CN1068571C - Laminated ceramical composition containing composite substituted bismuth and preparation thereof - Google Patents

Laminated ceramical composition containing composite substituted bismuth and preparation thereof Download PDF

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CN1068571C
CN1068571C CN98122859A CN98122859A CN1068571C CN 1068571 C CN1068571 C CN 1068571C CN 98122859 A CN98122859 A CN 98122859A CN 98122859 A CN98122859 A CN 98122859A CN 1068571 C CN1068571 C CN 1068571C
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composition
compound
formula
bismuth
ion
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CN1226539A (en
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晏海学
李承恩
朱为民
李毅
周家光
倪焕尧
王志超
傅剑
鲍军
姚烈
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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 present invention relates to a laminated bismuth ceramic composition with an empty position formed by partial replacement of composite ions, and a preparing method thereof, which belongs to the field of laminated bismuth ceramic materials. The composition provided by the present invention has the general formula of (Bi2O2)<2+>(Ca<x>M<(1-x)/2-y>*yCe<(1-x)/2>Bi2Ti4O13)<2->, wherein x is more than 0.8 and less than 1.0, *y is an A empty position, M is Li, Na and K, and y is more than 0 and less than 0.05; when x is 0.90, y is 0.01, and M is Na, the composition with optimum performance can be obtained; the curie temperature of the composition reaches 866 DEG C, d33 can reach 20 PC/N, Qm is 5440, and the composition has high cubic resistance (25 to 500 DEG C); the composition can be prepared into various piezoelectric sensors, and can be widely used in a measuring aspect, a detecting aspect and an automatic control aspect under a high-temperature (500 DEG C) condition.

