CN105837200A - Manganese-doped cerium lithium calcium titanoniobate-based ceramic material and preparation method thereof - Google Patents

Manganese-doped cerium lithium calcium titanoniobate-based ceramic material and preparation method thereof Download PDF

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CN105837200A
CN105837200A CN201610206658.7A CN201610206658A CN105837200A CN 105837200 A CN105837200 A CN 105837200A CN 201610206658 A CN201610206658 A CN 201610206658A CN 105837200 A CN105837200 A CN 105837200A
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based ceramic
additive
titanium niobate
bismuth titanium
cerium based
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朱建国
辛德琼
陈强
刘洪�
肖定权
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Sichuan University
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Sichuan University
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Abstract

The invention discloses a manganese-doped cerium lithium calcium titanoniobate-based ceramic material and a preparation method thereof. The method comprises the following steps: preparing a manganese-doped cerium lithium calcium titanoniobate-based powdery material through adopting a traditional solid phase technology; and granulating the powdery material, tabletting the granulated material, removing an adhesive, sintering, polymerizing with silver, and carrying out other processes contained in a traditional electronic ceramic preparation methdo to obtain the manganese-doped cerium lithium calcium titanoniobate-based ceramic. A-position lithium and cerium (Li, Ce) and B-position niobium (Nb) composite substitution reduces the sintering temperature of calcium titanoniobate (CBT) ceramic, obviously improves the piezoelectricity of the CBT ceramic at a low sintering temperature, obviously reduces the dielectric loss of the CBT ceramic at a low sintering temperature, and plays a great role in high-temperature field practical utilization of CBT-based ceramic materials.

Description

A kind of additive Mn bismuth titanium niobate calcium lithium cerium based ceramic material and preparation method thereof
Technical field
The present invention relates to a kind of bismuth titanium niobate calcium lithium cerium based ceramic material and preparation method thereof, specifically, be at bismuth calcium titanate (CBT) preparation process of sill mixes the lithium of certain content, cerium, niobium, manganese (Li, Ce, Nb, Mn) element simultaneously, And obtain high tension performance at a relatively low sintering temperature.The invention belongs to Materials Science and Engineering field.
Background technology
Along with the high speed development of modern science and technology, the energy, automobile, Aero-Space, petrochemical industry, geological prospecting, atom The electronic equipment that can work at a higher temperature is badly in need of in numerous industrial departments such as energy and scientific research institution.Nb steel piezoelectricity Pottery is because possessing high Tc, low-k, electromechanical coupling factor anisotropy ageing rate obvious, low, high resistivity, production The advantage such as with low cost and easily modified, has broad application prospects in high-temperature piezoelectric field.
Bismuth calcium titanate (CaBi4Ti4O15, hereinafter referred to as CBT) and it is a kind of bismuth layer structure piezoelectric material, by perovskite-like layer (CaBi2Ti4O13)2-(Bi2O2)2+Layer is the most alternately arranged to be formed, and Curie temperature is higher, has reached 790 DEG C, but Its piezoelectric property is relatively low, d33It is only 5～7pC/N.This is to put down owing to the spontaneous polarization of bismuth stratified material is predominantly located at a-b Face, its spontaneous polarization turns to and is limited by two dimensional surface, is difficult to obtain higher piezoelectric property by polarization.This external high temperature In sintering process, the volatilization of bismuth oxide causes Lacking oxygen, thus reduces the consistency of pottery, is unfavorable for carrying of its piezoelectric activity Rise.In order to solve this problem, domestic and international researcher improves preparation technology, and it is doped modification, obtains Some impressive progresses, Peng Zhihang etc. reports employing conditional electronic ceramic process, CBT pottery A position is carried out (Li, Ce) Compound replacement, the CBT base piezoelectric ceramic performance obtained has the biggest lifting, and Curie temperature reaches 768 DEG C, piezoelectric constant d33For 18.5pC/N.Turn round and look at the researcheres such as big country simultaneously and find MnCO3Doping the resistivity of CBT base piezoelectric ceramic can be made to raise, And effectively lower its dielectric loss.At present CBT base pottery A, B position is combined the report replacing and adulterating little.
