CN103992107A - Low-loss multilayer ceramic capacitor dielectric material - Google Patents
Low-loss multilayer ceramic capacitor dielectric material Download PDFInfo
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- CN103992107A CN103992107A CN201410174177.3A CN201410174177A CN103992107A CN 103992107 A CN103992107 A CN 103992107A CN 201410174177 A CN201410174177 A CN 201410174177A CN 103992107 A CN103992107 A CN 103992107A
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Abstract
The invention discloses a low loss multilayer ceramic capacitor dielectric material using BaTiO3 powder as a basic material, and on the basis of the BaTiO3 powder, the low loss multilayer ceramic capacitor dielectric material also comprises 0.4-0.6% by mass of MnCO3; 0.6-1.8% by mass of (NiO) 1-x (NbO2.5) x (x =0.6-0.8); 0.5-3.0% by mass of CaZrO3 and 4-7% by mass of a glass fluxing agent; the (NiO) 1-x (NbO2.5) x compound is synthesized from NiO and Nb2O5 in the molar ratio of 1-x:x / 2(x =0.6-0.8); by addition of the MnCO3, the ceramic microstructure can be effectively improved, the ceramic dielectric properties can be improved, the dielectric loss can be lowered, and the room temperature loss value can reach below 0.5% (tan delta < 0.5%); the low loss multilayer ceramic capacitor dielectric material has excellent dielectric properties; in the temperature range of-55 to 150 DEG C, the rate of change of capacitance is within +/-15%, and the low loss multilayer ceramic capacitor dielectric material has a high room temperature dielectric constant (-2700).
Description
Technical field
The invention belongs to a kind of ceramic composition that composition is feature of take, be specifically related to a kind of low-loss and there is X8R type medium material for multilayer ceramic capacitors of temperature stability and preparation method thereof
Background technology
Chip multilayer ceramic capacitor (Multilayer Ceramic Capacitor, be called for short MLCC) as base electronic components and parts, except generally using, in industries such as the Military Electronic Equipment such as aerospace, tank electronics, military mobile communication, the control of weapon bullet and military signal monitoring and petroleum prospectings, all there is application quite widely in the products for civilian use such as smart mobile phone, panel computer, broadcast television, mobile communication, home computer, household electrical appliance, surveying instrument, medical facilities and consumer electronics.Barium titanate (BaTiO
3) base temperature-stable MLCC because of its environmental sound, is the focus of research with dielectric material always, use at present maximum be EIA X7R (55 ℃～125 ℃, Δ C/C
25 ℃≤ ± 15%) dielectric material.Develop rapidly along with MLCC, to MLCC with researching and proposing of dielectric material higher requirement, in higher temperature environment, still keep stable dielectric properties, as in summer, temperature in automobile engine nacelle can reach more than 130 ℃, now, X7R type dielectric material is just difficult to meet actual needs.Therefore, and X8R (55 ℃～150 ℃, Δ C/C
25 ℃≤ ± 15%) development of dielectric material for type MLCC, has very important practical significance.
But within the scope of this operation temperature area, though this series ceramic condenser dielectric Capacitance Shift Rate can reach the requirement of X8R, but its room temperature dielectric loss is still more than 1%, affect work-ing life and the stability of components and parts, restrict its application in some aspects, as low-loss EMI filtering laminated ceramic capacitor, therefore reduce the loss of ceramic condenser, become the key that promotes capacitor performance.
Summary of the invention
Object of the present invention, though the Capacitance Shift Rate that is to overcome the ceramic capacitor dielectric of prior art can reach the requirement of X8R, but its dielectric loss is still more than 1%, the defect that can not adapt to some special occasions needs completely, provides a kind of low-loss (tan δ≤0.5%) and has intermediate sintering temperature X8R type medium material for multilayer ceramic capacitors of high dielectric constant and preparation method thereof.This
The present invention is achieved by following technical solution.