Description

Compound displacement contains vacant ceramic layered composition of bismuth and preparation method
The present invention relates to a class compound ion and partly replace ceramic layered composition of bismuth and the preparation method who replaces and form omission, belong to bismuth laminated piezoelectric ceramic material field.
From twentieth century since the 60 to 70's, as widespread uses such as the barium titanate of piezoceramic material, Pb-based lanthanumdoped zirconate titanates, lead titanate, especially lead titanate is because of having 490 ℃ high-curie temperature, thus under high-temperature atmosphere Ultrasonic Cleaners with oscillator and oil engine with piezoelectric elements such as vibration-measuring sensors.
On the other hand, during bismuth was ceramic layered, molecular formula was PbBi 4Ti 4O 15And CaBi 4Ti 4O 15Ceramic composition demonstrates higher Curie temperature (being respectively 570 ℃ and 790 ℃) and good piezoelectricity, has proposed to replace as lead titanate the piezoceramic material of usefulness.
Calcium-bismuth-titanium system is the piezoceramic material of an eka-bismuth layered-type compound, and it is formed general formula and can be write as: (Bi 2O 2) 2+(A M-1B mO 3m+1) 2-, wherein A is suitable for 12 coordinate one, two, three, quadrivalent cation or theirs is compound; B be suitable for octahedral coordination three, four, five, sexavalence positively charged ion or theirs is compound; M is a positive integer, the lamellated number of plies of expression bismuth, and its value is 1-5.L.KORZUNOVA passes through at CaBi 4Ti 4O 15Middle 7～the 10wt%BiWO that adds 6And 0.2wt%Cr 2O 3Sintering temperature is reduced, make d 33From 4.4 * 10 -12Bring up to (10～14) * 10 -12, and the further raising of heating and cooling stability, but regrettably this constituent is being stable below 700 ℃ only, and desire using him to advise adopting Bi more than 800 ℃ 3TiNbO 9The systematize compound; SU1458356A and for example, the contriver is at CaBi 4Ti 4O 15Also add BiWO in the system 6And Cr 2O 3(concrete component sees Table 1) can make Curie temperature bring up to 865 even 875, the highest d 33Reach 16.1, but corresponding quality factor is very low, has only 3817.As can be seen from Table 1, Ca-Bi-Ti system up to now, Tc has improved and has surpassed 850 ℃ after modification, but d 33Between 14～16, and d 33Qm is lower than 4000 after surpassing 15.So still have unsatisfactory part.How further to improve the performance of Ca-Bi-Ti based material, become the target that this area scientific research personnel lays siege to.Table 1 has been reported the rerum natura of stupalith
Numbering Constituent Performance Data Source
Tc (℃) d 33(PC/N) ε 33T/ε 0 tanδ (％) Qm
1 PbBi 4Ti 4O 15 790 4.4 130 LANDOLT-BORNSTEIN Vol.16.P.239
2 PbBi 4Ti 4O 15Add Cr 2O 3 0.2wt％ Bi 2WO 67～10wt％ ＜700 10～ 14 L.KORZUNOVA Ferroelectrics,Vol.134, P.175～180(1992)
3 CaBi 4Ti 4O 15 98.27wt％ Bi 2WO 6 1.72wt％ Cr 2O 3 0.01wt％ 865 14.0 121 0.23 5230 HOBHKOBA waits Su 1458356 A1
4 CaBi 4Ti 4O 15 97.62wt％ Bi 2WO 6 2.18wt％ Cr 2O 3 0.20wt％ 865 16.1 118 0.37 3817 The same
5 CaBi 4Ti 4O 15 98.24wt％ Bi 2WO 6 1.71wt％ Cr 2O 3 0.05wt％ 865 14.2 120 0.24 4013 The same
The object of the present invention is to provide a class partly to replace to replace and form vacant ceramic layered constituent of bismuth and corresponding preparation method thereof through compound ion.Make it on existing other people working foundation, when Curie temperature improves, make that body resistivity further improves under the piezoelectric property of material and the high temperature.