Summary of the invention
It is an object of the invention to provide a kind of additive Mn bismuth titanium niobate calcium lithium cerium based ceramic material and preparation method thereof.The method Not only improve bismuth calcium titanate-based (CBT) base ceramic material in sintering process, need to reach the deficiency of very high sintering temperature, Also substantially increase the piezoelectric property of CBT pottery.
Additive Mn bismuth titanium niobate calcium lithium cerio piezoceramic material is by formula Ca1-x(Li,Ce)x/2Bi4Ti4-yNbyO15-zMnCO3Table Show, 0.05≤x≤0.20 in formula, 0.00≤y≤0.10,0.01≤z≤0.10.
The preparation method of additive Mn bismuth titanium niobate calcium lithium cerium based ceramic material comprises the following steps:
(1) solid phase method prepares additive Mn bismuth titanium niobate calcium lithium cerium based ceramic powder body
Raw material is pressed respectively formula Ca1-x(Li,Ce)x/2Bi4Ti4-yNbyO15-zMnCO3, wherein x, y, z represents lithium, cerium respectively (Li, Ce), niobium (Nb) and the molar fraction of manganese (Mn) element, the scope of numerical value is: 0.05≤x≤0.20,0.00≤y≤0.10, 0.01≤z≤0.10；Doped chemical adds with oxide or carbonate for raw material, carries out weighing, dispensing, is put in polyurethane ball milling In tank, with dehydrated alcohol as disperse medium, after planetary ball mill ball milling 8～24h, rotating speed is 100～450rpm, is drying Toasting 2～3h under lamp, then in temperature programmed control batch-type furnace, continuous warming, to 800～950 DEG C, is incubated 2～4h, obtains manganese and mix Miscellaneous bismuth titanium niobate calcium lithium cerium based ceramic powder body；
(2) secondary ball milling
Prepared additive Mn bismuth titanium niobate calcium lithium cerium based ceramic powder body is put in polyurethane ball-milling pot, with dehydrated alcohol for dispersion Medium, after planetary ball mill ball milling 8～24h, rotating speed is 100～450rpm, toasts 2 to 3h under drying lamp；
(3) pelletize tabletting
The powder body of above-mentioned drying adds after the poly-vinyl alcohol solution that concentration is 5～10at% is sufficiently mixed and carry out pelletize, so After under pressure is 16～20MPa, be pressed into diameter 10～15mm, thickness be 0.8～1.2mm additive Mn bismuth titanium niobate Calcium lithium cerium based ceramic disk；
(4) binder removal sintering
By above-mentioned additive Mn bismuth titanium niobate calcium lithium cerium based ceramic disk at temperature 700～950 DEG C of binder removals, then in temperature 1000 DEG C～1200 DEG C sintering 2～4h make additive Mn bismuth titanium niobate calcium lithium cerium based ceramic disk；
(5) by galactic pole
After the additive Mn bismuth titanium niobate calcium lithium cerium based ceramic disk surfaces obtained after above-mentioned sintering is polished to 0.4～0.6mm again On brush, concentration is the silver slurry of 5～15wt%, then makes sample in temperature 700～800 DEG C of sintering 10～15min.Sample is put Entering in the silicone oil bath of 120～250 DEG C and polarize, Polarization field strength is 8～15kV/mm, and the dwell time is 15～45min, system Become additive Mn bismuth titanium niobate calcium lithium cerio piezoelectric ceramics.
Additive Mn bismuth titanium niobate calcium lithium cerium based ceramic material in high temperature environments for piezoelectric transducer, transducer, driver, Wave filter and capacitor element.
Performance test
1, utilize X-ray diffractometer (XRD, DX-2700X) that additive Mn bismuth titanium niobate calcium lithium cerium based ceramic disk is carried out Phase structure is analyzed；
2, ultramicroscope (SEM, S-3400N) is utilized to observe the surface of additive Mn bismuth titanium niobate calcium lithium cerium based ceramic disk Pattern；
3, utilize Archimedes method test and calculate the relative density of additive Mn bismuth titanium niobate calcium lithium cerium based ceramic
4, d is utilized33Piezoelectricity tester (ZJ-3A) tests the d of additive Mn bismuth titanium niobate calcium lithium cerium based ceramic disk33。
5, numeral megger (PC68) is utilized to test the resistivity of additive Mn bismuth titanium niobate calcium lithium cerium based ceramic.
