CN100464382C - Zinc-magnesium titanate system ceramic dielectric material and prepared ceramic capacitor - Google Patents
Zinc-magnesium titanate system ceramic dielectric material and prepared ceramic capacitor Download PDFInfo
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- CN100464382C CN100464382C CNB2003101176385A CN200310117638A CN100464382C CN 100464382 C CN100464382 C CN 100464382C CN B2003101176385 A CNB2003101176385 A CN B2003101176385A CN 200310117638 A CN200310117638 A CN 200310117638A CN 100464382 C CN100464382 C CN 100464382C
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Abstract
This invention discloses a high frequency thermal stable ceramic material and its ceramic capacitor. The material comprises the main component and assistant components, wherein the main components are 40-55% of Mg(1-x)ZnxTiO3(0.0001<=X<=0.05) and 20-25% of Mg(2-y)ZnySiO4(0.0001<=X<=0.05); the assistant components are 10-15% of ZnO and 3.0-7.0% of Al2O3 and 2.0-6.0% of SrO. The assistant components also comprise the following: 1.0-2.5% of B2O3,0.5-2.0% of Nd2O5,0.1-0.5% of MnO2,0.1-0.4% of Co3O4 and one or more materials from K2O,Fe2O3,CeO2 and SnO.
Description
Technical field
The present invention relates to the ceramic capacitor of low be situated between heat-staple ceramic medium material and gained of a kind of high frequency, more particularly, the present invention relates to ceramic capacitor harmful elements such as a kind of not leaded, arsenic, cadmium, zinc-magnesium titanate system ceramic medium material and gained.
Background technology
MLCC is little with its volume, high reliability, mount characteristics such as convenient, is used widely in the manufacture process of electronic equipment.Market is also increasing to the demand of high frequency capacitor, requires also highlyer, and frequency of utilization is to the development of hundreds of megahertz even a few Gigahertz microwave section.There is deficiency in traditional high-frequency dielectric ceramic material performance aspect thermal stability, dielectric property usually, and all contains lead (Pb), arsenic (As), cadmium harmful elements such as (Cd), to environment and human body harmful.Therefore, be necessary to develop a kind of low ceramic medium material that is situated between of environment-friendly type high frequency, and use it for the manufacturing of multilayer chip capacitor with good frequency characteristic and dielectric property.
Chinese patent application CN00809330.x discloses a kind of by (Zn
1-xM
x) TiO
3And yTiO
2Mix the high-frequency dielectric ceramic that constitutes, satisfy following condition: wherein, M is Mg, Co or Ni, is under the situation of Mg at M, and O≤x≤0.6 is under the situation of Co at M, and 0≤x≤1 is under the situation of Ni at M, 0≤x≤0.8.Though a kind of principal component of this high-frequency dielectric ceramic can be Zn
1-xMg
xTiO
3, but its another kind of principal component is TiO
2, and the dielectric constant of this media ceramic is in 20～50 scope.
Summary of the invention
One of purpose of the present invention provides the low Jie's thermally stable ceramic media material of environment-friendly type high frequency of a kind of unleaded (Pb), arsenic (As), cadmium harmful elements such as (Cd).
In the present invention, the low Jie's thermally stable ceramic media material of high frequency comprises principal component and auxiliary element; By mole percentage, its principal component is 40～60% Mg
(1-x)Zn
xTiO
3With 15～30% Mg
(2-y)Zn
ySiO
4, wherein, 0.0001≤x≤0.05,0.0001≤y≤0.05 is preferably 0.001≤x≤0.05,0.001≤y≤0.05; Its auxiliary element is 10～15% ZnO, 3.0～7.0% Al
2O
3With 2.0～6.0% SrO.
Preferably, the auxiliary element of above-mentioned ceramic medium material can also comprise 1.0～2.5% B
2O
3With 0.5～2.0% Nd
2O
5More preferably, the auxiliary element of above-mentioned ceramic medium material can further include 0.1～0.5% MnO
2With 0.1～0.4% Co
3O
4
Further, the auxiliary element of above-mentioned ceramic medium material can also comprise 0.1～1.0%, be selected from K
2O, Fe
2O
3, CeO
2With one or more the material among the SnO.
Wherein, principal component Mg
(1-x)Zn
xTiO
3(0.0001≤x≤0.05) and Mg
(2-y)Zn
ySiO
4(0.0001≤y≤0.05) can form the congruent melting solid solution when high temperature sintering, thereby can improve the structure of system effectively, widens and burns temperature, improves dielectric property and frequency characteristic.
