CN1699275A - Barium strontium titanate base electro-optical composite material and preparation method thereof - Google Patents

Barium strontium titanate base electro-optical composite material and preparation method thereof Download PDF

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CN1699275A
CN1699275A CN 200510025812 CN200510025812A CN1699275A CN 1699275 A CN1699275 A CN 1699275A CN 200510025812 CN200510025812 CN 200510025812 CN 200510025812 A CN200510025812 A CN 200510025812A CN 1699275 A CN1699275 A CN 1699275A
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strontium titanate
barium strontium
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CN100412030C (en
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陈莹
董显林
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Shanghai Institute of Ceramics of CAS
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Shanghai Institute of Ceramics of CAS
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Abstract

The invention relates to a barium strontium titanate base electro-optical composite material and preparation method, wherein the composition of these material being (1-y-z)Ba1-xSrxTiO3+yMe2SiO4+zMO, wherein x=0-0.75, y=5-60 wt%, z=0-30 wt%, y+z=5-60 wt%, the preparation comprises formulating Ba1-xSrxTiO3 and Mg2SiO4 by chemical measuring ratio, ball grinding, discharging, drying, pre-burning, thus obtaining Ba1-xSrxTiO3 and Mg2SiO4 powder, then mixing Me2SiO4 and MO into BSTO powder according to the designed composition, then carrying out ball grinding, drying, granulating, modeling, discharging adhesive, then calcining 2-4h at the furnace temperature of 1250-1350 deg. C, naturally cooling to obtain the needed samples.

