CN103936410B - Manganous carbonate doped high temperature stable form barium phthalate base dielectric material - Google Patents
Manganous carbonate doped high temperature stable form barium phthalate base dielectric material Download PDFInfo
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- CN103936410B CN103936410B CN201410133060.0A CN201410133060A CN103936410B CN 103936410 B CN103936410 B CN 103936410B CN 201410133060 A CN201410133060 A CN 201410133060A CN 103936410 B CN103936410 B CN 103936410B
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- manganous carbonate
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Abstract
The invention discloses a kind of preparation method of manganous carbonate doped high temperature stable form barium phthalate base dielectric material, first by Na
2cO
3, Bi
2o
3, TiO
2by mole% 1:1:4 batching, obtained Na after calcining
0.5bi
0.5tiO
3solid particulate; Again by Na
0.5bi
0.5tiO
3, BaTiO
3, Nb
2o
51:6.2:0.17 batching in mass ratio, in 1000 DEG C of pre-burnings, obtained frit; Again additional mass percent be 5% glass powder and mass percent be the manganous carbonate of 4 ~ 4.5%, ball milling post-drying; Again after granulation, shaping, de-waxing, in 1130 ~ 1160 DEG C of sintering, obtained manganous carbonate doped high temperature stable form barium phthalate base dielectric material.The powder component that the present invention obtains is homogeneous, and process is pollution-free; DIELECTRIC CONSTANT ε
r>=900, rate of change of capacitance Δ C/C within the scope of 100 DEG C ~ 310 DEG C
100dEG C≤± 15%.
Description
Technical field
The invention belongs to a kind of take composition as the ceramic composition of feature, particularly a kind of MnCO
3doped high temperature degree stable form BaTiO
3based dielectric material and preparation method thereof.
Background technology
Along with the high speed development of multiple mobile electronic device such as notebook computer, mobile telephone, digital camera, automotive electronics etc., chip electronic component progressively instead of conventional wire type electronic component.Chip multilayer ceramic capacitor (MLCC) is the maximum chip components and parts of current turnout, sales volume, and it electrode materials and ceramic body is replaced parallel connection with multilayer be superimposed together, and burn till an entirety simultaneously.
In recent years, the development trend of MLCC dielectric material is improve its over-all properties always, under the prerequisite ensureing its high reliability, expand its use temperature scope, successively occur meeting EIA(ElectronicIndustriesAssociate, International Electro TIA) X7R(operating temperature range is-55 ~ 125 DEG C), X8R(operating temperature range is-55 ~ 150 DEG C), X9R(operating temperature range is-55 ~ 200 DEG C) dielectric material of standard.But in fields such as aerospace, geological prospecting, automotive electronics, the environment for use of MLCC is harsher.In some field, the research of the dielectric material that specified temp section uses also has meaning.
Manganous carbonate doping BaTiO provided by the invention
3base dielectric cording has excellent dielectric properties (ε
r>=900, Δ C/C
100dEG C≤± 15%, 100 DEG C ~ 310 DEG C), its sintering temperature 1130 DEG C ~ 1160 DEG C is the very promising high-temperature stable medium material for multilayer ceramic capacitors of one.
Summary of the invention
Object of the present invention, for adapting to use under harsher temperature environment, provides the preparation method of high-temperature stable (100 DEG C-310 DEG C) ceramic capacitor dielectric material that a kind of Capacitance Shift Rate is less, operating temperature range is wider.
The present invention is achieved by following technical solution.
A preparation method for manganous carbonate doped high temperature stable form barium phthalate base dielectric material, step is as follows:
(1) by Na
2cO
3, Bi
2o
3, TiO
2by mole% 1:1:4 batching, with deionized water mixing and ball milling 4h post-drying, in 800 DEG C of calcinings, obtained Na
0.5bi
0.5tiO
3solid particulate;
(2) by Na
0.5bi
0.5tiO
3, BaTiO
3, Nb
2o
51:6.2:0.17 batching in mass ratio, with deionized water mixing and ball milling 4h post-drying, in 1000 DEG C of pre-burnings, obtained frit;
(3) be the glass powder of 5% to additional mass percent in step (2) pre-burning gained frit, and mass percent is the manganous carbonate of 4 ~ 4.5%, ball milling 2h in deionized water, dries;
(4) in the powder after step (3) is dried, additional mass percent is the paraffin granulation of 5 ~ 8%, then crosses 1000 holes/cm
3sub-sieve, then be pressed into green compact, forming pressure 6 ~ 10MPa;
(5) use the mode of burying material to sinter on green compact obtained for step (4), be first warming up to 550 DEG C of de-waxings through 3 ~ 4h, then rise to 1130 ~ 1160 DEG C of sintering through 1 ~ 3h, insulation 1h, obtained manganous carbonate doped high temperature stable form barium phthalate base dielectric material.