CaBi when specifically, the present invention is directed in the Ca-Bi-Ti system m=4 4Ti 4O 15Bismuth laminated piezoelectric ceramic is by A position Ca 2+Partly replace replacement by compound ion, compound substitution ion is (Na +, Ce 3+) or (K +, Ce 3+) or (Li +, Ce 3+), and have a mind to form monovalence M +The ion room, it forms general formula is (Bi 2O 2) 2+[Ca xM (1-x)/2-y_ yCe (1-x)/2Bi 2Ti 4O 13] 2-(0.8＜x in the formula＜1.0, _ y is M +Ion vacancy, 0.00＜y＜0.05).Work as y=0, that is form when vacant, then (M +, Ce 3+) the compound displacement general formula of part is Ca xM (1-x)/2Ce (1-x)/2Bi 4Ti 4O 15(M +Be the monovalent base metal ion, as: Na +, K +, Li +).
As (Na +, Ce 3+) compound replacement and forming when vacant, its composition general formula is:
(Bi 2O 2) 2+[Ca xNa [(1-x)/2]-y_ yCe (1-x)/2Bi 2Ti 4O 13] 2-
0.8＜x in the formula＜1.0,0＜y＜0.05;
As (Li +, Ce 3+) compound replacement and forming when vacant, its composition general formula is:
(Bi 2O 2) 2+[Ca xLi [(1-x)/2]-y_ yCe (1-x)/2Bi 2Ti 4O 13] 2-
0.8＜x in the formula＜1.0,0＜y＜0.05;
As (K +, Ce 3+) compound replacement and forming when vacant, its composition general formula is:
(Bi 2O 2) 2+[Ca xK [(1-x)/2]-y_ yCe (1-x)/2Bi 2Ti 4O 13] 2-
0.8＜x in the formula＜1.0,0＜y＜0.05;
Through compound replacement and vacant Ca-Bi-Ti is arranged is the ceramic layered constituent of bismuth, adopt general piezoelectric ceramics to prepare industry and be prepared, in order to make CeO 2Ce in the raw material 4+Be converted into Ce 3+, having adopted pre-synthesis technique, concrete preparation method is:
With Na 2CO 3(or K 2CO 3Or Li 2CO 3, chemical pure), TiO 2(electrical condenser specification) and CeO 2(technical pure) is raw material, by (Na) 0.5-y(_) y(Ce) 0.5TiO 3The stoichiometry weighing, add the citric acid (analytical pure) of 4～6wt% again, with raw spirit as medium, mixed 6～8 hours through ball milling, it is synthetic in advance under 400 ℃/30 minutes condition in the aluminum oxide crucible of semitight to pack into after the oven dry, after sieving then, in the alumina crucible of packing into, powder was synthetic in 1000 ℃/2 hours, sieving for standby.At last with above-mentioned synthetics and Ca (OH) 2(chemical pure), TiO 2And Bi 2O 3Raw materials such as (purity are 99.9%) is pressed Ca 0.92(Na, Ce) 0.04Bi 4Ti 4O 15And Ca0.90 (Na) 0.04_ 0.01Ce 0.05Bi 4Ti 4O 15Etc. a series of chemical formula weighing (seeing embodiment for details), mix through ball milling again, unlimited powder was synthetic in 850 ℃/4 hours, (forming pressure is 150～200MPa), (200 ℃ of plastic removals (800 ℃/1 hour), sintering (1100～1170 ℃/1～3 hour), cold working, ultrasonic cleaning, top electrode (vacuum metallizing), polarization through ball milling fine grinding, oven dry, adding additives, moulding again, 7～10kv/mm, 20～30 minutes), give birth to and can test at last, promptly operational high-temperature piezoelectric ceramic component.
The optimum performance (specifically seeing table 2 for details) that is the ceramic layered constituent of bismuth with the Ca-Bi-Ti through modification formation A omission provided by the invention is: ε 33T/ ε 0=135, tan δ=0.11%, Tc=866 ℃, d 33=20pc/N under room temperature and high temperature, has bigger body resistivity (ρ ν (25 ℃)=10 12Ω cm, ρ ν (100 ℃)=5.3 * 10 10Ω cm, ρ ν (200 ℃)=5.3 * 10 10Ω cm, ρ ν (300 ℃)=7 * 10 9Ω cm, ρ ν (400 ℃)=8 * 10 8Ω cm, ρ ν (450 ℃)=1.3 * 10 8Ω cm, ρ ν (500 ℃)=1.2 * 10 7Ω cm), can make different shape, dimension (diameter, length or width) 5～150mm, the piezo ceramic element of thick 0.2～1mm, and can in room temperature to 500 ℃ scope, use repeatedly.Utilize the ceramic component of this material, be assembled into various piezoelectric transducers, be expected to obtain widespread use aspect measurement, detection and the automatic control under hot conditions.
This shows that the present invention has outstanding effect.
1. improved the Curie temperature (bringing up to 866 ℃) of material from 570 ℃