Description

A kind of barium strontium titanate base electro-optical composite material and preparation method thereof
Technical field
The present invention relates to a kind of barium strontium titanate base electro-optical composite material and preparation method thereof, belong to the electrooptical material field.
Background technology
Material as phase shifter mainly is ferrite and PIN diode at present, but all there are some bigger shortcomings in they, and for example, the peak power of ferrite phase shifter is big, and transmission speed is restricted; Temperature-compensation circuit unavoidably causes the error in pointing of phased array antenna; Control circuit, compensating circuit not only make phase changer itself bulky, and cause the phased array antenna reliability to reduce; Complex manufacturing technology, production cost is higher.The PIN diode phase shifter is more cheap than ferrite phase shifter, but high insertion loss has limited its use.Therefore, ferrite phase shifter and PIN diode phase shifter all are difficult to satisfy the requirement of modern military technology to lightweight, miniaturization, high reliability and the high band of phased array antenna proposition of new generation.
The specific inductivity of strontium-barium titanate BSTO material changes with the variation of applying direct current electric field, when voltage from V (0)Change to V (app)The time, specific inductivity will produce an increment Delta ε r=[ε R (0)-ε R (app)], this increment and ε R (0)The percentage ratio of ratio is called adjustability, promptly uses Tunability=[ε R (0)-ε R (app)]/ε R (0)* 100% expression.And will produce corresponding differential phase shift when applying the light (microwave) of a particular frequencies simultaneously, reach the purpose that changes phase place.Material with this specific character is called electrooptical material.
Twentieth century end of the nineties, people such as US Naval Research Laboratory (NRL) J.L.Rao propose the thought of ferroelectric formula lens phase array system, adopt the monoblock type phase-shifting unit, can effectively reduce the quantity (become m+n by original m * n, wherein m, n are respectively the columns and the line number of phased array) of phase shifter, driving mechanism and controller.The personnel of United States Army research laboratory did a statistics: use ferrite to prepare 1000 unitary radar arrays, about 5,000,000 dollars of required expense, and adopt electrooptical material to replace ferrite only needs 200,000 dollars, and only the material cost is original 1/25.Because but the volume miniaturization improves with integrated level, make phased array radar more be applicable to airborne and On-Board System simultaneously.
Current, the BSTO ferroelectric material is generally believed it is the most promising phase shifter material, from earlier 1990s the ferroelectric ceramic(s) phase shifter since the U.S. enters the applicable feasibility Journal of Sex Research stage, states such as Britain, France, Japan, Sweden and Russia are also in the research of this respect of throwing oneself into, they have carried out doping vario-property to the BSTO material, discovery is mixed multiple metal oxide and is had similar modifying function in the BSTO material system, as the difference doped with Al 2O 3, ZrO 2, MgO the BSTO matrix material, their Curie temperature all decreases, and is in paraelectric phase during room temperature, and follows the increase of oxide compound add-on, the room temperature dielectric constant of material all shows downward trend, adjustability also obviously descends.
Compare with the material of other doping vario-property, BSTO/MgO, BSTO/MgO/ rare earth composite material have more excellent dielectric properties, according to U.S. Pat-5427988 and US-6074971Ba 0.6Sr 0.4TiO 3The DIELECTRIC CONSTANT of/60wt.%MgO R (0)Be 89.35 o'clock, under the direct-current biasing of 2.63kV/mm, its adjustability is 11.09%, DIELECTRIC CONSTANT R (0)Be 116.86 o'clock, under the direct-current biasing of 2kV/mm, its adjustability is 9.99%; Ba 0.55Sr 0.45TiO 3/ 60wt.%MgO/La 2O 3DIELECTRIC CONSTANT R (0)Be 79 o'clock, under the direct-current biasing of 2kV/mm, its adjustability is 7.85%.But these two kinds of matrix materials exist two big weak points: (1) along with the increase of oxide compound add-on, when specific inductivity reduced, its adjustability suppression ratio was more serious; (2) sintering temperature is higher, and usually between 1350 ℃-1450 ℃, and sintering temperature raises with the increase of oxide compound add-on.
Summary of the invention
The purpose of this invention is to provide a kind of barium strontium titanate base electro-optical composite material and preparation method thereof.This preparation method is simple, but densified sintering product at low temperatures, and material has low-k, low-loss, high adjustability, high insulation resistance, high breakdown characteristics simultaneously.Be suitable for and make phased array phase shifter electrooptical material.
Described material is by (1-y-z) Ba 1-xSr xTiO 3+ yMe 2SiO 4+ zMO forms, x=0～0.75 wherein, y=5～60wt.%; Z=0～30wt.%, y+z=5～60wt.%.
Wherein, Me 2SiO 4Can be CaSiO 3, BaSiO 3, SrSiO 3Can be the presoma of these compounds also, comprise MgO, MgCO 3, SiO 2, CaCO 3, BaCO 3, Mg 2Si 3O 8, SrCO 3Described MO can be MgTiO 3, MgZrO 3, MgAl 2O 4, Al 2O 3, ZrO 2
Preparation (1-y-z) Ba 1-xSr xTiO 3+ yMe 2SiO 4The concrete processing step of+zMO is as follows:
