CN102030526A - Anti-reduction ceramic dielectric material and preparation method thereof - Google Patents
Anti-reduction ceramic dielectric material and preparation method thereof Download PDFInfo
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- CN102030526A CN102030526A CN 201010538862 CN201010538862A CN102030526A CN 102030526 A CN102030526 A CN 102030526A CN 201010538862 CN201010538862 CN 201010538862 CN 201010538862 A CN201010538862 A CN 201010538862A CN 102030526 A CN102030526 A CN 102030526A
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Abstract
The invention discloses an anti-reduction ceramic dielectric material and a preparation method thereof. Ba1-xMgxTi1-ySiyO3 synthesized by a solid-phase reaction method serves as a main crystalline phase material, wherein x is more than or equal to 0.03 and less than or equal to 0.15, y is more than or equal to 0.02 and less than or equal to 0.10, and the main crystalline phase component accounts for 93 to 98 mole percent of the dielectric material; a modified additive is added and is selected from three or more of CaO, SrO, Y2O3, ZrO2, Eu2O3, MnO2, SiO2, Al2O3 and ZnO; the modified additive accounts for 2 to 7 mole percent of the dielectric material; therefore, a ceramic dielectric material with X7R characteristics, which can take nickel or a nickel alloy as an inner electrode and is suitable to be sintered in a reducing atmosphere is obtained by wet ball milling and drying. The material does not contain a heavy metal element, meets the environmentally-friendly requirement in an electronic industry, and has the characteristics of high uniformity and stable process performance.
Description
Technical field
The present invention relates to a kind of anti-reduction ceramic medium material and preparation method thereof.
Background technology
Laminated ceramic capacitor (MLCC) is meant metal electrode layer is superimposed with the stupalith medium layer is in the same place, and becomes a DB through high temperature sintering, and the system of reburning end outer electrode forms.Being adapted at carrying out agglomerating MLCC in the air atmosphere, all is to do interior electrode with precious metal palladium or palladium-silver alloy; And all contain poisonous metal elements such as lead, cadmium in the used ceramic medium material mostly.Because the price of palladium, silver is higher, make that the material cost of laminated ceramic capacitor is high.In the face of the market competition that is growing more intense, numerous MLCC manufacturer all reduces production costs seeking various ways; In addition along with the more and more attention of people to environmental protection, the use field of poisonous metal elements such as existing in the world relevant it is forbidden by decree to lead, cadmium, the MLCC product for using always is required unleaded especially.In the face of this situation, it is feasible being suggested and being confirmed very soon as the idea of interior electrode with cheap metal nickel or the alternative precious metal of nickelalloy, the more important thing is that this alternative energy is significantly descended the material cost of MLCC; But then, with nickel or nickelalloy MLCC, if sintering can cause interior anodizing in air, so must in reducing atmosphere, carry out sintering as interior electrode.And in reducing atmosphere sintering, the ceramic medium material of traditional coupling precious metal can reduce, cause the electrical property degradation phenomena such as insulation resistance decline, loss tangent rising of MLCC, therefore, when selecting nickel or nickelalloy for use as interior electrode, require used ceramic medium material must have resistance to reduction, in reducing atmosphere, have superior dielectric properties behind the sintering to guarantee corresponding M LCC product.
For a class ceramic medium material, normally with BaTiO with EIA standard x 7R temperature profile
3For carrying out doping vario-property, base obtains.So-called X7R, the electrical capacity when being meant with 25 ℃ is a benchmark, in-55 ℃～+ 125 ℃ temperature range, rate of change of capacitance is no more than ± 15% scope.In the correlative study of carrying out, the BaTiO for preparing with liquid phase method is disclosed at home as Chinese patent CN 101333105A, CN1626475A, CN1604245A, CN1594217A etc.
3Study the anti-reduction ceramic medium material that acquisition has the X7R characteristic.The technology that the employing liquid phase method prepares barium titanate is complicated, and will just can obtain tetragonal phase structure completely through high-temperature calcination, can loss-rate solid phase method height.
Summary of the invention
Purpose of the present invention is that a kind of anti-reduction ceramic medium material and preparation method thereof will be provided, and it adopts the synthetic single compd B a of solid phase method
1-xMg
xTi
1-ySi
yO
3As the principal crystalline phase composition; The ceramic medium material that is provided has good dispersiveness, homogeneity and technology stability; When being used to prepare laminated ceramic capacitor, can be good with electrode coupling in nickel or the nickelalloy, sintering in reducing atmosphere is realized grain refining, grain growing is even, the porcelain body densification, defective is few, has superior dielectric properties.