A low-loss medium material for multilayer ceramic capacitors, with BaTiO
3powder is base-material, on this basis, and the MnCO that additional mass percent is 0.4～0.6%
3; 0.6～1.8% (NiO)
1-x(NbO
2.5)
x, x=0.6～0.8 wherein; 0.5～3.0% CaZrO
3and 4～7% glass fusing assistant;
Described (NiO)
1-x(NbO
2.5)
xcompound is by NiO and Nb
2o
51-x:x/2 in molar ratio, wherein x=0.6～0.8 is synthetic;
Described CaZrO
3by CaCO
3and ZrO
21: 1 in molar ratio synthetic;
The feed composition of described glass fusing assistant and mass percentage content thereof are: 17% TiO
2, 34% H
3bO
3, 26% ZnO and 23%Bi
2o
3;
The preparation method of this low-loss medium material for multilayer ceramic capacitors, has following steps:
(1) synthetic (NiO)
1-x(NbO
2.5)
xcompound, wherein x=0.6～0.8
By NiO, Nb
2o
51-x:x/2 in molar ratio, x=0.6～0.8 batching wherein, after raw material mixes with deionized water, ball milling is 4 hours, in 120 ℃ of oven dry, 40 order sub-sieves, in 1000 ℃ of calcinings, then secondary ball milling 6 hours, oven dry, 80 order sub-sieves, make (NiO)
1-x(NbO
2.5)
x, x=0.6～0.8 wherein;
(2) synthetic CaZrO
3
By CaCO
3, ZrO
21:1 prepares burden in molar ratio, and after raw material mixes with deionized water, ball milling is 4 hours, in 120 ℃ of oven dry, mistake 40 order sub-sieves, in 1000 ℃ of calcinings, makes CaZrO
3;
(3) synthetic glass fusing assistant
By mass percentage, by 17% TiO
2, 34% H
3bO
3, 26% ZnO and 23% Bi
2o
3fully mixing, melting, quenching, levigate, mistake 200 order sub-sieves, make glass fusing assistant;
(4) with BaTiO
3as base-material, add therein the composition of following mass percent: 0.4～0.6% MnCO
3, 0.6～1.8% (NiO)
1-x(NbO
2.5)
x, x=0.6～0.8 wherein; 0.5～3.0% CaZrO
3with 4～7% glass fusing assistant, after joined raw material is mixed with deionized water, ball milling is 4～8 hours, and after oven dry, adding mass percent is 7% binding agent, crosses 80 order sub-sieve granulations;
(5) the granulation powder of step (4) is pressed into green compact, after binder removal, in 1150 ℃ of sintering, is incubated 3 hours, make low-loss medium material for multilayer ceramic capacitors.
Described MnCO
3preferred addition be 0.5wt%.
The green compact of described step (5) are the disk green compact of Ф 15 * 1～1.3mm.
The green compact of described step (5) were warming up to 550 ℃ of binder removals through 3.5 hours, then through 1 hour, rose to 1150 ℃ of sintering, were incubated 3 hours.
Beneficial effect of the present invention is as follows:
1. medium material for multilayer ceramic capacitors of the present invention is by the interpolation of manganous carbonate, can effectively improve ceramic micro-structure, promote ceramic dielectric properties, reduce dielectric loss, room temperature loss value reaches (tan δ <0.5%) below 0.5%;
2. medium material for multilayer ceramic capacitors of the present invention has good dielectric properties: in-55 ℃～150 ℃ warm areas, rate of change of capacitance, in ± 15%, and has higher room temperature dielectric constant (～2700).
Embodiment
Below with reference to specific embodiment, the present invention is described in further detail.
Embodiment 1
First, use 2.2410g NiO and the 9.3033g Nb of electronic balance weighing analytical pure level (>=99%)
2o
5, mix, using deionized water as ball-milling medium, ball milling in 120 ℃ of oven dry, was crossed 40 order sub-sieves after 4 hours, in 1000 ℃ of calcinings, obtained (NiO)
0.3(NbO
2.5)
0.7compound, then secondary ball milling 6 hours, in 120 ℃ of oven dry, cross 80 order sub-sieves standby;
Again by 22.3291g CaCO
3with 27.5114g ZrO
2mix, using deionized water as ball-milling medium, ball milling in 120 ℃ of oven dry, mistake 40 order sub-sieves, in 1000 ℃ of calcinings, made CaZrO after 4 hours
3;
Again by 17g TiO
2, 34g H
3bO
3, 26g ZnO and 23g Bi
2o
3fully mixing, melting, quenching, levigate, mistake 200 order sub-sieves, make glass fusing assistant.
