CN107721418A - A kind of ceramic dielectric material of barium based perovskite structure - Google Patents

A kind of ceramic dielectric material of barium based perovskite structure Download PDF

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CN107721418A
CN107721418A CN201710943294.5A CN201710943294A CN107721418A CN 107721418 A CN107721418 A CN 107721418A CN 201710943294 A CN201710943294 A CN 201710943294A CN 107721418 A CN107721418 A CN 107721418A
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dielectric material
perovskite structure
ceramic dielectric
based perovskite
barium based
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李玲霞
孙正
于仕辉
郑浩然
乔坚栗
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Tianjin University
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Tianjin University
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    • C04B35/00Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/48Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on zirconium or hafnium oxides, zirconates, zircon or hafnates
    • C04B35/49Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on zirconium or hafnium oxides, zirconates, zircon or hafnates containing also titanium oxides or titanates
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    • C04B35/00Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
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    • C04B2235/00Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3205Alkaline earth oxides or oxide forming salts thereof, e.g. beryllium oxide
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    • C04B2235/00Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3205Alkaline earth oxides or oxide forming salts thereof, e.g. beryllium oxide
    • C04B2235/3215Barium oxides or oxide-forming salts thereof
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    • C04B2235/00Aspects relating to ceramic starting mixtures or sintered ceramic products
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    • C04B2235/30Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3231Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
    • C04B2235/3244Zirconium oxides, zirconates, hafnium oxides, hafnates, or oxide-forming salts thereof
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    • C04B2235/3249Zirconates or hafnates, e.g. zircon containing also titanium oxide or titanates, e.g. lead zirconate titanate (PZT)
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01PWAVEGUIDES; RESONATORS, LINES, OR OTHER DEVICES OF THE WAVEGUIDE TYPE
    • H01P1/00Auxiliary devices
    • H01P1/18Phase-shifters

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Abstract

The invention discloses a kind of ceramic dielectric material of barium based perovskite structure and preparation method thereof, its chemical formula is Ba1‑xSmx(Zr0.1Ti0.9)O3, wherein 0 < x≤0.003.First by BaCO3、Sm2O3、TiO2、ZrO2Stoichiometrically formula carries out dispensing, and after ball milling, drying, sieving, then at 1050~1250 DEG C of pre-burnings, then compressing after secondary ball milling is base substrate, and base substrate sinters in 1200 DEG C~1300 DEG C, and the ceramic dielectric material of barium based perovskite structure is made.The Ba of the present invention1‑xSmx(Zr0.1Ti0.9)O3Material, there is higher tuning characteristic (66%) and moderate sintering temperature (1270 DEG C).

Description

A kind of ceramic dielectric material of barium based perovskite structure
Technical field
The present invention be on electronic information material and component, it is more particularly to a kind of with more high dielectric tunability performance Ceramic dielectric material of barium based perovskite structure and preparation method thereof.
Background technology
Dielectric tuning material be exactly its dielectric constant can with extra electric field change and change material, this dielectric constant with The nonlinear change of extra electric field is exactly dielectric tuning, using this dielectric, nonlinear effect, can be designed that voltage control Adjustable condenser, so as to be applied to the tunable devices such as the adjustable phase shifter of various voltages, oscillator, wave filter and delayer In.Phased-array radar is exactly to realize scanning of the wave beam in space by controlling the phase of antenna array, is changed by phase shifter The phase difference of adjacent antennaValue, so that it may make radar beam space carry out electric scanning and antenna need not rotate.
Critical component of the phase shifter as phased array antenna, it is desirable to which it has high switching speed, low insertion loss, size Small, the features such as quality is small.At present, phase shifter material mainly includes PIN diode, ferrite and the class of dielectric material three.With other Material is compared, and dielectric material has good fast response time, system controlling, small volume, quality is small, low advantage is lost, and is one Phase shifter material of the kind with applications well prospect.Barium zirconium phthalate Ba (ZrxTi1-x)O3(BZT) it is BaTiO3Middle Zr4+Substitution portion Divide Ti4+The system solid solution formed afterwards, is a kind of new ferroelectric, and this kind of ferroelectric causes because it has some ferroelectric domains It there is the regularly arranged of dipole when without DC Electric Field, under the interaction of these dipoles, cause BZT to have There is higher dielectric tunability.But the sintering temperature of BZT ceramics is higher (~1400 DEG C), using addition sintering aid (such as CuO、LiCO3Deng) although the sintering temperature of BZT ceramics can be reduced, also result in the deterioration of tuning performance.
The content of the invention
Ceramic dielectric material of barium based perovskite structure provided by the present invention and preparation method thereof, it is therefore intended that overcome The shortcomings that reducing the penalty caused by sintering temperature in the prior art, product is improved by using the mode of ion doping Dielectric tunable properties, and reduce its sintering temperature.
The present invention is achieved by following technical solution:
A kind of ceramic dielectric material of barium based perovskite structure, its chemical formula are Ba1-xSmx(Zr0.1Ti0.9)O3, wherein 0 < x≤0.003;
The preparation method of the ceramic dielectric material of the barium based perovskite structure, specific implementation step are as follows:
(1) respectively by BaCO3、Sm2O3、TiO2、ZrO2Stoichiometrically formula Ba1-xSmx(Zr0.1Ti0.9)O3, wherein 0 < x ≤ 0.003 carries out dispensing, and powder is put into ball grinder, after adding absolute ethyl alcohol and zirconium ball, ball milling 2~9 hours;
(2) powder after step (1) ball milling is put into drying box, in 80~120 DEG C of drying, then crosses 40 mesh sieves;
(3) it is placed in after the powder after sieving being put into alumina crucible in moderate oven, in 1050~1250 DEG C of pre-burnings, insulation 2~6 hours;
(4) by the raw material after step (3) pre-burning, it is put into ball grinder, addition zirconia ball and absolute ethyl alcohol, ball milling 8~ 14 hours, sieved after drying, then base substrate is pressed into 1~6MPa pressure with powder compressing machine;
(5) base substrate of step (4) is incubated 2~8 hours, barium based perovskite knot is made in 1200 DEG C~1300 DEG C sintering The ceramic dielectric material of structure.
The powder of the step (1) carries out ball milling using planetary ball mill, and drum's speed of rotation is 400 revs/min.
Step (1) Ba1-xSmx(Zr0.1Ti0.9)O3Middle Sm content is x=0.002.
The sintering temperature of the step (5) is 1270 DEG C.
Ba produced by the present invention1-xSmx(Zr0.1Ti0.9)O3Material, there is higher tuning characteristic (66%) and moderate burning Junction temperature (1270 DEG C).
Embodiment
The present invention is with BaCO3、Sm2O3、TiO2、ZrO2For initial feed, prepared by solid phase method a kind of with compared with high tuning The dielectric substance of characteristic, specific embodiment are as follows:
1. by BaCO3、Sm2O3、TiO2、ZrO2Stoichiometrically formula (Ba0.998Sm0.002)(Zr0.1Ti0.9)O3Carry out dispensing, Match and be:8.37257g BaCO3、0.01468g Sm2O3、3.0568gTiO2, 0.5238gZrO2About 10g mixed powder is put Enter in nylon tank, add 150ml absolute ethyl alcohols, after adding 100g zirconium ball, ball milling 6 hours, rotating speed on planetary ball mill For 400 revs/min;
2. the raw material after ball milling is placed in drying box, in 80 DEG C of drying, 40 mesh sieves are then crossed;
3. the powder after drying sieving is put into moderate oven, in 1100 DEG C of pre-burnings, 4 hours are incubated;
4. the powder after step 3 pre-burning is added into 0.5wt.%PVA to be mixed, it is put into ball grinder, adds zirconium oxide Ball and absolute ethyl alcohol, ball milling 12 hours, sieve after drying, then are pressed into base substrate with powder compressing machine with 4MPa pressure;
5. green compact are sintered at 1270 DEG C, 4 hours are incubated, the pottery of the barium based perovskite structure with high tuning characteristic is made Porcelain dielectric substance.
6. using TH2828S and HF3013, test its dielectric constant and calculate tuning rate,
Tuning rate calculation formula:
FOM calculation formula:
7. the tuning rate of embodiment 1:66%, FOM:20.
Embodiment 2-8
Embodiment 2-8 is different Sm contents Ba from embodiment 11-xSmx(Zr0.1Ti0.9)O3, its calcined temperature, sintering temperature, Sintering time refers to table 1 with dielectric properties, and remaining preparation process is identical with embodiment 1.
The invention is not limited in above-described embodiment, the change of many details is possible, but therefore this does not run counter to this The scope and spirit of invention.