2. improved material piezo-electric modulus (from 4.4PC/N bring up to 17PC/N with
20PC/N)
3. improved the Qm (reaching 5440) of material;
4. improved the temperature profile of resistivity under 300 ℃～500 ℃ of material.
Further specify the present invention below in conjunction with embodiment.Obviously, embodiment only illustrates goal of the invention, limits the present invention absolutely not.
Embodiment 1:
With Na 2CO 3(chemical pure), TiO 2(electrical condenser specification) and CeO 2(technical pure) is raw material, by (Na) 0.5-y(Ce) 0.5TiO 3The stoichiometry weighing, add the citric acid (analytical pure) of 5wt% again, with raw spirit as medium, ball milling mixed 6 hours, oven dry back under the anoxybiotic condition behind 400 ℃/30 minutes pre-synthetic, the powder that carries out 1000 ℃/2 hours again is synthetic, sieving for standby.With above-mentioned synthetics, with Ca (OH) 2(chemical pure), TiO 2(electrical condenser specification) and Bi 2O 3Raw materials such as (purity are 99.9%) is got x=0.90, and y=0 is by formula Ca 0.90(Na, Ce) 0.05Bi 4Ti 4O 15Proportioning, with common ceramic preparation technology prepare burden, ball milling mixes, dry, 850 ℃/4 hours unlimited powder are synthetic, fine grinding (ball milling), oven dry, adding additives, moulding (forming pressure is 150MPa), plastic removal (800 ℃/1 hour), sintering (1120 ℃/2 hours), this moment, constituent was (Na +, Ce 3+) compound displacement and do not have Na +Vacant Ca-Bi-Ti is the stratiform constituent, and its performance perameter is listed in table 2.
Embodiment 2:
Get x=0.90, y=0.005 forms Na +Vacant _ 0.005, forming pressure 180MPa, 1130 ℃ of its sintering temperatures, other are with embodiment 1, and performance is listed in table 2.Table 2 forms Na +Vacant component and performance gather
The embodiment numbering Form Ca xNa (1-ｘ)/2-y_ yCe (1-x)/2Bi 4Ti 4O 15 Performance Sintering condition (℃)
x y Tc (℃) d 33(PC/N) ε 33T/ε 0 tanδ (％) Qm Kt Kp
1 0.90 0.000 784 16.5 131 0.14 4360 1120
2 0.90 0.005 812 18.5 133 0.12 1130
3 0.90 0.010 866 20.0 134 0.11 5440 0.29 0.052 1150
4 0.90 0.015 772 17.0 130 0.12 1170
5 0.90 0.020 770 16.0 130 0.18 1170
Embodiment 3～5:
Component/sintering condition and performance are listed in table 2, and its technological process is with embodiment 1.
Embodiment 6:
With (Na +, Ce 3+) compound replacement partly replaces and replace CaBi 4Ti 4O 15A position Ca in the pottery 2+Ion, composition consist of Ca 0.92Na 0.04Ce 0.04Bi 4Ti 40 15, its sintering condition is 1100 ℃, is incubated 1 hour, and all the other are with embodiment 1, and its performance is listed in table 3.
Embodiment 7～10:
Respectively with (Li +, Ce 3+) or (K +, Ce 3+) part displacement replacement Ca 2+Ion, composition is respectively Ca 0.92Li 0.04Ce 0.04Bi 4Ti 4O 15And Ca 0.92K 0.04Ce 0.04Bi 4Ti 4O 15And Ca 0.90Li 0.045_ 0.005Ce 0.05Bi 4Ti 4O 15And Ca 0.90K 0.035_ 0.015Ce 0.05Bi 4Ti 4O 15, its sintering condition and performance are also listed in table 3.
Table 3 (M +, Ce 3+) compound ion partly replaces and replace composition and performance and gather
The embodiment numbering Form Performance Sintering condition (℃)
Tc (℃) d 33(PC/N) ε 33T/ε 0 (％) tanδ Kt Kp
6 Ca 0.92Na 0.04Ce 0.04Bi 4Ti 4O 15 790 17.0 140 0.20 0.25 0.054 1100
7 Ca 0.92Li 0.04Ce 0.04Bi 4Ti 4O 15 800 18.0 129 0.30 0.31 0.06 1100
8 Ca 0.92K 0.04Ce 0.04Bi 4Ti 4O 15 787 17 135 0.18 0.05 1100
9 Ca 0.90Li 0.045_ 0.005Ce 0.05Bi 4Ti 4O 15 890 18 134 0.22 1115
10 Ca 0.90K 0.035_ 0.015Ce 0.05Bi 4Ti 4O 15 860 17 138 0.21 1120
Contrast as can be known from table 2 and table 3: (1) (M +, Ce 3+) compound replacement and form vacant component property the best (especially Tc and d 33); (2) (M +, Ce 3+) component property of compound replacement is than superior before replacing.(3) the Li omission is the most remarkable to improving Tc.

