CN100999410A - Temperature stable type barium titanate system ceramic and its preparation method - Google Patents
Temperature stable type barium titanate system ceramic and its preparation method Download PDFInfo
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- CN100999410A CN100999410A CN 200610130611 CN200610130611A CN100999410A CN 100999410 A CN100999410 A CN 100999410A CN 200610130611 CN200610130611 CN 200610130611 CN 200610130611 A CN200610130611 A CN 200610130611A CN 100999410 A CN100999410 A CN 100999410A
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Abstract
This invention relates to a temperature-stable BaTiO3 system ceramic, its components and raw materials for the percentage of weight: BaTiO3 55-85%, P frit 10-45%, Nb2O5 0.2-1.0%, CoCO3 0 - 0.5%, CeO2 0-0 .8%, MgO 0.3 - 1.2%, Bi2O3 3-4%; P frit described is Pb (Ti1 - xSnx) O3, where x = 0.2 to 0.8. Preparation methods include: (a) Preparation of frit; (2) Preparation of BaTiO3 system ceramics, at 1130 ~ 1160 deg. The invention provides a BaTiO3 composite materials that can work in the harshest conditions (-55 to +190 C), high reliability, high dielectric constant. It is in particular suit for electronic equipment working under adverse conditions (-55 to +190 C), such as spacecraft, satellite missiles, aircraft, tanks and civilian VLSI, automobile air bags and anti-shock system of electronic control devices and other applications .
Description
Technical field
The invention relates to the composition is ceramic composition of feature and preparation method thereof, especially about barium titanate ceramics and preparation method thereof.
Background technology
Barium titanate ceramics need high specific inductivity, and little velocity of variation is arranged in operating temperature range.Reaching this purpose method is to use multiple doping agent to BaTiO
3Modification, BaTiO
3System's existing piezoelectricity of pottery has ferroelectricity again, is used widely because of its dielectric coefficient is high.BaTiO
3System's pottery is used for the existing nearly 50 years history of high dielectric container, and the research of this system's porcelain and application are deepened continuously and develop.People such as B.Hennings and G.Rosenstein is to adding Nb
5+Co
2+BaTiO
3The brilliant heart-brilliant the shell structure of pottery has carried out detailed report, and Youichi Enomoto and Akihiko Yamaji study the BaTiO3 that mixes Dy.People such as Wu Shunhua have studied interpolation Nb
5+Co
2+BaTiO
3. ferroelectric ceramic(s), the influence of glass to this system's pottery: Nb has been discussed
5+Co
2+And the Bi in the glass
3+Enter lattice and form the brilliant heart-brilliant shell structure.Glass mainly concentrates on crystal boundary, reduces sintering temperature to middle temperature, makes specific inductivity-temperature curve become smooth.Within the specific limits, but with the increase of Nb/Co atomic ratio, specific inductivity descends, and Curie shifts to high temperature in the peak.These materials satisfy X7R characteristic (that is, satisfying Δ ε/ε≤0 ± 15% in-55～+ 125 ℃ of temperature ranges) usually.These system's potteries generally have fine crystalline structure, i.e. nucleocapsid structure, and its main technique factor is control sintering temperature and soaking time, the main ratio of various concentration of dopant and alms giver/be subjected to.Problem and shortcoming that the above X7R system stupalith exists are: operating temperature range is narrow, especially can not satisfy the requirement of aspects such as growing electronics, communication, radar, automobile in the high temperature direction.The present inventor had once studied and had been operated in 150 ℃ BaTiO
3Material.Although in the world the X7R stupalith has been carried out a large amount of research, but because the electrology characteristic of X7R stupalith self makes that dielectric parameter can be undergone mutation the performance rapid deterioration when temperature rises to more than 125 ℃, circuitry was lost efficacy, thereby cause the generation of accident.In order to adapt to the application under the rapid changing environment of specific high temperature, must carry out big change to existing stupalith system, make its dielectric properties particularly temperature stability reach a new height (improve the upper limit use temperature reach 190 ℃), the key issue that the present invention that Here it is will solve.Another advantage of porcelain of the present invention is the specific inductivity height, (up to 2300) and this type porcelain specific inductivity of present inventor's development in the past is 1300.