6, utilize electric impedance analyzer (HP4294A) test additive Mn bismuth titanium niobate calcium lithium cerium based ceramic Jie frequency curve and kp；
7, LCR tester (HP4980A) is utilized to test Jie's temperature curve of additive Mn bismuth titanium niobate calcium lithium cerium based ceramic；
Shown in test result as Fig. 1～9.Result shows, utilizes additive Mn bismuth titanium niobate calcium lithium prepared by the method for the present invention Cerium based ceramic, owing to crystal grain is dense, crystal grain uniform, improves sintering activity, and sintering effect is more preferable, at relatively low sintering At temperature (～1090 DEG C), the compactness of additive Mn bismuth titanium niobate calcium lithium cerium based ceramic is higher.Additive Mn bismuth titanium niobate calcium lithium cerium Base pottery has higher piezoelectric constant d33, its maximal pressure electric constant d33Up to 19.6pC/N, Curie temperature TC>=780 DEG C, Dielectric constant is 160, also reduces its dielectric loss simultaneously, and dielectric loss is 0.16%.
The present invention compared with prior art, has the advantage that
1. additive Mn bismuth titanium niobate calcium lithium cerium based ceramic material has more excellent piezoelectric property, and A, B position is combined and replaces, The advantage that multiple-composite doped spinel is modified more can be played in combination with additive Mn.
2., under suitable polarization condition, additive Mn bismuth titanium niobate calcium lithium cerium based ceramic can fully polarize, and farthest carries Its piezoelectric property high.
Accompanying drawing explanation
Fig. 1 is in embodiment 1,2,31#、2#、3#The X-ray of sample additive Mn bismuth titanium niobate calcium lithium cerium based ceramic material Diffracting spectrum.
Fig. 2 is in embodiment 1,2,31#、2#、3#The lattice of sample additive Mn bismuth titanium niobate calcium lithium cerium based ceramic material is normal Number curve.
Fig. 3 is in enforcement 22#Scanning electron microscope (SEM) photo of sample additive Mn bismuth titanium niobate calcium lithium cerium based ceramic material.
Fig. 4 is in embodiment 1,2,31#、2#、3#Sample additive Mn bismuth titanium niobate calcium lithium cerium based ceramic material the closeest Degree.
Fig. 5 is in embodiment 1,2,31#、2#、3#The d of sample additive Mn bismuth titanium niobate calcium lithium cerium based ceramic material33,kp And resistivity.
Fig. 6 is in embodiment 22#、4#、5#The d of sample additive Mn bismuth titanium niobate calcium lithium cerium based ceramic material33。
Fig. 7 is in embodiment 1,2,31#、2#、3#Jie Wen Qu of sample additive Mn bismuth titanium niobate calcium lithium cerium based ceramic material Line.
Fig. 8 is in embodiment 1,2,31#、2#、3#Jie's frequency of sample additive Mn bismuth titanium niobate calcium lithium cerium based ceramic material is bent Line.
Fig. 9 is in embodiment 1,2,31#、2#、3#The depolarization of sample additive Mn bismuth titanium niobate calcium lithium cerium based ceramic material Curve.
Detailed description of the invention
Below by embodiment, the present invention is specifically described, it is necessary to it is pointed out here that be the present embodiment be served only for this Invention is further described, it is impossible to be interpreted as limiting the scope of the invention, and the person skilled in the art in this field is permissible Content according to the invention described above makes some nonessential improvement and adjustment.