Claims (4)

1. a class is characterized in that through compound displacement and contain the vacant ceramic layered composition of bismuth: (1) is with (M +, Ce 3+) compound ion partly replaces and replace CaBi 4Ti 4O 15Ca in the pottery 2+
Ion, M +Be the monovalent base metal ion, the composition general formula is:
Ca xM (1-x)/2Ce (1-x)/2Bi 4Ti 4O 15(0.8＜x＜1.0); (2) partly replace on the basis of replacement at compound ion, form the monovalent ion room again, its
The composition general formula is:
(Bi 2O 2) 2+[Ca xM [(1-x)/2]-y_ yCe (1-x)/2Bi 2Ti 4O 13] 2-
0.8＜x in the formula＜1.0,0＜y＜0.05;
2. described through compound displacement and contain the vacant ceramic layered composition of bismuth by claim 1,
It is characterized in that the monovalent base metal ion can be Li, Na, K.(1) as (Na +, Ce 3+) compound replacement, its composition general formula is:
Ca xNa (1-x)/2Ce (1-x)/2Bi 4Ti 4O 15With
(Bi 2O 2) 2+[Ca xNa [(1-x)/2]-y_ yCe (1-x)/2Bi 2Ti 4O 13] 2-
0.8＜x in the formula＜1.0,0＜y＜0.05; (2) as (Li +, Ce 3+) compound replacement, its composition general formula is:
Ca xLi (1-x)/2Ce (1-x)/2Bi 4Ti 4O 15With
(Bi 2O 2) 2+[Ca xLi [(1-x)/2]-y_ yCe (1-x)/2Bi 2Ti 4O 13] 2-
0.8＜x in the formula＜1.0,0＜y＜0.05; (3) as (K +, Ce 3+) compound replacement, its composition general formula is:
CaxK (1-x)/2Ce (1-x)/2Bi 4Ti 4O 15With (Bi 2O 2) 2+[Ca xK [(1-x)/2]-y_ yCe (1-x)/2Bi 2Ti 4O 13] 2-0.8＜x in the formula＜1.0,0＜y＜0.05;
3. described through compound displacement and contain the vacant ceramic layered composition of bismuth by claim 1, it is characterized in that (Na +, Ce 3+) compound replacement, form Na +Best group becomes x=0.90 during the room, y=0.01;
4. by claim 1 or 2 or 3 described through compound displacement and contain the vacant ceramic layered preparation method of composition of bismuth, comprising Technologies such as synthetic, sintering, polarization, it is characterized in that: (1) adopts Na 2CO 3, CeO 2And TiO 2Pre-synthetic technology, its synthetic technology is when batch mixing, the analytical pure citric acid that adds 4-6wt%, pack into after the oven dry in the aluminum oxide crucible of semitight then under the anoxybiotic condition, stand 400 ℃/30 minutes pre-synthesizing, after to be cooled the sieving, the unlimited powder that carries out 1000 ℃/2 hours again is synthetic.At last with above-mentioned synthetics and chemical pure Ca (OH) 2, TiO 2With purity be 99.9% Bi 2O 3Raw material is pressed Ca 0.92(Na, Ce) 0.04Bi 4Ti 4O 15And Ca 0.90(Na) 0.04_ 0.01Ce 0.05Bi 4Ti 4O 15The chemical formula weighing mixes through ball milling again, and unlimited powder was synthetic in 850 ℃/4 hours, again through ball milling fine grinding, oven dry, adding additives, at 150～200MPa forming under the pressure, 800 ℃/1 hour plastic removal; (2) sintering temperature is 1100-1170 ℃, is incubated 1-3 hour; (3) polarization condition: 200 ℃ of temperature, voltage 7-10KV/mm, time 20-30 minute.
CN98122859A 1998-12-18 1998-12-18 Laminated ceramical composition containing composite substituted bismuth and preparation thereof Expired - Fee Related CN1068571C (en)

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Cited By (1)

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Publication number Priority date Publication date Assignee Title
CN1986485B (en) * 2006-12-25 2012-08-08 中国科学院上海硅酸盐研究所 Piezoelectric ceramic material with high bulk resistivity and laminated bismuth structure and its preparing method

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CN1994966B (en) * 2006-12-25 2012-10-03 中国科学院上海硅酸盐研究所 Laminated structure bismuth piezoelectric ceramic material stably used under high temperature and its preparation method
CN101928139B (en) * 2010-09-02 2013-04-17 同济大学 Bismuth calcium titanate-based luminous piezoelectric ceramic material and preparation method
CN104529435B (en) * 2014-12-26 2018-03-30 中国科学院声学研究所 Laminated structure bismuth piezoelectric ceramic material and preparation method thereof
CN105837200A (en) * 2016-04-05 2016-08-10 四川大学 Manganese-doped cerium lithium calcium titanoniobate-based ceramic material and preparation method thereof
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Publication number Priority date Publication date Assignee Title
CN1986485B (en) * 2006-12-25 2012-08-08 中国科学院上海硅酸盐研究所 Piezoelectric ceramic material with high bulk resistivity and laminated bismuth structure and its preparing method

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