred and are transferred in conical flask, are stirred and oil bath heating, standing are cold
But to room temperature, mixed liquor is obtained；
(2) 1:50 in mass ratio, tetrabutylammonium bromide is added in mixed liquor, is stirred and oil bath heating, standing cool down
To room temperature, modification sol liquid is obtained；
(3) 200 mesh silver powder are added in modification sol liquid by 1:1 in mass ratio, are stirred and grinding distribution, collection disperse
Slurries and drying are collected in dry particle juxtaposition Muffle furnace, heating heating, heat preservation calcining, and standing is cooled to room temperature and grinds point
It dissipates, crosses 500 meshes, obtain modified coated silver；
(4) according to parts by weight, respectively weigh 25~30 parts of modified coated silvers, 10~15 parts of glass powders, 3~5 parts of tin oxide,
3~5 parts of Indium Tris acetylacetonates, 25~30 parts of acetone are placed in mortar, and grinding distribution simultaneously collects dispersion slurries, and dispersion slurries are stood
Deaeration is simultaneously screen printed onto clean ceramic base plate surface by hand, stands, is dry, heating heating, heat preservation calcining, and standing is cooled to
Room temperature, take off film can be prepared into anti-oxidative conductive silver paste thick-film material.
2. a kind of preparation method of anti-oxidative conductive silver paste thick-film material according to claim 1, it is characterised in that: step
Suddenly oil bath heating temperature described in (1) is 100~110 DEG C.
3. a kind of preparation method of anti-oxidative conductive silver paste thick-film material according to claim 1, it is characterised in that: step
Suddenly heating described in (3), which is heated to be, is warming up to 750~800 DEG C by 1 DEG C/min.
4. a kind of preparation method of anti-oxidative conductive silver paste thick-film material according to claim 1, it is characterised in that: step
Suddenly heat preservation calcination temperature described in (4) is 600~650 DEG C.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112071464A (en) * | 2020-09-09 | 2020-12-11 | 西安宏星电子浆料科技股份有限公司 | Co-fired hole-filling conductor slurry and preparation method thereof |
| CN114023511A (en) * | 2021-11-11 | 2022-02-08 | 中国有色桂林矿产地质研究院有限公司 | Method for preparing high-temperature electronic paste based on organic phosphorus salt |
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| CN102502673A (en) * | 2011-11-23 | 2012-06-20 | 陕西科技大学 | Method for preparing flaky silicic acid zirconium nanocrystalline |
| CN108172337A (en) * | 2017-12-26 | 2018-06-15 | 西安工程大学 | A kind of preparation method of the good MAX phases series electronic slurry of antioxygenic property |
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Patent Citations (5)
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| CN101054179A (en) * | 2007-05-29 | 2007-10-17 | 景德镇陶瓷学院 | Method of synthesizing zirconium silicate powder at low temperature by unhydrolyzed sol-gel method |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112071464A (en) * | 2020-09-09 | 2020-12-11 | 西安宏星电子浆料科技股份有限公司 | Co-fired hole-filling conductor slurry and preparation method thereof |
| CN114023511A (en) * | 2021-11-11 | 2022-02-08 | 中国有色桂林矿产地质研究院有限公司 | Method for preparing high-temperature electronic paste based on organic phosphorus salt |
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