Claims (4)

1. a kind of ceramic dielectric material of barium based perovskite structure, its chemical formula is Ba1-xSmx(Zr0.1Ti0.9)O3, wherein 0 < x≤0.003。
The preparation method of the ceramic dielectric material of the barium based perovskite structure, specific implementation step are as follows:
(1) respectively by BaCO3、Sm2O3、TiO2、ZrO2Stoichiometrically formula Ba1-xSmx(Zr0.1Ti0.9)O3, wherein 0 < x≤ 0.003 carries out dispensing, and powder is put into ball grinder, after adding absolute ethyl alcohol and zirconium ball, ball milling 2~9 hours;
(2) powder after step (1) ball milling is put into drying box, in 80~120 DEG C of drying, then crosses 40 mesh sieves;
(3) it is placed in after the powder after sieving being put into alumina crucible in moderate oven, in 1050~1250 DEG C of pre-burnings, insulation 2~6 Hour;
(4) by the raw material after step (3) pre-burning, it is put into ball grinder, adds zirconia ball and absolute ethyl alcohol, ball milling 8~14 are small When, sieved after drying, then base substrate is pressed into 1~6MPa pressure with powder compressing machine;
(5) base substrate of step (4) is incubated 2~8 hours, barium based perovskite structure is made in 1200 DEG C~1300 DEG C sintering Ceramic dielectric material.
A kind of 2. ceramic dielectric material of barium based perovskite structure according to claim 1, it is characterised in that the step Suddenly the powder of (1) carries out ball milling using planetary ball mill, and drum's speed of rotation is 400 revs/min.
A kind of 3. ceramic dielectric material of barium based perovskite structure according to claim 1, it is characterised in that the step Suddenly (1) Ba1-xSmx(Zr0.1Ti0.9)O3Middle Sm content is x=0.002.
A kind of 4. ceramic dielectric material of barium based perovskite structure according to claim 1, it is characterised in that the step Suddenly the sintering temperature of (5) is 1270 DEG C.
CN201710943294.5A 2017-10-11 2017-10-11 A kind of ceramic dielectric material of barium based perovskite structure Pending CN107721418A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109589910A (en) * 2018-12-13 2019-04-09 大连海事大学 The preparation method and application of barium cobalt-based properties of perovskite mixed-oxide oxygen carrier

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109589910A (en) * 2018-12-13 2019-04-09 大连海事大学 The preparation method and application of barium cobalt-based properties of perovskite mixed-oxide oxygen carrier
CN109589910B (en) * 2018-12-13 2022-03-01 大连海事大学 Preparation method and application of barium-cobalt-based perovskite composite metal oxide oxygen carrier

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