In the low Jie's thermally stable ceramic media material of high frequency, add auxiliary element ZnO, can promote the sintering of each material of dielectric material effectively.Preferably, adopt ZnO and B
2O
3In conjunction with as the glass flux, the glass flux can be diffused into grain boundary layer effectively.Control ZnO and B
2O
3Component, can improve the dielectric property and the insulation resistance of porcelain body effectively.In the low Jie's thermally stable ceramic media material of per 100 moles of high frequencies, the ZnO composition preferably is controlled between the 10-15 mole, B
2O
3Composition preferably is controlled between the 1.0-2.5 mole.If ZnO and B
2O
3Content surpasses the above-mentioned upper limit, and then glass ingredient is too much in the porcelain body, and the condenser dielectric loss is bigger than normal, and porcelain body intensity is low; If ZnO and B
2O
3Content is low excessively, and then insulation resistance descends.
Auxiliary element Al
2O
3Can improve the sintering characteristic of ceramic body, strengthen the mechanical strength of porcelain body, improve the quality factor under the capacitor high-frequency section, make the good frequency characteristic of its tool.Al in the low Jie's thermally stable ceramic media material of per 100 moles of high frequencies
2O
3Preferably be controlled between the 3.0-7.0 mole, more preferably be controlled between the 4.0-5.5 mole; If Al
2O
3Addition very little, then capacitor porcelain body bad mechanical strength can not guarantee the frequency characteristic under the high-frequency section; If Al
2O
3Addition is too many, and then the capacitor sintering becomes difficult.
Auxiliary element SrO can guarantee that capacitor volume satisfies the COG characteristic of EIA standard for variation of temperature.SrO content preferably is controlled between the 2.0-6.0 mole in the low Jie's thermally stable ceramic media material of per 100 moles of high frequencies.If the content of SrO exceeds this scope, then capacitor can't satisfy the COG characteristic.
Auxiliary element Nb
2O
5Can increase powder lattice activity, be beneficial to sintering, improve the reliability of ceramic capacitor, Nb in the low Jie's thermally stable ceramic media material of per 100 moles of high frequencies
2O
5Preferably be controlled between the 0.5-2.0 mole, if Nb
2O
5Exceed this scope, then be unfavorable for the reliability of the sintering and the assurance capacitor of capacitor.
Auxiliary element MnO
2Can guarantee has lower dielectric loss under the capacitor high band, improve the Q value of capacitor.Per 100 moles of high frequencies hang down Jie's thermally stable ceramic media material content MnO
2Amount preferably be controlled between the 0.2-0.5 mole, if MnO
2Content can make capacitor dielectric loss value under high band increase very little, and capacitor easily generates heat; If MnO
2Content surpasses 0.5 mole, and then the electric capacity sintering character is poor, and ceramic structure is loose.
Auxiliary element Co
3O
4The insulation resistance that can improve and improve capacitor reaches the equivalent series resistance that reduces capacitor under the high band effectively.Contain Co in the low Jie's thermally stable ceramic media material of per 100 moles of high frequencies
3O
4Content preferably is controlled at the 0.1-0.4 mole.If Co
3O
4Content is on the low side, then is unfavorable for the raising of capacitor insulation resistance; If content is higher, then the capacitor sintering becomes difficult.
Select K
2O, Fe
2O
3, CeO
2With one or more material among the SnO as auxiliary element, help to prevent the aging of capacitor, guarantee the capacitor dielectric property.Several auxiliary elements can be to add alone or in combination, and preferably, addition is 0.1～1.0 mole in the low Jie's thermally stable ceramic media material of per 100 moles of high frequencies.