(1) prepares Ba respectively by stoichiometric ratio 1-xSr xTiO 3, and Me 2SiO 4, raw material can adopt pulverous BaCO 3, SrCO 3, TiO 2, Mg 2Si 3O 8And MgO, be medium then with water, agate ball is situated between for mill, behind ball milling 12h～24h, discharging, oven dry, powder pre-burning 2h～4h in 1100 ℃～1200 ℃ scopes obtains Ba respectively 1-xSr xTiO 3, and Mg 2SiO 4Powder;
(2) according to forming design, in the BSTO powder, mix the Me of different amounts 2SiO 4And MO, be medium with water, agate ball is situated between ball milling 24-36h hour for mill;
(3) with the said mixture of oven dry, add the PVA granulation of 3～8wt.%, under the pressure of 50～200Mpa with the pressed by powder moulding;
(4) 800 ℃ below the temperature, be incubated 2 hours, get rid of the organic substance in the green compact, the heat-up rate of binder removal process is not higher than 30 ℃/min;
(5) green compact sintering in 1250 ℃～1350 ℃ scopes, insulation 2h～4h.Behind the naturally cooling, promptly obtain the body material of required excellent property.
The invention has the advantages that by material prescription of the present invention, can be in 1250 ℃～1350 ℃ scopes sintering, and this material to have a specific inductivity low, loss is low, adjustability height, insulation resistance height, excellent properties such as breakdown characteristics height.Successfully obtained the result that high-performance and low fever have both simultaneously.
Description of drawings
Fig. 1 is the change curve of the dielectric constant with temperature of embodiment 1 sample 1
Fig. 2 is the change curve of the specific inductivity of embodiment 1 sample 1 with bias voltage
Fig. 3 is the change curve of the dielectric constant with temperature of embodiment 2 samples 2
Fig. 4 is the change curve of the specific inductivity of embodiment 2 samples 2 with bias voltage
Fig. 5 is the change curve of the dielectric constant with temperature of embodiment 3 samples 3
Fig. 6 is the change curve of the specific inductivity of embodiment 3 samples 3 with bias voltage
Fig. 7 is the change curve of the dielectric constant with temperature of embodiment 4 samples 4
Fig. 8 is the change curve of the specific inductivity of embodiment 4 samples 4 with bias voltage
Embodiment
Further illustrate substantial characteristics of the present invention and obvious improvement below by embodiment, yet the present invention absolutely not only is confined to described embodiment.
Embodiment 1, with pulverous BaCO 3, SrCO 3, TiO 2, Me 2Si 3O 8With MO be raw material, prepare Ba respectively by stoichiometric ratio 1-xSr xTiO 3(x=0.4) and Me 2SiO 4, behind the wet ball grinding 24h, discharging, oven dry, powder obtains Ba respectively at 1150 ℃ of following pre-burning 2h 0.6Sr 0.4TiO 3And Me 2SiO 4Powder; According to (1-y-z) Ba 1-xSr xTiO 3+ yMe 2SiO 4+ zMO (x=0.4 wherein, y=14wt.%, z=6wt.%) proportioning, wet ball grinding 24h; Discharging, oven dry add the PVA granulation of 6wt.%, under the pressure of 100Mpa with the pressed by powder moulding; Through 800 ℃/2h binder removal, 1320 ℃/2h sintering.Sample after burning till is processed through fine grinding, by silver electrode, can be used for the dielectric properties test after the ultrasonic cleaning.The electric property of sample 1 sees Table 1.Fig. 1 has provided the change curve of the dielectric constant with temperature of sample 1, and Fig. 2 has provided the change curve of the specific inductivity of sample 1 at bias voltage.
Embodiment 1 sample 1 electric property
Moiety Specific inductivity (25 ℃) ??tgδ Adjustability (at 2kV/mm) Curie temperature Insulation resistivity (at 100V/mm) Voltage breakdown (kV/mm)
Ba 0.6Sr 0.4TiO 3+14wt.％Mg 2SiO 4+6wt.％MgO 806.06 ??0.002 ??12.77 ??-31.6℃ ??8.24×10 14??Ω·cm ??9.1
Embodiment 2, according to (1-y-z) Ba 1-xSr xTiO 3+ yMe 2SiO 4+ zMO (x=0.4 wherein, y=25wt.%, z=10wt.%) proportioning preparation, concrete technology is same with embodiment 1.Sample 2 electric properties see Table 2.Fig. 3 has provided the change curve of the dielectric constant with temperature of sample 2, and Fig. 4 has provided the change curve of the specific inductivity of sample 2 with bias voltage.
Embodiment 2 samples 2 electric properties
Moiety Specific inductivity (25 ℃) ?tgδ Adjustability (at 2kV/mm) Curie temperature Insulation resistivity (at 100V/mm) Voltage breakdown (kV/mm)
Ba 0.6Sr 0.4TiO 3+25wt.％Mg 2SiO 4+10wt.％MgO ??346 ?0.0006 ??12.79 ????-29.1℃ ??8.45×10 14??Ω·cm ????12
Embodiment 3, according to (1-y-z) Ba 1-xSr xTiO 3+ yMe 2SiO 4+ zMO (x=0.4 wherein, y=35wt.%, z=15wt.%) proportioning preparation, concrete technology is same with embodiment 1.Sample 3 electric properties see Table 3.Fig. 5 has provided the change curve of the dielectric constant with temperature of sample 3, and Fig. 6 has provided the change curve of the specific inductivity of sample 3 with bias voltage.
Embodiment 3 samples 3 electric properties
Moiety Specific inductivity (25 ℃) ????tgδ Adjustability (at 2kV/mm) Curie temperature Insulation resistivity (at 100V/mm) Voltage breakdown (kV/mm)
Ba 0.6Sr 0.4TiO 3+35wt.％Mg 2SiO 4+15wt.％MgO ??118.40 ????0.001 ??13.18 ??-37℃ ??8.87×10 14??Ω·cm ??10
Embodiment 4, according to (1-y-z) Ba 1-xSr xTiO 3+ yMe 2SiO 4+ zMO (x=0.4 wherein, y=40wt.%, z=20wt.%) proportioning preparation, concrete technology is same with embodiment 1.Sample 4 electric properties see Table 4.Fig. 7 has provided the change curve of the dielectric constant with temperature of sample 4, and Fig. 8 has provided the change curve of the specific inductivity of sample 4 with bias voltage.
Embodiment 4 samples 4 electric properties
Moiety (25 ℃ of specific inductivity ??tgδ Adjustability (at 2kV/mm) Curie temperature Insulation resistivity (at 100V/mm) Voltage breakdown (kV/mm)
Ba 0.6Sr 0.4TiO 3+40wt.％Mg 2SiO 4+20wt.％MgO ????65.10 ??0.002 ??8.9 ??-33.6℃ ??1.05×10 15??Ω·cm ????7.5

