CN102030526B - 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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- CN102030526B CN102030526B CN 201010538862 CN201010538862A CN102030526B CN 102030526 B CN102030526 B CN 102030526B CN 201010538862 CN201010538862 CN 201010538862 CN 201010538862 A CN201010538862 A CN 201010538862A CN 102030526 B CN102030526 B CN 102030526B
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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 dielectric material and preparation method thereof.
Background technology
Laminated ceramic capacitor (MLCC) refers to metal electrode layer is superimposed with the stupalith medium layer and is in the same place, and becomes a DB through high temperature sintering, and the end processed outer electrode that reburns forms.Being adapted at carrying out in the air atmosphere MLCC of sintering, all is to do interior electrode with precious metal palladium or palladium-silver alloy; And mostly all contain the harmful metal elements such as lead, cadmium in the used ceramic medium material.Because the price of palladium, silver is higher, so 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 the harmful metal elements such as existing relevant it is forbidden by decree to lead, cadmium in the world, the MLCC product for commonly using 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 the nickelalloy MLCC as interior electrode, if sintering can cause interior anodizing in air, so must in reducing atmosphere, carry out sintering.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 as interior electrode, require used ceramic medium material must have resistance to reduction, in reducing atmosphere, have good dielectric properties behind the sintering to guarantee corresponding MLCC product.
For the class ceramic medium material with EIA standard x 7R temperature profile, normally with BaTiO
3For carrying out doping vario-property, base obtains.So-called X7R, the electrical capacity when referring to take 25 ℃ is as benchmark, and in-55 ℃～+ 125 ℃ temperature range, rate of change of capacitance is no more than ± 15% scope.In the correlative study of carrying out at home, the BaTiO that uses Liquid preparation methods is disclosed such as Chinese patent CN 101333105A, CN1626475A, CN1604245A, CN1594217A etc.
3Study the anti-reduction ceramic dielectric material that acquisition has the X7R characteristic.Adopt the technique of Liquid preparation methods barium titanate complicated, and will just can obtain completely tetragonal phase structure through high-temperature calcination, energy loss-rate solid phase method is high.
Summary of the invention
Purpose of the present invention is that a kind of anti-reduction ceramic dielectric 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 provides has good dispersiveness, homogeneity and technology stability; During for the preparation of laminated ceramic capacitor, can be good with electrode coupling in nickel or the nickelalloy, sintering in reducing atmosphere is realized grain refining, and grain growing is even, and porcelain body is fine and close, and defective is few, has good dielectric properties.
The present invention is achieved in that described a kind of anti-reduction ceramic dielectric material, it is characterized in that: be comprised of principal crystalline phase composition and property-modifying additive; With the synthetic Ba of solid phase method
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 forms 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 forms is 2～7 mol%.
The preparation method of a kind of anti-reduction ceramic dielectric 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, then carry out drying with spray-drying tower or other drying plant, 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 forms, 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 dielectric material of the present invention.
Anti-reduction ceramic dielectric 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, in order to make laminated ceramic capacitor.
The invention has the beneficial effects as follows, prepared ceramic medium material has good dispersiveness, homogeneity and technology stability; During for the preparation of 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 good dielectric properties, and reduces production costs.
Embodiment
A kind of anti-reduction ceramic dielectric material of the present invention is comprised of principal crystalline phase composition and property-modifying additive; With the synthetic Ba of solid phase method
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 forms 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 forms is 2～7 mol%.
The preparation method of a kind of anti-reduction ceramic dielectric 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, then carry out drying with spray-drying tower or other drying plant, 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 forms, 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.Ball milling is complete to carry out drying afterwards with spray-drying tower or other drying plant, obtains 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, after ball milling fully mixes, 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 Ultrafine Grinding is carried out analysis monitoring, size-grade distribution is carried out drying with spray-drying tower or other drying plant after reaching requirement, obtains at last ceramic medium material powder of the present invention.
(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, upper copper or the copper alloy outer electrode; Wherein the condition of sintering 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 dielectric material is characterized in that: be comprised of principal crystalline phase composition and property-modifying additive; With the synthetic Ba of solid phase method
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 forms 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 forms is 2～7 mol%.
2.
As claimed in claim 1A kind of preparation method of anti-reduction ceramic dielectric 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, then carry out drying with spray-drying tower or other drying plant, 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 forms, place ultra-fine grinding mill, add deionized water by weight the ratio for material: deionized water=1:0.9～1.8 and carry out wet ball grinding; Then the good material of ball milling is carried out drying, obtain anti-reduction ceramic dielectric material.
3. the preparation method of described a kind of anti-reduction ceramic dielectric material according to claim 2, it is characterized in that: described anti-reduction ceramic dielectric material at room temperature has 2500-3500 specific inductivity; Electrode in coupling nickel or the nickelalloy; The temperature range that is adapted in the reducing atmosphere 1200 ℃～1280 ℃ is carried out sintering, in order to make laminated ceramic capacitor.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102531579B (en) * | 2011-11-10 | 2014-07-23 | 厦门万明电子有限公司 | Ceramic dielectric material and manufacture method thereof and ceramic capacitor and manufacture method thereof |
| 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 |
| 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 |
| 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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| CN1332131A (en) * | 2000-07-05 | 2002-01-23 | 三星电机株式会社 | Dielectric ceramic composition, ceramic capacitor using the same and manufacture thereof |
| CN1404080A (en) * | 2002-10-14 | 2003-03-19 | 清华大学 | Dielectric material for thermostable laminated ceramic capacitor with basic-metal inner electrode |
| US7358208B2 (en) * | 2005-01-20 | 2008-04-15 | Tdk Corporation | Dielectric ceramic composition and electronic device |
| CN101659546A (en) * | 2008-08-27 | 2010-03-03 | 北京有色金属研究总院 | Barium strontium titanate ceramic capacitor material and preparation method thereof |
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| JP2002187770A (en) * | 2000-12-15 | 2002-07-05 | Toho Titanium Co Ltd | Dielectric porcelain composition and laminated ceramic capacitor using the same |
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Patent Citations (4)
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|---|---|---|---|---|
| CN1332131A (en) * | 2000-07-05 | 2002-01-23 | 三星电机株式会社 | Dielectric ceramic composition, ceramic capacitor using the same and manufacture thereof |
| CN1404080A (en) * | 2002-10-14 | 2003-03-19 | 清华大学 | Dielectric material for thermostable laminated ceramic capacitor with basic-metal inner electrode |
| US7358208B2 (en) * | 2005-01-20 | 2008-04-15 | Tdk Corporation | Dielectric ceramic composition and electronic device |
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