Embodiment 1:
(1) solid phase method prepares CBT based ceramic powder body
Raw material is pressed respectively formula Ca0.85(Li,Ce)0.075Bi4Ti4O15-0.01MnCO3, x=0.15, y=0.00, z=0.01, compile Number 1#, carry out weighing, dispensing, be put in polyurethane ball-milling pot, with dehydrated alcohol as disperse medium, use planetary ball mill ball After mill 12, rotating speed is 300rpm, toasts 3h under lamp make it become dry drying, and then in temperature programmed control batch-type furnace, continuous warming is extremely 850 DEG C, it is incubated 2h, obtains additive Mn bismuth titanium niobate calcium lithium cerium based ceramic powder body；
(2) secondary ball milling
Prepared additive Mn bismuth titanium niobate calcium lithium cerium based ceramic powder body is put in polyurethane ball-milling pot, with dehydrated alcohol for dispersion Medium, after planetary ball mill ball milling 12h, rotating speed is 300rpm, toasts 3h and make it become dry under drying lamp；
(3) pelletize tabletting
The powder body of above-mentioned drying adds after the poly-vinyl alcohol solution that concentration is 7wt% is sufficiently mixed and carry out pelletize, then exist Pressure be pressed into diameter 10mm under 20MPa, thickness is the additive Mn bismuth titanium niobate calcium lithium cerium based ceramic disk of 0.8mm；
(4) binder removal sintering
By above-mentioned additive Mn bismuth titanium niobate calcium lithium cerium based ceramic disk at 850 DEG C of binder removals of temperature, then at temperature 1090 DEG C sintering 2h makes additive Mn bismuth titanium niobate calcium lithium cerium based ceramic disk；
(5) by galactic pole
Brush upper the denseest after the additive Mn bismuth titanium niobate calcium lithium cerium based ceramic disk surfaces obtained after above-mentioned sintering is polished to 0.5mm again The silver slurry that degree is 10at%, then makes sample at temperature 700 DEG C sintering 10min.Put into sample in the silicone oil bath of 180 DEG C Row polarization, Polarization field strength is 12kV/mm, and the dwell time is 20min, makes 1#Additive Mn bismuth titanium niobate calcium lithium cerio piezoelectricity is made pottery Porcelain.
Embodiment 2:
(1) solid phase method prepares CBT based ceramic powder body
Raw material is pressed formula Ca0.85(Li,Ce)0.075Bi4Ti3.98Nb0.02O15-0.01MnCO3, x=0.15, y=0.02, z=0.01, Carry out weighing, dispensing, be put in polyurethane ball-milling pot, with dehydrated alcohol as disperse medium, after planetary ball mill ball milling 12, Rotating speed is 300rpm, toasts 3h under lamp make it become dry drying, then in temperature programmed control batch-type furnace continuous warming to 850 DEG C, Insulation 2h, obtains additive Mn bismuth titanium niobate calcium lithium cerium based ceramic powder body；
(2) secondary ball milling
Prepared additive Mn bismuth titanium niobate calcium lithium cerium based ceramic powder body is put in polyurethane ball-milling pot, with dehydrated alcohol for dispersion Medium, after planetary ball mill ball milling 12h, rotating speed is 300rpm, toasts 3h and make it become dry under drying lamp；
(3) pelletize tabletting
The powder body of above-mentioned drying adds after the poly-vinyl alcohol solution that concentration is 7wt% is sufficiently mixed and carry out pelletize, then exist Pressure be pressed into diameter 10mm under 20MPa, thickness is the additive Mn bismuth titanium niobate calcium lithium cerium based ceramic disk of 0.8mm；
(4) binder removal sintering
By above-mentioned additive Mn bismuth titanium niobate calcium lithium cerium based ceramic disk at 850 DEG C of binder removals of temperature, sample is divided into three parts compiled respectively Number it is 2#、4#、5#, then by 2#At temperature 1090 DEG C, by 4#2h is sintered, by 5 at lower 1080 DEG C#At lower 1100 DEG C Sintering 2h makes additive Mn bismuth titanium niobate calcium lithium cerium based ceramic disk；
(4) binder removal sintering
By above-mentioned additive Mn bismuth titanium niobate calcium lithium cerium based ceramic disk at 850 DEG C of binder removals of temperature, then at temperature 1090 DEG C sintering 2h makes additive Mn bismuth titanium niobate calcium lithium cerium based ceramic disk；
(5) by galactic pole
Brush upper the denseest after the additive Mn bismuth titanium niobate calcium lithium cerium based ceramic disk surfaces obtained after above-mentioned sintering is polished to 0.5mm again The silver slurry that degree is 10at%, then makes sample at temperature 700 DEG C sintering 10min.Put into sample in the silicone oil bath of 180 DEG C Row polarization, Polarization field strength is 12kV/mm, and the dwell time is 20min.