Ceramic medium material of the present invention can make by calcining behind the powder of simple mixing said ingredients, also can mix by predetermined ratio by two or more powder that will be wherein, then mixture being carried out precalcining handles, thereby synthetic main burning piece and pair are expected, the more main piece that burns are expected to calcine to make with pair.Since the back a kind of mode can make each powder in ceramic dielectric, distribute more evenly after the precalcining and crystal phase structure more stable, compare with preceding a kind of mode, greatly reduced the dielectric property deviation of capacitor.Therefore, preferably, the present invention adopts a kind of mode in back.The precalcining temperature can be carried out under 1080-1180 ℃ temperature, and calcining heat can not be low excessively, otherwise the calcining effect is insufficient, required crystal phase structure instability; And if temperature is too high, then powder active reduces, and is unfavorable for sintering.For example, Mg
(1-x)Zn
xTiO
3Can be by Mg (OH)
2ZnO and TiO
2After the mixed in proportion also refinement, make after 1.5～4 hours 1080～1130 ℃ of following precalcinings; And Mg
(2-y)Zn
ySiO
4Can be by Mg (OH)
2, ZnO and SiO
2After the mixed in proportion also refinement, under 1140～1180 ℃, this mixture of precalcining made after 1.5～4 hours.With giving main piece and the secondary material etc. of burning that pre-burning is handled, mix in proportion, after ball milling refinement and drying, promptly get the low Jie's thermally stable ceramic media material of high frequency, its average grain diameter generally is controlled between 0.7～1.4 micron, preferably is controlled between 0.9～1.2 micron.
On the other hand, another object of the present invention provides the low Jie's thermally stable ceramic media material multiple-layer sheet ceramic capacitor (MLCC) of the above-mentioned high frequency of a kind of employing.
This MLCC adopts following structure usually: have a plurality of dielectric layers and the alternately laminated potsherd of a plurality of internal electrode, in the both ends of the surface of potsherd pair of external electrodes being set is connected with internal electrode, internal electrode is made of silver (Ag)-palladium (Pd) alloy, and outer electrode is made of silver (Ag) metal or silver (Ag) alloy.
The manufacture method of MLCC of the present invention can adopt following step:
(1) the low Jie's thermally stable ceramic media material of described high frequency and organic bond (account for dielectric material 45～55%), solvent (account for dielectric material 40～50%) are mixed in proportion, refinement is even, the formation slurry;
(2) slurry that step (1) is made adopts traditional casting technique to make diaphragm, adopt screen printing technique electrode in printed silver (Ag)-palladium (Pd) on film, and alternately laminated have the medium diaphragm of internal electrode and not with in the medium diaphragm of electrode, the storied bad sheet of cambium layer, technology such as repressed cutting forms the green compact capacitor chip again;
(3) chip that step (2) is made is at predetermined sintering temperature, and sintering temperature preferably is controlled at 1100-1140 ℃, thereby obtains the multiple-layer sheet ceramic capacitor sheet;
(4) the multiple-layer sheet ceramic capacitor sheet that step (3) is sintered is handled through surface finish, pair of external electrodes is sealed up at two ends at sheet, outer electrode is connected with internal electrode, heat treatment external electrode in 700-900 ℃ of temperature range, after electroplating processes, can obtain multiple-layer sheet ceramic capacitor.
Certainly, the manufacturing of MLCC of the present invention also can be adopted additive method.
High frequency low permittivity ceramic dielectric material of the present invention is irreplaceable aspect manufacturing low capacity, high-precision high-frequency ceramic capacitor (MLCC).Adopt the MLCC of ceramic medium material of the present invention to have good frequency characteristic and dielectric property, dielectric constant is roughly in the scope of 10-20, has higher reliability, meet the COG characteristic, and the more common high-frequency dielectric ceramic dielectric material of homogeneity of product is good, and reliability and shooting straight satisfies the higher frequency section and uses, dimensions can be 0201,0402,0603,0805,1206,1812 etc., the minimum 0.1PF that accomplishes of nominal capacity.
Embodiment
Embodiment 1
With purity is raw material more than 99.5, with 0.999 mole of Mg (OH)
2, 0.001 mole of ZnO and 1 mole of TiO
2Mixing ratio, ball milling mixes, and in this mixture of 1080～1130 ℃ of temperature precalcinings 2.5 hours, promptly the winner burnt piece metatitanic acid zinc-magnesium Mg
(1-x)Zn
xTiO
3(x=0.001).
With purity is raw material more than 99.5, with 1.999 moles of Mg (OH)
2, 0.001 mole of ZnO and 1 mole of SiO
2Mixing ratio, ball milling mixes, and in this mixture of 1140～1180 ℃ of temperature precalcinings 2.5 hours, promptly the winner burnt piece Magnesium zinc silicate Mg
(2-y)Zn
ySiO
4(y=0.001).