Summary of the invention
The objective of the invention is to overcome the deficiencies in the prior art, a kind of BaTiO that can be operated in (55～+ 190 ℃) under the exceedingly odious condition is provided
3Matrix material has high reliability, and high-k is to satisfy under the limiting condition particular requirement to electronic devices and components.
The present invention is achieved by following technical solution.
A kind of temperature-stable BaTiO
3System's pottery, its component and raw material weight per-cent thereof are BaTiO
355--85%, frit 10-45%, Nb
2O
50.2-1.0%, CoCO
30-0.5%, CeO
20-0.8%, MgO 0.3-1.2%, Bi
2O
33-4%: described frit is Pb (Ti
1-xSn
x) O
3X=0.2～0.8 wherein.
A kind of temperature-stable BaTiO
3The preparation method of system's pottery comprises the steps:
(1) preparation frit: press Pb (Ti
1-xSn
x) O
3, wherein prescription is calculated in x=0.2～0.8, prepares burden, and ball milling 3-4.5 hour, in 120 ℃ of dryings, crosses 120-250 hole/cm
2Sub-sieve is heated to 880 ℃ of-920 ℃ of pre-burnings by the temperature rise rate of 10 ℃/min, is incubated 1.5-2 hour, makes molten fast;
(2) preparation BaTiO
3System's pottery: BaTiO by weight percentage
355-85%, frit 10-45%, Nb
2O
50.2-1.0%, CoCO
30-0.5%, CeO
20-0.8%, MgO0.3-1.2%, Bi
2O
3The 3-4% batching, ball milling 8 hours in 120 ℃ of dryings, is crossed 250 holes/cm
2Sub-sieve adds the granulation of 6 ~ 7wt% paraffin, suppresses green compact under 80Mpa pressure, is heated to 500 ℃, is heated to 1130 ~ 1160 ℃ by the temperature rise rate of 3 ~ 4 ℃/min again and burns till by the temperature rise rate of 3 ℃/min earlier, is incubated 4 hours, makes ceramic dielectic after the cooling.
Described step (1) adopts electronic ceramics solid phase method technology.
The green compact of described step (2) compacting are circular.
The invention has the beneficial effects as follows, a kind of BaTiO that can be operated in (55～+ 190 ℃) under the exceedingly odious condition is provided
3Matrix material has high reliability, high-k, satisfied under the limiting condition particular requirement to electronic devices and components.
Description of drawings
Fig. 1: be the specific inductivity graphic representation under the differing temps;
Fig. 2: be the rate of change curve chart under the differing temps.
Embodiment
The present invention is described in further detail below in conjunction with embodiment and accompanying drawing.
The Curie temperature that the present invention is based on submicron BaTiO3 material is removable, the mechanism of broadening, raising, suitably add additive, adopt rational technology, produce ultrahigh-temperature (190 ℃) stable form BaTiO3 matrix material, satisfy under the limiting condition particular requirement electronic devices and components.
BaTiO3 of the present invention is a ceramic dielectic, in a lower sintering range (1130 ~ 1160 ℃), its DIELECTRIC CONSTANT is greater than 1230, and dielectric loss is little, and has good thermostability (satisfying the requirement of Δ ε/ε≤0 ± 15% in-55～+ 190 ℃ of temperature ranges).In the sintering process sintering temperature is controlled in the comparatively accurate scope, ceramic dielectic will obtain extremely good performance.
The components and parts made of X7R stupalith can only be operated in-55～+ 125 ℃ of temperature ranges BaTiO of the present invention in the past
3The components and parts that matrix material is made can be operated in (55～+ 190 ℃) under the exceedingly odious working conditions.
It is raw material that the present invention adopts chemical pure or analytical pure, and specific embodiment is as follows:
Embodiment one:
(1) preparation frit:
PbO?65.95g?TiO
2?11.80g?SnO
2?22.25g；
By the prescription weighing, with zirconium white ask add the deionized water mixing and ball milling after 4 hours in 120 ℃ of dryings, cross 200 holes/cm then
2Sub-sieve is put into the sintering oven pre-burning, is heated to 900 ℃ by the temperature rise rate of 10 ℃/min, is incubated 1.5 hours, makes frit;
(2) preparation BaTiO
3System's pottery:
BaTiO
357.6g, frit 28.524g, Nb
2O
5O.6243g, CoCO
30.1896g, CeO
20.2919g, MgO0.66g, Bi
2O
34.358g;
By the prescription weighing, add deionized water ball milling 10 hours in 120 ℃ of dryings with zirconia ball, cross 250 holes/cm then
2Sub-sieve, add the granulation of 6 ~ 7wt% paraffin, under 80Mpa pressure, be pressed into the disk green compact of the thick 1.2mm of diameter 15mm, put into the sintering kiln roasting at last, temperature rise rate by 3 ℃/min is heated to 500 ℃ earlier, temperature rise rate by 4 ℃/min is heated to 1160 ℃ again, is incubated 4 hours, makes ceramic dielectic after the cooling.