Claims (6)

1, a kind of barium strontium titanate base electro-optical composite material is characterized in that material is by (1-y-z) Ba 1-xSr xTiO 3+ yMe 2SiO 4+ zMO forms, x=0～0.75 wherein, y=5～60wt.%; Z=0～30wt.%, y+z=5～60wt.%;
Described Me 2SiO 4Can be CaSiO 3, BaSiO 3, SrSiO 3, also can be the presoma of these compounds; Described MO can be MgTiO 3, MgZrO 3, MgAl 2O 4, Al 2O 3, ZrO 2
2, by the described a kind of barium strontium titanate base electro-optical composite material of claim 1, the presoma that it is characterized in that described compound can be MgO, MgCO 3, SiO 2, CaCO 3, BaCO 3, Mg 2Si 3O 8, SrCO 3
3, by the preparation method of claim 1 or 2 described a kind of barium strontium titanate base electro-optical composite materials, it is characterized in that comprising the steps:
(1) prepares Ba respectively by stoichiometric ratio 1-xSr xTiO 3, and Me 2SiO 4, through ball milling, discharging, oven dry, powder obtains Ba respectively through pre-burning 1-xSr xTiO 3, and Me 2SiO 4Powder;
(2) according to forming proportioning, at Ba 1-xSr xTiO 3Mix Me in the powder 2SiO 4And MO, ball milling 24～36h hour;
(3) with the said mixture granulation and the compression moulding green compact of drying;
(4) insulation is to get rid of the organic substance in the green compact;
(5) green compact naturally cooling behind sintering.
4, by the preparation method of the described a kind of barium strontium titanate base electro-optical composite material of claim 3, it is characterized in that preparing Ba 1-xSr xTiO 3, and Me 2SiO 4Raw material be pulverous BaCO 3, SrCO 3, TiO 2, Mg 2Si 3O 8And MgO.
5,, it is characterized in that the agglomerating condition is sintered heat insulating 2h～4h in 1250 ℃～1350 ℃ scopes by the preparation method of claim 3 or 4 described a kind of barium strontium titanate base electro-optical composite materials.
6,, it is characterized in that the pre-burning condition is pre-burning 2h～4h in 1100 ℃～1200 ℃ scopes by the preparation method of claim 3 or 4 described a kind of barium strontium titanate base electro-optical composite materials.
CNB2005100258122A 2005-05-13 2005-05-13 Barium strontium titanate base electro-optical composite material and preparation method thereof Active CN100412030C (en)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101955356A (en) * 2010-10-09 2011-01-26 同济大学 Tunable dielectric barium strontium titanate based composite silicate microwave dielectric material and preparation thereof
CN102320826A (en) * 2011-05-31 2012-01-18 武汉理工大学 Multi-case-layer structure X8R capacitor dielectric ceramic and preparation method thereof
CN102491745A (en) * 2011-11-25 2012-06-13 中国科学院上海硅酸盐研究所 Ferroelectric/non-ferroelectric composite columnar ceramic material and preparing method thereof
CN103708825A (en) * 2013-12-19 2014-04-09 中国科学院上海硅酸盐研究所 High-tuning low-loss barium strontium titanate-zinc aluminate composite material and preparation method thereof
CN113321496A (en) * 2021-07-01 2021-08-31 宜宾红星电子有限公司 Composite microwave dielectric ceramic material and preparation method thereof

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1181010C (en) * 2003-05-23 2004-12-22 华中科技大学 Composite microwave tuning strontium barium titanate ceramics
CN1238301C (en) * 2004-07-08 2006-01-25 中国电子科技集团公司第五十五研究所 Process for preparing barium strontium titanate and cordierite glass ceramic composite medium material
CN100344575C (en) * 2004-08-13 2007-10-24 中国科学院上海硅酸盐研究所 Low temperature sitering and prparing method for lithium blended strontium-barium titanate ceramics

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101955356A (en) * 2010-10-09 2011-01-26 同济大学 Tunable dielectric barium strontium titanate based composite silicate microwave dielectric material and preparation thereof
CN101955356B (en) * 2010-10-09 2012-12-05 同济大学 Tunable dielectric barium strontium titanate based composite silicate microwave dielectric material and preparation thereof
CN102320826A (en) * 2011-05-31 2012-01-18 武汉理工大学 Multi-case-layer structure X8R capacitor dielectric ceramic and preparation method thereof
CN102320826B (en) * 2011-05-31 2013-07-17 武汉理工大学 Multi-case-layer structure X8R capacitor dielectric ceramic and preparation method thereof
CN102491745A (en) * 2011-11-25 2012-06-13 中国科学院上海硅酸盐研究所 Ferroelectric/non-ferroelectric composite columnar ceramic material and preparing method thereof
CN103708825A (en) * 2013-12-19 2014-04-09 中国科学院上海硅酸盐研究所 High-tuning low-loss barium strontium titanate-zinc aluminate composite material and preparation method thereof
CN113321496A (en) * 2021-07-01 2021-08-31 宜宾红星电子有限公司 Composite microwave dielectric ceramic material and preparation method thereof

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