Then, in principal component, add auxiliary element by predetermined ratio, as shown in table 1.Porcelain is made in manufacture of materials technological process routinely; Then, the making flow process of pressing chip MLCC again adds organic bond and ethanol equal solvent, thereby formation slurry, slurry stream is made into the diaphragm of 20 micron thickness, electrode in printed silver on diaphragm (Ag)-palladium (Pd), the alternately laminated required number of plies, form the green compact capacitor chip, then at 280～400 ℃ of heat-treated green compact capacitor chips, to get rid of organic bond and solvent, at 1100-1140 ℃ of temperature sintering capacitor chip, then, handle through surface finish, seal up pair of outer silver (Ag) electrode again at the two ends of sheet, outer electrode is connected, heat treatment external electrode in 700-900 ℃ of temperature range with internal electrode, through electroplating processes, can obtain multiple-layer sheet ceramic capacitor again.
At room temperature, utilize HP4278, test capacitors capacity under 1MHz, 1.0V (AC); Utilize the SF2512 machine that insulate fast, apply the DC rated voltage 10 seconds of 100V, the test insulation resistance; Utilize high-low temperature chamber, between-55～+ 125 ℃, the test temperature coefficient of permittivity; Utilize HP4991A test capacitors frequency characteristic etc., test result sees Table 2.
Table 1
Table 2
| The invention material | Dielectric constant | Dielectric loss DF (* 10 -4) | Temperature coefficient (PPM/ ℃) | Insulation resistance (Ω) |
| 1 | 13.5 | 2 | 10 | >10 11 |
| 2 | 14.0 | 1.3 | 11 | >10 11 |
| 3 | 15.0 | 1.5 | 12 | >10 11 |
| 4 | 15.3 | 1.8 | 10 | >10 11 |
| 5 | 15.8 | 1.2 | 11 | >10 11 |
| 6 | 16.9 | 2 | 10 | >10 11 |
| 7 | 15.0 | 2 | 12 | >10 11 |
| 8 | 14.8 | 1.5 | 11 | >10 11 |
| 9 | 15.2 | 1.8 | 11 | >10 11 |
| 10 | 15.2 | 2.0 | 8 | >10 11 |
| 11 | 15.3 | 1.5 | 7 | >10 11 |
| 12 | 15.2 | 1.4 | 10 | >10 11 |
From table 2, can see, not only satisfy the COG characteristic of EIA standard, and show the good frequency characteristic of high insulation resistance according to multiple-layer sheet ceramic capacitor of the present invention.Be in particular in: IR 10
11Ω, dielectric constant is about 13～17, dielectric loss DF＜2 * 10
-4Between-55～+ 125 ℃, temperature coefficient of permittivity TCC is 0 ± 30ppm/ ℃.
Embodiment 2
With purity is raw material more than 99.5, with 0.999 mole of Mg (OH)
2, 0.001 mole of ZnO and 1 mole of TiO
2Mixing ratio, ball milling mixes, and in this mixture of 1080～1130 ℃ of temperature precalcinings 2.5 hours, promptly the winner burnt piece metatitanic acid zinc-magnesium Mg
(1-x)Zn
xTiO
3(x=0.001).
With purity is raw material more than 99.5, with 1.999 moles of Mg (OH)
2, 0.001 mole of ZnO and 1 mole of SiO
2Mixing ratio, ball milling mixes, and in this mixture of 1140～1180 ℃ of temperature precalcinings 2.5 hours, promptly the winner burnt piece Magnesium zinc silicate Mg
(2-y)Zn
ySiO
4(y=0.001).
Purity is the raw material more than 99.5, mixes ZnO and H by predetermined ratio
3BO
3, ball milling is even, and this mixture of precalcining is 2.5 hours then, obtains uniform auxiliary element ZnO and B2O3 mixture thus.
Add auxiliary element by predetermined ratio in principal component then, as shown in table 3, by the method Computer-Assisted Design, Manufacture And Test of example 1, the multiple-layer sheet ceramic capacitor test result sees Table 4.
Table 3
Table 4
| The invention material | Dielectric constant | Dielectric loss DF (* 10 -4) | Temperature coefficient (PPM/ ℃) | Insulation resistance (Ω) |
| 13 | 14.0 | 1.3 | 9 | >10 11 |
| 14 | 14.1 | 1.2 | 12 | >10 11 |
| 15 | 14.8 | 1.7 | 11 | >10 11 |
| 16 | 15.0 | 1.5 | 13 | >10 11 |
| 17 | 15.7 | 1.8 | 12 | >10 11 |
| 18 | 16.0 | 2 | 15 | >10 11 |
From table 4, can see, not only satisfy the COG characteristic of EIA standard, and show the good frequency characteristic of high insulation resistance according to multiple-layer sheet ceramic capacitor of the present invention.Be in particular in: IR 10
11Ω, dielectric constant is about 14～16, dielectric loss DF＜2 * 10
-4, between-55～+ 125 ℃, temperature coefficient of permittivity TCC is 0 ± 30ppm/ ℃.