Described step (1), (2), (3) all use QM-3SP4 planetary ball mill to carry out ball milling, drum's speed of rotation 400 revs/min.
The glass powder composition of described step (3) and mass percentage content thereof are: 20%Bi
2o
3, 30%Pb
3o
4, 30%TiO
2, 20%H
3bO
3.
Described step (4) adopts 769YP-24B type powder compressing machine to be pressed, and uses Φ 20 mould.
The sintering temperature of described step (5) is 1140 DEG C.
Manganous carbonate doping BaTiO provided by the invention
3the preparation method of based dielectric material, its sintering temperature is: 1130 ~ 1160 DEG C, material dielectric constant ε
r>=900, rate of change of capacitance Δ C/C within the scope of 100 DEG C ~ 310 DEG C
100dEG C≤± 15%.It is a kind of high-temperature stable medium material for multilayer ceramic capacitors.In addition, the component that this preparation technology obtains powder is homogeneous, and process is pollution-free.
Embodiment
The present invention is raw materials used all adopts analytical pure raw material, and specific embodiment is as follows.
Embodiment 1:
First by Na
2cO
3, Bi
2o
3, TiO
2prepare burden by matter molar percentage 1:1:4, with deionized water mixing and ball milling, use QM-3SP4 planetary ball mill (drum's speed of rotation 400 revs/min) ball milling 4h post-drying and in 800 DEG C of pre-burnings, obtain Na
0.5bi
0.5tiO
3solid particulate; By Na
0.5bi
0.5tiO
3, BaTiO
3, Nb
2o
51:6.2:0.17 batching in mass ratio, with deionized water mixing and ball milling, uses QM-3SP4 planetary ball mill (drum's speed of rotation 400 revs/min) ball milling 4h post-drying in 1000 DEG C of pre-burnings; In pre-burning gained frit additional mass percent 5% glass powder (glass powder composition and mass percentage content be: 20%Bi
2o
3, 30%Pb
3o
4, 30%TiO
2, 20%H
3bO
3), the manganous carbonate of mass percent 4%, mixing and ball milling in deionized water, uses QM-3SP4 planetary ball mill (drum's speed of rotation 400 revs/min) ball milling 2h, dries.Again gained is dried in powder and add the paraffin granulation that mass percent is 5%, then cross 1000 holes/cm
3sub-sieve, uses Φ 20 mould, on 769YP-24B type powder compressing machine, is pressed into green compact, forming pressure 6MPa.First be warming up to 550 DEG C of de-waxings through 3h during sintering, then rise to 1130 DEG C of sintering through 1.5h, insulation 1h, obtained manganous carbonate doped high temperature stable form barium phthalate base dielectric material.Then, then the upper and lower surface of resulting product is evenly applied silver slurry, prepare electrode through 840 DEG C of burning infiltrations, the ceramic condenser of obtained wide operating temperature range.