The present invention is achieved in that described a kind of anti-reduction ceramic medium material, it is characterized in that: be made up of principal crystalline phase composition and property-modifying additive; With solid phase method synthetic Ba
1-xMg
xTi
1-ySi
yO
3(wherein 0.03≤x≤0.15,0.02≤y≤0.10) as the principal crystalline phase composition, principal crystalline phase composition shared molfraction in the prescription of dielectric material is formed is 93～98 mol%; Property-modifying additive is selected from CaO, SrO, Y
2O
3, ZrO
2, Eu
2O
3, MnO
2, SiO
2, Al
2O
3, among the ZnO more than three kinds or three kinds; Various oxide compounds in the property-modifying additive shared molfraction in described dielectric material is that CaO accounts for 0.2～3 mol%, SrO and accounts for 0～2 mol%, Y
2O
3Account for 0～2 mol%,, ZrO
2Account for 0～1 mol%, Eu
2O
3Account for 0～1mol%, MnO
2Account for 0.1～0.8 mol%, SiO
2Account for 0～3 mol%, Al
2O
3Account for 0～2 mol%, ZnO accounts for 0～3 mol%; Property-modifying additive shared molfraction in the prescription of dielectric material is formed is 2～7 mol%.
The preparation method of a kind of anti-reduction ceramic medium material of the present invention is characterized in that: described principal crystalline phase composition Ba
1-xMg
xTi
1-ySi
yO
3The acquisition of (wherein 0.03≤x≤0.15,0.02≤y≤0.10) is BaCO
3, MgO, SiO
2And TiO
2Place ball mill, by weight for material: deionized water=1:(1.0～2.0) ratio add deionized water and carry out wet ball grinding and mix, carry out drying with spray-drying tower or other drying plant then, the calcining of 1050 ℃～1200 ℃ temperature range was synthesized in 1.5～6 hours in the air atmosphere stove; With above-mentioned property-modifying additive, weigh by the mol ratio that prescription is formed, place ultra-fine grinding mill, by weight for material: deionized water=1:(0.9～1.8) ratio add deionized water and carry out wet ball grinding, then the good material of ball milling is carried out drying, obtain anti-reduction ceramic medium material of the present invention.
Anti-reduction ceramic medium material of the present invention has the specific inductivity more than at least 2500; Electrode in coupling nickel or the nickelalloy; The temperature range that is adapted in the reducing atmosphere 1200 ℃～1280 ℃ is carried out sintering, so that make laminated ceramic capacitor.
The invention has the beneficial effects as follows that prepared ceramic medium material has good dispersiveness, homogeneity and technology stability; When being used to prepare laminated ceramic capacitor, can be good with electrode coupling in nickel or the nickelalloy, sintering in reducing atmosphere; The laminated ceramic capacitor of making has superior dielectric properties, and reduces production costs.
Embodiment
A kind of anti-reduction ceramic medium material of the present invention is made up of principal crystalline phase composition and property-modifying additive; With solid phase method synthetic Ba
1-xMg
xTi
1-ySi
yO
3(0.03≤x≤0.15,0.02≤y≤0.10) as the principal crystalline phase composition, principal crystalline phase composition shared molfraction in the prescription of dielectric material is formed is 93～98 mol%; Property-modifying additive is selected from CaO, SrO, Y
2O
3, ZrO
2, Eu
2O
3, MnO
2, SiO
2, Al
2O
3, among the ZnO more than three kinds or three kinds; Various oxide compounds in the property-modifying additive shared molfraction in described dielectric material is that CaO accounts for 0.2～3 mol%, SrO and accounts for 0～2 mol%, Y
2O
3Account for 0～2 mol%,, ZrO
2Account for 0～1 mol%, Eu
2O
3Account for 0～1mol%, MnO
2Account for 0.1～0.8 mol%, SiO
2Account for 0～3 mol%, Al
2O
3Account for 0～2 mol%, ZnO accounts for 0～3 mol%; Property-modifying additive shared molfraction in the prescription of dielectric material is formed is 2～7 mol%.