Embodiment 3
Purity is the raw material more than 99.5, with 0.995 mole of Mg (OH)
2, 0.005 mole of ZnO and 1 mole of TiO
2Mixing ratio, ball milling mixes, and in this mixture of 1080～1130 ℃ of temperature precalcinings 2.5 hours, promptly the winner burnt piece metatitanic acid zinc-magnesium Mg
(1-x)Zn
xTiO
3(x=0.005).
Purity is the raw material more than 99.5, with 1.98 moles of Mg (OH)
2, 0.02 mole of ZnO and 1 mole of SiO
2Mixing ratio, ball milling mixes, and in this mixture of 1140～1180 ℃ of temperature precalcinings 2.5 hours, promptly the winner burnt piece Magnesium zinc silicate Mg
(2-y)Zn
ySiO
4(y=0.02).
Purity is the raw material more than 99.5, mixes ZnO and H by predetermined ratio
3BO
3, ball milling is even, and this mixture of precalcining is 2.5 hours then, obtains uniform auxiliary element ZnO and B2O3 mixture thus.
In principal component, add auxiliary element by predetermined ratio then, as shown in table 5, by the method Computer-Assisted Design, Manufacture And Test of example 1, in multiple-layer sheet ceramic capacitor test result such as the table 6.
Table 5
Table 6
| The invention material | Dielectric constant | Dielectric loss DF (* 10 -4) | Temperature coefficient (PPM/ ℃) | Insulation resistance (Ω) |
| 19 | 13.7 | 1.5 | 10 | >10 11 |
| 20 | 14.1 | 1.1 | 9 | >10 11 |
| 21 | 14.8 | 1.8 | 10 | >10 11 |
| 22 | 15.0 | 1.7 | 11 | >10 11 |
| 23 | 15.7 | 1.6 | 14 | >10 11 |
| 24 | 16.6 | 1.9 | 13 | >10 11 |
From table 6, can see, not only satisfy the COG characteristic of EIA standard, and show the good frequency characteristic of high insulation resistance according to multiple-layer sheet ceramic capacitor of the present invention.Be in particular in: IR 10
11Ω, dielectric constant is about 13～17, dielectric loss DF＜2 * 10
-4, between-55～+ 125 ℃, temperature coefficient of permittivity TCC is 0 ± 30ppm/ ℃.
Claims (10)
1. a high frequency hangs down Jie's thermally stable ceramic media material, and this ceramic medium material comprises principal component and auxiliary element; By mole percentage, its principal component is 47～56% Mg
(1-x)Zn
xTiO
3With 20～27% Mg
(2-y)Zn
ySiO
4, wherein, 0.001≤x≤0.005,0.001≤y≤0.02; Its auxiliary element is 10～15% ZnO, 3.0～7.0% Al
2O
3With 2.0～6.0% SrO.
2. ceramic medium material as claimed in claim 1 is characterized in that, by mole percentage, the auxiliary element of described ceramic medium material also comprises 1.0～2.5% B
2O
3With 0.5～2.0% Nd
2O
5
3. ceramic medium material as claimed in claim 1 or 2 is characterized in that, by mole percentage, the auxiliary element of described ceramic medium material also comprises 0.1～0.5% MnO
2With 0.1～0.4% Co
3O
4
4. ceramic medium material as claimed in claim 3 is characterized in that, by mole percentage, the auxiliary element of described ceramic medium material also comprise 0.1～1.0%, be selected from K
2O, Fe
2O
3, CeO
2With one or more the material among the SnO.
5. ceramic medium material as claimed in claim 1 or 2 is characterized in that, described Mg
(1-x)Zn
xTiO
3Be by Mg (OH)
2ZnO and TiO
2After mixed, the refinement, make 1080～1180 ℃ of following precalcinings.
6. ceramic medium material as claimed in claim 1 or 2 is characterized in that, described Mg
(2-y)Zn
ySiO
4Be by Mg (OH)
2, ZnO and SiO
2After mixed, the refinement, make 1080～1180 ℃ of following precalcinings.