Embodiment 2:
First by Na
2cO
3, Bi
2o
3, TiO
2prepare burden by matter molar percentage 1:1:4, with deionized water mixing and ball milling, use QM-3SP4 planetary ball mill (drum's speed of rotation 400 revs/min) ball milling 4h post-drying and in 800 DEG C of pre-burnings, obtain Na
0.5bi
0.5tiO
3solid particulate; By Na
0.5bi
0.5tiO
3, BaTiO
3, Nb
2o
51:6.2:0.17 batching in mass ratio, with deionized water mixing and ball milling, uses QM-3SP4 planetary ball mill (drum's speed of rotation 400 revs/min) ball milling 4h post-drying in 1000 DEG C of pre-burnings; In pre-burning gained frit additional mass percent 5% glass powder (glass powder composition and mass percentage content be: 20%Bi
2o
3, 30%Pb
3o
4, 30%TiO
2, 20%H
3bO
3), the manganous carbonate of mass percent 4.3%, mixing and ball milling in deionized water, uses QM-3SP4 planetary ball mill (drum's speed of rotation 400 revs/min) ball milling 2h, dries.Again gained is dried in powder and add the paraffin granulation that mass percent is 5%, then cross 1000 holes/cm
3sub-sieve, uses Φ 20 mould, on 769YP-24B type powder compressing machine, is pressed into green compact, forming pressure 6MPa.First be warming up to 550 DEG C of de-waxings through 3h during sintering, then rise to 1140 DEG C of sintering through 1.5h, insulation 1h, obtained manganous carbonate doped high temperature stable form barium phthalate base dielectric material.Then, then the upper and lower surface of resulting product is evenly applied silver slurry, prepare electrode through 840 DEG C of burning infiltrations, the ceramic condenser of obtained wide operating temperature range.
Embodiment 3
First by Na
2cO
3, Bi
2o
3, TiO
2prepare burden by matter molar percentage 1:1:4, with deionized water mixing and ball milling, use QM-3SP4 planetary ball mill (drum's speed of rotation 400 revs/min) ball milling 4h post-drying and in 800 DEG C of pre-burnings, obtain Na
0.5bi
0.5tiO
3solid particulate; By Na
0.5bi
0.5tiO
3, BaTiO
3, Nb
2o
51:6.2:0.17 batching in mass ratio, with deionized water mixing and ball milling, uses QM-3SP4 planetary ball mill (drum's speed of rotation 400 revs/min) ball milling 4h post-drying in 1000 DEG C of pre-burnings; In pre-burning gained frit additional mass percent 5% glass powder (glass powder composition and mass percentage content be: 20%Bi
2o
3, 30%Pb
3o
4, 30%TiO
2, 20%H
3bO
3), the manganous carbonate of mass percent 4.5%, mixing and ball milling in deionized water, uses QM-3SP4 planetary ball mill (drum's speed of rotation 400 revs/min) ball milling 2h, dries.Again gained is dried in powder and add the paraffin granulation that mass percent is 5%, then cross 1000 holes/cm
3sub-sieve, uses Φ 20 mould, on 769YP-24B type powder compressing machine, is pressed into green compact, forming pressure 6MPa.First be warming up to 550 DEG C of de-waxings through 3h during sintering, then rise to 1160 DEG C of sintering through 1.5h, insulation 1h, obtained manganous carbonate doped high temperature stable form barium phthalate base dielectric material.Then, then the upper and lower surface of resulting product is evenly applied silver slurry, prepare electrode through 840 DEG C of burning infiltrations, the ceramic condenser of obtained wide operating temperature range.
Testing method of the present invention and test set as follows: (AC test signals: frequency is 1kHz, voltage is 1V).
(1) test of specific inductivity and loss
Use electrical capacity C and the loss tan δ of HEWLETTPACKARD4278A type capacitance tester test sample, and converse the specific inductivity of sample.For wafer capacitance device, conversion relation is as follows:
In formula: C-electrical capacity, unit is pF; D, D are respectively thickness, the diameter of sample, unit cm.
(2) TC characteristic test
Measure sample is in the electrical capacity of warm area 100 DEG C ~ 310 DEG C.Then adopt following formulae discovery volume temperature velocity of variation:
In formula: C1 is the electrical capacity at 100 DEG C, nF; C2 is the electrical capacity of arbitrary temp point in 100 DEG C ~ 310 DEG C warm areas, nF; Δ C/C
100for the relative change rate of electrical capacity.
Experiment utilizes GZ-ESPEK high-low temperature chamber and STH-120 type high-temperature cabinet jointly to create the probe temperature environment of 100 DEG C ~ 310 DEG C, and adopts HM27002 type electrical condenser C-T/V characteristic dedicated tester and HEWLETTPACKARD4278A test display.HM27002 type electrical condenser C-T/V characteristic dedicated tester is set to " interior inclined ", tests from 100 DEG C, finally rise to 310 DEG C, by the electrical capacity of 4278A type capacitance measuring tester measure sample in whole warm area.
Main technologic parameters and the dielectric properties test result thereof of above-described embodiment refer to table 1.