By 50g BaTiO
3, 0.25g MnCO
3, 0.45g (NiO)
0.3(NbO
2.5)
0.7, 0.5g CaZrO
3after mixing with deionized water with 2.5g glass fusing assistant, ball milling is 4 hours, and the paraffin that after drying, additional mass percent is 7%, crosses 80 order sub-sieve granulations.
Moulding and sintering:
(1) powder after granulation is pressed under 3MPa to the disk green compact of Ф 15 * 1.2mm, through 3.5 hours, is warming up to 550 ℃ of binder removals, then through 1 hour, rise to 1150 ℃ of sintering, be incubated 3 hours, make low-loss medium material for multilayer ceramic capacitors.
In resulting product upper and lower surface, evenly apply silver slurry, through 850 ℃ of burning infiltrations, prepare electrode, make testing sample, test dielectric properties and TC characteristic.
The concrete proportioning raw materials of embodiment 1-5 refers to table 1, and other manufacture craft of embodiment 2-5 is same as embodiment 1.
Table 1
Testing method of the present invention and test set are as follows:
(1) dielectric properties tests (AC test signals: frequency is 1kHz, voltage is 1V)
Use electrical capacity C and the loss tan δ of HEWLETT PACKARD4278A type capacitance tester test sample, and calculate the specific inductivity of sample, calculation formula is:
(2) TC characteristic test
Utilize the high low temperature circulation warm of GZ-ESPEC MPC-710P type case, HM27002 type electrical condenser C-T/V characteristic dedicated tester and HEWLETT PACKARD4278A to test.The electrical capacity of measure sample in warm area-55 ℃～150 ℃, adopts following formula to calculate rate of change of capacitance:
The dielectric properties of embodiment 1-5 disc-shaped medium material for multilayer ceramic capacitors are in Table 2.
Table 2
The present invention is not limited to above-described embodiment, and the variation of a lot of details is possible, but therefore this do not run counter to scope and spirit of the present invention.
Claims (4)
1. a low-loss medium material for multilayer ceramic capacitors, with BaTiO
3powder is base-material, on this basis, and the MnCO that additional mass percent is 0.4～0.6%
3; 0.6～1.8% (NiO)
1-x(NbO
2.5)
x, x=0.6～0.8 wherein; 0.5～3.0% CaZrO
3and 4～7% glass fusing assistant;
Described (NiO)
1-x(NbO
2.5)
xcompound is by NiO and Nb
2o
51-x:x/2 in molar ratio, wherein x=0.6～0.8 is synthetic;
Described CaZrO
3by CaCO
3and ZrO
21: 1 in molar ratio synthetic;
The feed composition of described glass fusing assistant and mass percentage content thereof are: 17% TiO
2, 34% H
3bO
3, 26% ZnO and 23%Bi
2o
3;
The preparation method of this low-loss medium material for multilayer ceramic capacitors, has following steps:
(1) synthetic (NiO)
1-x(NbO
2.5)
xcompound, wherein x=0.6～0.8
By NiO, Nb
2o
51-x:x/2 in molar ratio, x=0.6～0.8 batching wherein, raw material mixes afterwards ball milling 4 hours with deionized water, in 120 ℃ of oven dry, mistake 40 order sub-sieves, in 1000 ℃ of calcinings, make (NiO)
1-x(NbO
2.5)
x, x=0.6～0.8 wherein; Secondary ball milling is 6 hours again, dries, crosses 80 order sub-sieves,
(2) synthetic CaZrO
3
By CaCO
3, ZrO
21:1 prepares burden in molar ratio, and after raw material mixes with deionized water, ball milling is 4 hours, in 120 ℃ of oven dry, mistake 40 order sub-sieves, in 1000 ℃ of calcinings, makes CaZrO
3;
(3) synthetic glass fusing assistant
By mass percentage, by 17% TiO
2, 34% H
3bO
3, 26% ZnO and 23% Bi
2o
3fully mixing, melting, quenching, levigate, mistake 200 order sub-sieves, make glass fusing assistant;
(4) with BaTiO
3as base-material, add therein the composition of following mass percent: 0.4～0.6% MnCO
3, 0.6～1.8% (NiO)
1-x(NbO
2.5)
x, x=0.6～0.8 wherein; 0.5～3.0% CaZrO
3with 4～7% glass fusing assistant, after joined raw material is mixed with deionized water, ball milling is 4～8 hours, and after oven dry, adding mass percent is 7% binding agent, crosses 80 order sub-sieve granulations;
(5) the granulation powder of step (4) is pressed into green compact, after binder removal, in 1150 ℃ of sintering, is incubated 3 hours, make low-loss medium material for multilayer ceramic capacitors.