7. ceramic medium material as claimed in claim 1 or 2 is characterized in that the average grain diameter of described ceramic medium material is between 0.7～1.4 micron.
8. multiple-layer sheet ceramic capacitor, this ceramic capacitor comprises that dielectric layer, interior electrode a plurality of and that dielectric layer replaces reach the termination electrode that is connected with interior electrode, it is characterized in that the dielectric layer of described ceramic capacitor adopts and makes as the described ceramic medium material of one of claim 1-7.
9. ceramic capacitor as claimed in claim 8 is characterized in that, the dielectric constant of described ceramic capacitor is 10～20.
10. ceramic capacitor as claimed in claim 8 or 9 is characterized in that, described ceramic capacitor adopts Ag-Pd as interior electrode.
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|---|---|---|---|
| CNB2003101176385A CN100464382C (en) | 2003-12-31 | 2003-12-31 | Zinc-magnesium titanate system ceramic dielectric material and prepared ceramic capacitor |
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|---|---|---|---|
| CNB2003101176385A CN100464382C (en) | 2003-12-31 | 2003-12-31 | Zinc-magnesium titanate system ceramic dielectric material and prepared ceramic capacitor |
Publications (2)
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| CN100464382C true CN100464382C (en) | 2009-02-25 |
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Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100335442C (en) * | 2005-12-23 | 2007-09-05 | 北京科技大学 | Method for preparing zinc titanite based microwave ceramic under low temperature |
| CN101367651B (en) * | 2008-09-26 | 2012-11-21 | 广东风华高新科技股份有限公司 | High-frequency low-temperature sintered ceramics dielectric material and method of manufacturing obtained electrical condenser |
| CN101475371B (en) * | 2009-01-22 | 2013-02-13 | 华南理工大学 | Low temperature sintered ZnO-MgO-TiO2 system microwave ceramic material and preparation thereof |
| CN101786866B (en) | 2009-12-22 | 2012-12-05 | 广东风华高新科技股份有限公司 | Anti-reduction dielectric ceramic material matched with copper inner electrode and sintered under high frequency and low temperature |
| CN102167580A (en) * | 2010-12-23 | 2011-08-31 | 西安科技大学 | Dielectric ceramic for high-frequency section and preparation method thereof |
| CN102992755B (en) * | 2012-12-17 | 2014-08-13 | 北京元六鸿远电子技术有限公司 | Preparation process of MgO-CoO-TiO2 series microwave ceramics dielectric material |
| CN110372347B (en) * | 2018-04-12 | 2021-10-01 | 中国科学院上海硅酸盐研究所 | Low-loss low-dielectric-constant microwave ceramic material and preparation method thereof |
| CN114920302B (en) * | 2022-04-29 | 2023-08-01 | 山东昭文新能源科技有限公司 | Mesoporous multilayer cake-shaped bimetallic oxygen evolution electrocatalyst and preparation method and application thereof |
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| JPH10259055A (en) * | 1997-03-17 | 1998-09-29 | Taiyo Yuden Co Ltd | Dielectric ceramic composition and ceramic condenser |
| CN1212442A (en) * | 1997-09-19 | 1999-03-31 | 广东肇庆风华电子工程开发有限公司 | Low dielectric microwave medium material for medium temp. sintered multilayer ceramic capacitor |
| US5916834A (en) * | 1996-12-27 | 1999-06-29 | Kyocera Corporation | Dielectric ceramics |
| CN1356967A (en) * | 2000-04-21 | 2002-07-03 | 韩国科学技术研究院 | Low temp sinterable and low loss dielectric ceramic compsns. and method thereof |
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2003
- 2003-12-31 CN CNB2003101176385A patent/CN100464382C/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5916834A (en) * | 1996-12-27 | 1999-06-29 | Kyocera Corporation | Dielectric ceramics |
| JPH10259055A (en) * | 1997-03-17 | 1998-09-29 | Taiyo Yuden Co Ltd | Dielectric ceramic composition and ceramic condenser |
| CN1212442A (en) * | 1997-09-19 | 1999-03-31 | 广东肇庆风华电子工程开发有限公司 | Low dielectric microwave medium material for medium temp. sintered multilayer ceramic capacitor |
| CN1356967A (en) * | 2000-04-21 | 2002-07-03 | 韩国科学技术研究院 | Low temp sinterable and low loss dielectric ceramic compsns. and method thereof |
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