The preparation method of a kind of anti-reduction ceramic medium material of the present invention, described principal crystalline phase composition Ba
1-xMg
xTi
1-ySi
yO
3The acquisition of (0.03≤x≤0.15,0.02≤y≤0.10) is BaCO
3, MgO, SiO
2And TiO
2Place ball mill, by weight for material: deionized water=1:(1.0～2.0) ratio add deionized water and carry out wet ball grinding and mix, carry out drying with spray-drying tower or other drying plant then, the calcining of 1050 ℃～1200 ℃ temperature range was synthesized in 1.5～6 hours in the air atmosphere stove, obtained Ba
1-xMg
xTi
1-ySi
yO
3Powder; With above-mentioned property-modifying additive, weigh by the mol ratio that prescription is formed, place ultra-fine grinding mill, by weight for material: deionized water=1:(0.9～1.8) ratio add deionized water and carry out wet ball grinding, the requirement mixing of materials is even, and reach certain granularity, preferably make the powder average particle size particle size behind the ball milling be lower than 0.6 micron.Carry out drying with spray-drying tower or other drying plant after ball milling finishes, obtain ceramic medium material powder of the present invention.
Ceramic medium material of the present invention can be in reducing atmosphere 1200 ℃～1280 ℃ temperature range realize sintering, room temperature dielectric constant is 2500～3500, the electrical capacity temperature profile reaches the requirement of X7R.
The process of the ceramic medium material that the preparation laminated ceramic capacitor is used is as follows.
Embodiment
(1) with ultra-fine, analytically pure BaCO
3, MgO, SiO
2And TiO
2Be raw material,, press the proportion of composing of table 1, mix placing ball mill, add deionized water, through the ball milling thorough mixing evenly after, place spray-drying tower or other drying plant to carry out drying, then the synthetic Ba of calcining in air atmosphere
1-xMg
xTi
1-ySi
yO
3Powder.
(2) with ultra-fine, analytically pure CaO, SrO, Y
2O
3, ZrO
2, Eu
2O
3, MnO
2, SiO
2, Al
2O
3, ZnO is raw material, press the proportion of composing of table 1, mix and place ultra-fine grinding mill, add deionized water and carry out superfine grinding, size-grade distribution to slurry in the process of ultra-fine mill is carried out analysis monitoring, size-grade distribution is carried out drying with spray-drying tower or other drying plant after reaching requirement, obtains ceramic medium material powder of the present invention at last.
(3) process of preparation electrical condenser sample:
Get the ceramic medium material powder that aforesaid method obtains, calculate in proportion, in the powder of 100 grams, the dehydrated alcohol that adds 40～60 grams, the PVB based adhesive of 30～45 grams, ball milling evenly forms slurry, and obtaining thickness through curtain coating again is 20 microns ceramic dielectic diaphragm green compact, with the nickel slurry as interior electrode carry out double exposure, etc. obtain laminated ceramic capacitor behind static pressure, cutting, binder removal, sintering, chamfering, last copper or the copper alloy outer electrode; Wherein the agglomerating condition is: 1200 ℃～1280 ℃ temperature range in the reducing atmosphere, soaking time is 1.5～6 hours.
The composition of table 1 embodiment of the invention
The respective electrical The performance test results of table 2 embodiment of the invention
Claims (3)
1. an anti-reduction ceramic medium material is characterized in that: be made up of principal crystalline phase composition and property-modifying additive; With solid phase method synthetic Ba
1-xMg
xTi
1-ySi
yO
3, wherein 0.03≤x≤0.15,0.02≤y≤0.10 is as the principal crystalline phase composition, and principal crystalline phase composition shared molfraction in the prescription of dielectric material is formed is 93～98 mol%;
Property-modifying additive is selected from CaO, SrO, Y
2O
3, ZrO
2, Eu
2O
3, MnO
2, SiO
2, Al
2O
3, among the ZnO more than three kinds or three kinds; Various oxide compounds in the property-modifying additive shared molfraction in described dielectric material is: CaO accounts for 0.2～3 mol%, SrO and accounts for 0～2 mol%, Y
2O
3Account for 0～2 mol%,, ZrO
2Account for 0～1 mol%, Eu
2O
3Account for 0～1mol%, MnO
2Account for 0.1～0.8 mol%, SiO
2Account for 0～3 mol%, Al
2O
3Account for 0～2 mol%, ZnO accounts for 0～3 mol%; Property-modifying additive shared molfraction in the prescription of dielectric material is formed is 2～7 mol%.