Embodiment two:
(1) preparation frit:
PbO?63.93g?TiO
28.01g?SnO
2?28.06g
By the prescription weighing, with zirconium white ask add the deionized water mixing and ball milling after 4.5 hours in 120 ℃ of dryings, cross 250 holes/cm then
2Sub-sieve is put into the sintering oven pre-burning, is heated to 920 ℃ by the temperature rise rate of 10 ℃/min, is incubated 2 hours, makes molten fast;
(2) preparation BaTiO
3System's pottery:
BaTiO
357.6g, frit 28.524g, Nb
2O
50.6243g, CoCO
30.1896g, CeO
2O.2919g, MgO 0.66g, Bi
2O
34.358g
By the prescription weighing, add deionized water ball milling 10 hours in 120 ℃ of dryings with zirconia ball, cross 250 holes/cm then
2Sub-sieve, add the granulation of 6 ~ 7wt% paraffin, under 80Mpa pressure, be pressed into the thick 1.2mm disk of diameter 15mm green compact, put into the sintering kiln roasting at last, temperature rise rate by 3 ℃/min is heated to 500 ℃ earlier, temperature rise rate by 4 ℃/min is heated to 1160 ℃ again, is incubated 4 hours, makes ceramic dielectic after the cooling.
Embodiment three:
(1) preparation frit:
PbO65.95g?TiO
211.80g?SnO
222.25g
By the prescription weighing, with zirconium white ask add the deionized water mixing and ball milling after 4.5 hours in 120 ℃ of dryings, cross 250 holes/cm then
2Sub-sieve is put into the sintering oven pre-burning, is heated to 920 ℃ by the temperature rise rate of 10 ℃/min, is incubated 2 hours, makes molten fast;
(2) preparation BaTiO
3System's pottery:
BaTiO
357.6g, frit 28.524g, Nb
2O
50.6243g, CoCO
30.1896g, CeO
20.2919g, MgO0.66g, Bi
2O
36.045g
By the prescription weighing, add deionized water ball milling 10 hours in 120 ℃ of dryings with zirconia ball, cross 250 holes/cm then
2Sub-sieve, add the granulation of 6 ~ 7wt% paraffin, under 80Mpa pressure, be pressed into the thick 1.2mm disk of diameter 15mm green compact, put into the sintering kiln roasting at last, temperature rise rate by 3 ℃/min is heated to 500 ℃ earlier, temperature rise rate by 4 ℃/min is heated to 1130 ℃ again, is incubated 4 hours, makes ceramic dielectic after the cooling.
In the above-mentioned example, two kinds of frit prescriptions and two kinds of Bi have been provided respectively
2O
3Content.Frit plays the effect of moving with broadening Curie peak, Bi
2O
3Influence sintering temperature and specific inductivity, thereby the present invention is met the temperature-stable BaTiO of different sintering temperatures, differing dielectric constant
3System's pottery series.
Burned ceramic dielectic is coated with silver, solder taul, survey the relative permittivity ε of its electrical capacity C (pf) and calculation medium with Agilent 4285A LCR Meter under 1 KHz, 1kHz is down with the temperature coefficient of permittivity of 4278RLC electric bridge and GZ-ESPEC MC-710F type thermostat container test specimen.
Provided test result of the present invention in the accompanying drawing, system's specific inductivity is (Fig. 1) in the 2000-2100 scope, and temperature factor remains on 15% with interior (Fig. 2) under the temperature condition (55～+ 190 ℃) requiring.Based on above characteristics, the electrical condenser that the present invention makes can be used as high frequency filter, resonator, duplexer, polyrod antenna and Medium Wave Guide etc. in high-end electronic devices, obviously improved the job stability of electronics under mal-condition.