2. a kind of low-loss medium material for multilayer ceramic capacitors according to claim 1, is characterized in that described MnCO
3preferred addition be 0.5wt%.
3. a kind of low-loss medium material for multilayer ceramic capacitors according to claim 1, is characterized in that, the green compact of described step (5) are the disk green compact of Ф 15 * 1～1.3mm.
4. a kind of low-loss medium material for multilayer ceramic capacitors according to claim 1, is characterized in that, the green compact of described step (5) were warming up to 550 ℃ of binder removals through 3.5 hours, then through 1 hour, rose to 1150 ℃ of sintering, was incubated 3 hours.
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|---|---|---|---|
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|---|---|---|---|
| CN201410174177.3A CN103992107B (en) | 2014-04-28 | 2014-04-28 | A kind of low-loss medium material for multilayer ceramic capacitors |
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|---|---|
| CN103992107A true CN103992107A (en) | 2014-08-20 |
| CN103992107B CN103992107B (en) | 2015-12-02 |
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ID=51306482
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Cited By (6)
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|---|---|---|---|---|
| CN105016727A (en) * | 2015-08-05 | 2015-11-04 | 天津大学 | Method for preparing high-pressure-resisting and multi-layer ceramic capacitor dielectric material |
| CN105084891A (en) * | 2015-08-05 | 2015-11-25 | 天津大学 | Intermediate-temperature sintering unleaded multilayer ceramic capacitor dielectric material and preparing method thereof |
| CN106478092A (en) * | 2015-09-01 | 2017-03-08 | 华北理工大学 | A kind of preparation method of high-intensity high-density calcium zirconate ceramics |
| CN109293353A (en) * | 2018-09-03 | 2019-02-01 | 中国科学院上海硅酸盐研究所 | A kind of unleaded BiFeO of high energy storage density and high energy storage efficiency3Base ferroelectric ceramic material and preparation method thereof |
| CN113248252A (en) * | 2021-06-10 | 2021-08-13 | 天津大学 | Stable dielectric material for MLCC and preparation method thereof |
| CN115141013A (en) * | 2022-07-28 | 2022-10-04 | 电子科技大学 | BaTiO 3 X8R-based ceramic substrate material and preparation method thereof |
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| CN103601486A (en) * | 2013-11-14 | 2014-02-26 | 天津大学 | Medium-temperature sintered multiplayer ceramic capacitor dielectric material and preparation method thereof |
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2014
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105016727A (en) * | 2015-08-05 | 2015-11-04 | 天津大学 | Method for preparing high-pressure-resisting and multi-layer ceramic capacitor dielectric material |
| CN105084891A (en) * | 2015-08-05 | 2015-11-25 | 天津大学 | Intermediate-temperature sintering unleaded multilayer ceramic capacitor dielectric material and preparing method thereof |
| CN106478092A (en) * | 2015-09-01 | 2017-03-08 | 华北理工大学 | A kind of preparation method of high-intensity high-density calcium zirconate ceramics |
| CN106478092B (en) * | 2015-09-01 | 2019-10-29 | 华北理工大学 | A kind of preparation method of high-intensity high-density calcium zirconate ceramics |
| CN109293353A (en) * | 2018-09-03 | 2019-02-01 | 中国科学院上海硅酸盐研究所 | A kind of unleaded BiFeO of high energy storage density and high energy storage efficiency3Base ferroelectric ceramic material and preparation method thereof |
| CN109293353B (en) * | 2018-09-03 | 2021-05-25 | 中国科学院上海硅酸盐研究所 | Lead-free BiFeO with high energy storage density and high energy storage efficiency3Ferroelectric ceramic material and its preparation method |
| CN113248252A (en) * | 2021-06-10 | 2021-08-13 | 天津大学 | Stable dielectric material for MLCC and preparation method thereof |
| CN115141013A (en) * | 2022-07-28 | 2022-10-04 | 电子科技大学 | BaTiO 3 X8R-based ceramic substrate material and preparation method thereof |
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