Embodiment 3:
(1) solid phase method prepares CBT based ceramic powder body
Raw material is pressed respectively formula Ca0.85(Li,Ce)0.075Bi4Ti3.9Nb0.1O15-0.01MnCO3, x=0.15, y=0.10, z=0.01, Numbering 3#, carry out weighing, dispensing, be put in polyurethane ball-milling pot, with dehydrated alcohol as disperse medium, use planetary ball mill ball After mill 12, rotating speed is 300rpm, toasts 3h under lamp make it become dry drying, and then in temperature programmed control batch-type furnace, continuous warming is extremely 850 DEG C, it is incubated 2h, obtains additive Mn bismuth titanium niobate calcium lithium cerium based ceramic powder body；
(2) secondary ball milling
Prepared additive Mn bismuth titanium niobate calcium lithium cerium based ceramic powder body is put in polyurethane ball-milling pot, with dehydrated alcohol for dispersion Medium, after planetary ball mill ball milling 12h, rotating speed is 300rpm, toasts 3h and make it become dry under drying lamp；
(3) pelletize tabletting
The powder body of above-mentioned drying adds after the poly-vinyl alcohol solution that concentration is 7wt% is sufficiently mixed and carry out pelletize, then exist Pressure be pressed into diameter 10mm under 20MPa, thickness is the additive Mn bismuth titanium niobate calcium lithium cerium based ceramic disk of 0.8mm；
(4) binder removal sintering
By above-mentioned additive Mn bismuth titanium niobate calcium lithium cerium based ceramic disk at 850 DEG C of binder removals of temperature, then at temperature 1090 DEG C sintering 2h makes additive Mn bismuth titanium niobate calcium lithium cerium based ceramic disk；
(5) by galactic pole
Brush upper the denseest after the additive Mn bismuth titanium niobate calcium lithium cerium based ceramic disk surfaces obtained after above-mentioned sintering is polished to 0.5mm again The silver slurry that degree is 10at%, then makes sample at temperature 700 DEG C sintering 10min.Put into sample in the silicone oil bath of 180 DEG C Row polarization, Polarization field strength is 12kV/mm, and the dwell time is 20min.

Claims (3)

1. an additive Mn bismuth titanium niobate calcium lithium cerio piezoceramic material, it is characterised in that this ceramic material is by formula Ca1-x(Li,Ce)x/2Bi4Ti4-yNbyO15-zMnCO3Represent, 0.05≤x≤0.20 in formula, 0.00≤y≤0.10,0.01≤z≤0.10.
2. the preparation method of additive Mn bismuth titanium niobate calcium lithium cerium based ceramic material as claimed in claim 1, it is characterised in that should Method comprises the following steps:
(1) solid phase method prepares additive Mn bismuth titanium niobate calcium lithium cerium based ceramic powder body
Raw material is pressed respectively formula Ca1-x(Li,Ce)x/2Bi4Ti4-yNbyO15-zMnCO3, wherein x, y, z represents lithium, cerium respectively (Li, Ce), niobium (Nb) and the molar fraction of manganese (Mn) element, the scope of numerical value is: 0.05≤x≤0.20,0.00≤y≤0.10, 0.01≤z≤0.10；Doped chemical adds with oxide or carbonate for raw material, carries out weighing, dispensing, is put in polyurethane ball milling In tank, with dehydrated alcohol as disperse medium, after planetary ball mill ball milling 8～24h, rotating speed is 100～450rpm, is drying Toasting 2～3h under lamp, then in temperature programmed control batch-type furnace, continuous warming, to 800～950 DEG C, is incubated 2～4h, obtains manganese and mix Miscellaneous bismuth titanium niobate calcium lithium cerium based ceramic powder body；
(2) secondary ball milling
Prepared additive Mn bismuth titanium niobate calcium lithium cerium based ceramic powder body is put in polyurethane ball-milling pot, with dehydrated alcohol for dispersion Medium, after planetary ball mill ball milling 8～24h, rotating speed is 100～450rpm, toasts 2～3h under drying lamp；
(3) pelletize tabletting
The powder body of above-mentioned drying adds after the poly-vinyl alcohol solution that concentration is 5～10at% is sufficiently mixed and carry out pelletize, so After under pressure is 16～20MPa, be pressed into diameter 10～15mm, thickness be 0.8～1.2mm additive Mn bismuth titanium niobate Calcium lithium cerium based ceramic disk；
(4) binder removal sintering
By above-mentioned additive Mn bismuth titanium niobate calcium lithium cerium based ceramic disk at temperature 700～950 DEG C of binder removals, then in temperature 1000 DEG C～1200 DEG C sintering 2～4h make additive Mn bismuth titanium niobate calcium lithium cerium based ceramic disk；
(5) by galactic pole
After the additive Mn bismuth titanium niobate calcium lithium cerium based ceramic disk surfaces obtained after above-mentioned sintering is polished to 0.4～0.6mm again On brush, concentration is the silver slurry of 5～15wt%, then makes sample in temperature 700～800 DEG C of sintering 10～15min.Sample is put Entering in the silicone oil bath of 120～250 DEG C and polarize, Polarization field strength is 8～15kV/mm, and the dwell time is 15～45min, system Become additive Mn bismuth titanium niobate calcium lithium cerio piezoelectric ceramics.