Max| Δ C/C in table 1
20dEG C | the warm area scope of (%) value is 100 DEG C ~ 310 DEG C.
Table 1
Wide operating temperature range medium material for multilayer ceramic capacitors of the present invention, sintering temperature 1130 ~ 1160 DEG C, operating temperature range is 100 DEG C ~ 310 DEG C, and meets following dielectric properties:
Specific inductivity: ε >=900;
Loss: tan δ≤5.0%;
Temperature profile: Δ C/C
100dEG C≤± 15%, 100 DEG C ~ 310 DEG C.
Claims (5)
1. a preparation method for manganous carbonate doped high temperature stable form barium phthalate base dielectric material, step is as follows:
(1) by Na
2cO
3, Bi
2o
3, TiO
2by mole% 1:1:4 batching, with deionized water mixing and ball milling 4h post-drying, in 800 DEG C of calcinings, obtained Na
0.5bi
0.5tiO
3solid particulate;
(2) by Na
0.5bi
0.5tiO
3, BaTiO
3, Nb
2o
51:6.2:0.17 batching in mass ratio, with deionized water mixing and ball milling 4h post-drying, in 1000 DEG C of pre-burnings, obtained frit;
(3) be the glass powder of 5% to additional mass percent in step (2) pre-burning gained frit, and mass percent is the manganous carbonate of 4 ~ 4.5%, ball milling 2h in deionized water, dries;
(4) in the powder after step (3) is dried, additional mass percent is the paraffin granulation of 5 ~ 8%, then crosses 1000 holes/cm
3sub-sieve, then be pressed into green compact, forming pressure 6 ~ 10MPa;
(5) use the mode of burying material to sinter on green compact obtained for step (4), be first warming up to 550 DEG C of de-waxings through 3 ~ 4h, then rise to 1130 ~ 1160 DEG C of sintering through 1 ~ 3h, insulation 1h, obtained manganous carbonate doped high temperature stable form barium phthalate base dielectric material.
2. the preparation method of manganous carbonate doped high temperature stable form barium phthalate base dielectric material according to claim 1, it is characterized in that, described step (1), (2), (3) all use QM-3SP4 planetary ball mill to carry out ball milling, drum's speed of rotation 400 revs/min.
3. the preparation method of manganous carbonate doped high temperature stable form barium phthalate base dielectric material according to claim 1, is characterized in that, the glass powder composition of described step (3) and mass percentage content thereof are: 20%Bi
2o
3, 30%Pb
3o
4, 30%TiO
2, 20%H
3bO
3.
4. the preparation method of manganous carbonate doped high temperature stable form barium phthalate base dielectric material according to claim 1, is characterized in that, described step (4) adopts 769YP-24B type powder compressing machine to be pressed, and uses Φ 20 mould.
5. the preparation method of manganous carbonate doped high temperature stable form barium phthalate base dielectric material according to claim 1, it is characterized in that, the sintering temperature of described step (5) is 1140 DEG C.
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| CN104291811A (en) * | 2014-09-26 | 2015-01-21 | 天津大学 | Preparation method of ceramic capacitor dielectric with high dielectric constant and superwide working temperature |
| CN105036734B (en) * | 2015-06-25 | 2017-08-25 | 武汉理工大学 | High-k X8R type multilayer ceramic capacitor dielectric materials and preparation method thereof |
| 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 |
| CN106938928A (en) * | 2017-03-31 | 2017-07-11 | 天津大学 | A kind of anti-reduction huge dielectric constant low loss, high value ceramic capacitor dielectric material |
| CN107399970A (en) * | 2017-07-13 | 2017-11-28 | 天津大学 | A kind of medium material for multilayer ceramic capacitors with superior insulation characteristics |
| CN114213120B (en) * | 2021-11-29 | 2023-03-07 | 深圳市信维通信股份有限公司 | Dielectric material for small-size MLCC (multilayer ceramic capacitor), preparation method thereof and capacitor |
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| CN101747036B (en) * | 2009-12-22 | 2012-07-04 | 河北理工大学 | Low-frequency dielectric ceramic with low-temperature sintering and ultralow temperature change ratio and preparation method thereof |
| CN102199035B (en) * | 2011-03-22 | 2013-06-26 | 清华大学 | X9r ceramic capacitor dielectric material and preparation method thereof |
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