2. the preparation method of an anti-reduction ceramic medium material is characterized in that: described principal crystalline phase composition Ba
1-xMg
xTi
1-ySi
yO
3, the wherein acquisition of 0.03≤x≤0.15,0.02≤y≤0.10 is BaCO
3, MgO, SiO
2And TiO
2Place ball mill, carrying out wet ball grinding by weight the ratio adding deionized water for material: deionized water=1:1.0～2.0 mixes, carry out drying with spray-drying tower or other drying plant then, the calcining of 1050 ℃～1200 ℃ temperature range was synthesized in 1.5～6 hours in the air atmosphere stove; With the property-modifying additive in the claim 1, weigh by the mol ratio that prescription is formed, place ultra-fine grinding mill, add deionized water by weight ratio and carry out wet ball grinding for material: deionized water=1:0.9～1.8; Then the good material of ball milling is carried out drying, obtain anti-reduction ceramic medium material of the present invention.
3. according to the preparation method of the described a kind of anti-reduction ceramic medium material of claim 2, it is characterized in that: described anti-reduction ceramic medium material has the specific inductivity more than at least 2500; Electrode in coupling nickel or the nickelalloy; The temperature range that is adapted in the reducing atmosphere 1200 ℃～1280 ℃ is carried out sintering, so that make laminated ceramic capacitor.
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| CN 201010538862 CN102030526B (en) | 2010-11-11 | 2010-11-11 | Anti-reduction ceramic dielectric material and preparation method thereof |
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Cited By (7)
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| CN102531579A (en) * | 2011-11-10 | 2012-07-04 | 厦门万明电子有限公司 | Ceramic dielectric material and manufacture method thereof and ceramic capacitor and manufacture method thereof |
| CN102531592A (en) * | 2011-11-10 | 2012-07-04 | 厦门万明电子有限公司 | Reduction-resistant Y5P ceramic capacitor dielectric porcelain |
| CN106892659A (en) * | 2017-03-31 | 2017-06-27 | 天津大学 | A kind of anti-reduction huge dielectric constant medium material for multilayer ceramic capacitors |
| CN107500755A (en) * | 2017-10-12 | 2017-12-22 | 厦门松元电子有限公司 | A kind of low sintering MLCC ceramic medium materials and preparation method thereof |
| CN107500754A (en) * | 2017-09-30 | 2017-12-22 | 厦门松元电子有限公司 | It is a kind of to be used for high ceramic medium material for holding high pressure MLCC and preparation method thereof |
| CN108911722A (en) * | 2018-09-30 | 2018-11-30 | 太原师范学院 | A kind of high dielectric stable type ceramic medium material and preparation method thereof |
| CN114262219A (en) * | 2021-12-31 | 2022-04-01 | 北京元六鸿远电子科技股份有限公司 | Microwave dielectric ceramic material with ultrahigh temperature stability and preparation method and application thereof |
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102531579A (en) * | 2011-11-10 | 2012-07-04 | 厦门万明电子有限公司 | Ceramic dielectric material and manufacture method thereof and ceramic capacitor and manufacture method thereof |
| CN102531592A (en) * | 2011-11-10 | 2012-07-04 | 厦门万明电子有限公司 | Reduction-resistant Y5P ceramic capacitor dielectric porcelain |
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| CN102531592B (en) * | 2011-11-10 | 2014-10-29 | 厦门万明电子有限公司 | Reduction-resistant Y5P ceramic capacitor dielectric porcelain |
| CN106892659A (en) * | 2017-03-31 | 2017-06-27 | 天津大学 | A kind of anti-reduction huge dielectric constant medium material for multilayer ceramic capacitors |
| CN107500754A (en) * | 2017-09-30 | 2017-12-22 | 厦门松元电子有限公司 | It is a kind of to be used for high ceramic medium material for holding high pressure MLCC and preparation method thereof |
| CN107500754B (en) * | 2017-09-30 | 2020-01-14 | 厦门松元电子有限公司 | Ceramic dielectric material for high-capacity high-voltage MLCC and preparation method thereof |
| CN107500755A (en) * | 2017-10-12 | 2017-12-22 | 厦门松元电子有限公司 | A kind of low sintering MLCC ceramic medium materials and preparation method thereof |
| CN108911722A (en) * | 2018-09-30 | 2018-11-30 | 太原师范学院 | A kind of high dielectric stable type ceramic medium material and preparation method thereof |
| CN114262219A (en) * | 2021-12-31 | 2022-04-01 | 北京元六鸿远电子科技股份有限公司 | Microwave dielectric ceramic material with ultrahigh temperature stability and preparation method and application thereof |
| CN114262219B (en) * | 2021-12-31 | 2022-09-06 | 北京元六鸿远电子科技股份有限公司 | Microwave dielectric ceramic material with ultrahigh temperature stability and preparation method and application thereof |
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