3. the purposes of additive Mn bismuth titanium niobate calcium lithium cerium based ceramic material as claimed in claim 1, it is characterised in that this manganese is mixed Miscellaneous bismuth titanium niobate calcium lithium cerium based ceramic material in high temperature environments for piezoelectric transducer, transducer, driver, wave filter with And capacitor element.
CN201610206658.7A 2016-04-05 2016-04-05 Manganese-doped cerium lithium calcium titanoniobate-based ceramic material and preparation method thereof Pending CN105837200A (en)

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CN110078508A (en) * 2019-05-07 2019-08-02 哈尔滨工业大学 A kind of additive Mn niobium indium zincic acid lead-lead titanate piezoelectric ceramics, preparation method and applications
CN110698195A (en) * 2019-11-12 2020-01-17 杭州电子科技大学 High-resistivity and high-voltage electroactive bismuth calcium titanate-based high-temperature piezoelectric ceramic and preparation method thereof
CN112759385A (en) * 2021-01-06 2021-05-07 中国科学院福建物质结构研究所 Perovskite ceramic material and preparation method and application thereof
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CN109369174A (en) * 2018-11-01 2019-02-22 中国科学院上海硅酸盐研究所 A kind of bismuth laminated high temperature piezoceramics and preparation method thereof
CN109369174B (en) * 2018-11-01 2021-04-16 中国科学院上海硅酸盐研究所 Bismuth layer-structured high-temperature piezoelectric ceramic material and preparation method thereof
CN110078508A (en) * 2019-05-07 2019-08-02 哈尔滨工业大学 A kind of additive Mn niobium indium zincic acid lead-lead titanate piezoelectric ceramics, preparation method and applications
CN110078508B (en) * 2019-05-07 2021-09-10 哈尔滨工业大学 Manganese-doped lead indium niobate zincate-lead titanate piezoelectric ceramic, and preparation method and application thereof
CN110698195A (en) * 2019-11-12 2020-01-17 杭州电子科技大学 High-resistivity and high-voltage electroactive bismuth calcium titanate-based high-temperature piezoelectric ceramic and preparation method thereof
CN110698195B (en) * 2019-11-12 2022-05-17 杭州电子科技大学 High-resistivity and high-piezoelectric-activity bismuth calcium titanate-based high-temperature piezoelectric ceramic and preparation method thereof
CN112759385A (en) * 2021-01-06 2021-05-07 中国科学院福建物质结构研究所 Perovskite ceramic material and preparation method and application thereof
CN112759385B (en) * 2021-01-06 2021-12-14 中国科学院福建物质结构研究所 Perovskite ceramic material and preparation method and application thereof
CN114455944A (en) * 2022-01-28 2022-05-10 厦门乃尔电子有限公司 Bismuth layer-structured piezoelectric ceramic material and preparation method thereof
CN114455944B (en) * 2022-01-28 2022-11-11 厦门乃尔电子有限公司 Bismuth layer-structured piezoelectric ceramic material and preparation method thereof
CN116120054A (en) * 2023-02-10 2023-05-16 厦门乃尔电子有限公司 Bismuth calcium titanate-based piezoelectric ceramic material and preparation method thereof
CN116120054B (en) * 2023-02-10 2024-03-12 厦门乃尔电子有限公司 Bismuth calcium titanate-based piezoelectric ceramic material and preparation method thereof

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