Though the present invention discloses as above with preferred embodiment, it is not in order to limit the present invention; Any those skilled in the art without departing from the spirit and scope of the present invention, can carry out various changes and retouching to described invention, therefore, protection scope of the present invention should look the application claim limited is as the criterion.
BaTiO3 matrix material of the present invention is used for wave filter, duplexer, anti-electromagnetic interference (EMI) filter condenser, components and parts of using always in the laminated ceramic capacitor electronic machines such as (MLCC) and the filtering in the communication system, signal transmitting and receiving, signal storage, the manufacturing of components and parts such as energy storage, be particularly useful for requiring electronic system to be equipped in (55～+ 190 ℃) works better under the various mal-conditions, has high reliability, as spacecraft, satellite missile, aircraft, tank and civilian super large-scale integration, the Application Areass such as electronic controls of automotive airbag and shock resistance system etc.
Claims (4)
1. temperature-stable BaTiO
3System's pottery is characterized in that, its component and raw material weight per-cent thereof are BaTiO
355-85%, frit 10-45%, Nb
2O
50.2-1.0%, CoCO
30-0.5%, CeO
20-0.8%, MgO 0.3-1.2%, Bi
2O
33-4%; Described frit is Pb (Ti
1-xSn
x) O
3, x=0.2～0.8 wherein.
2. the temperature-stable BaTiO of a claim 1
3The preparation method of system's pottery is characterized in that, comprises the steps:
(1) preparation frit: press Pb (Ti
1-xSn
x) O
3, wherein prescription is calculated in x=0.2～0.8, prepares burden, and ball milling 3-4.5 hour, in 120 ℃ of dryings, crosses 120-250 hole/cm
2Sub-sieve is heated to 880 ℃ of-920 ℃ of pre-burnings by the temperature rise rate of 10 ℃/min, is incubated 1.5-2 hour, makes molten fast;
(2) preparation BaTiO
3System's pottery: BaTiO by weight percentage
355-85%, frit 10-45%, Nb
2O
50.2-1.0%, CoCO
30-0.5%, CeO
20-0.8%, MgO 0.3-1.2%, Bi
2O
3The 3-4% batching, ball milling 8 hours in 120 ℃ of dryings, is crossed 250 holes/cm
2Sub-sieve adds the granulation of 6 ~ 7wt% paraffin, suppresses green compact under 80Mpa pressure, and the temperature rise rate by 3 ℃/min is heated to 500 ℃ earlier, is heated to 1130 ~ 1160 ℃ by the temperature rise rate of 3 ~ 4 ℃/min again and burns till, and is incubated 4 hours, makes ceramic dielectic after the cooling.
3. according to the manufacture method of claim 2, it is characterized in that described step (1) adopts electronic ceramics solid phase method technology.
4. according to the manufacture method of claim 2, it is characterized in that the green compact of described step (2) compacting are circular.
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|---|---|---|---|
| CNB2006101306113A CN100415682C (en) | 2006-12-27 | 2006-12-27 | Temperature stable type barium titanate system ceramic and its preparation method |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006101306113A CN100415682C (en) | 2006-12-27 | 2006-12-27 | Temperature stable type barium titanate system ceramic and its preparation method |
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| Publication Number | Publication Date |
|---|---|
| CN100999410A true CN100999410A (en) | 2007-07-18 |
| CN100415682C CN100415682C (en) | 2008-09-03 |
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|---|---|---|---|
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108752009A (en) * | 2018-04-27 | 2018-11-06 | 湖南省美程陶瓷科技有限公司 | A kind of sintering method of electronic ceramics |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1623955A (en) * | 2004-11-16 | 2005-06-08 | 清华大学 | Ceramic material of middle-low temp. sintered temp stable type multirayer ceramic capacitor |
| CN100452257C (en) * | 2005-07-15 | 2009-01-14 | 天津大学 | Barium titanate ceramic capacitor medium and preparing method thereof |
| CN1304328C (en) * | 2005-10-13 | 2007-03-14 | 浙江大学 | Temperature-stabilized electronic ceramic material with ultra-high dielectric constant and production thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108752009A (en) * | 2018-04-27 | 2018-11-06 | 湖南省美程陶瓷科技有限公司 | A kind of sintering method of electronic ceramics |
| CN108752009B (en) * | 2018-04-27 | 2023-04-14 | 湖南省美程陶瓷科技有限公司 | Sintering method of electronic ceramic |
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