CN1844044A - ZnO-Bi2O3 pressure-sensitive ceramic dielectric doped with rare-earth oxide - Google Patents

ZnO-Bi2O3 pressure-sensitive ceramic dielectric doped with rare-earth oxide Download PDF

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CN1844044A
CN1844044A CN 200610042720 CN200610042720A CN1844044A CN 1844044 A CN1844044 A CN 1844044A CN 200610042720 CN200610042720 CN 200610042720 CN 200610042720 A CN200610042720 A CN 200610042720A CN 1844044 A CN1844044 A CN 1844044A
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zno
earth oxide
rare
sensitive ceramic
doped
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CN100415681C (en
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李盛涛
成鹏飞
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Xian Jiaotong University
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Xian Jiaotong University
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Abstract

The invention discloses a process for preparing rare earth oxide doped ZnO-Bi2O3 family pressure-sensitive ceramic slurry, which comprises the following components (by molar portion): ZnO 91-98%, Bi2O3, Cr2O3, Co2O3, Ni2O3, MnCO3 and SiO2 each 0.1-1.0%, H3BO3 0.01-0.2%, Al(NO3)3 * 9H2O 0.001-0.01%, Sb2O3 0.5-2%, rare-earth oxide Ce2O3 or Gd2O3 0.1-1.0%.

Description

A kind of ZnO-Bi of doped with rare-earth oxide 2O 3The series pressure-sensitive ceramic medium
Technical field
The present invention relates to a kind of ZnO-Bi 2O 3Series pressure-sensitive ceramic medium, particularly a kind of doped with rare-earth oxide ZnO-Bi 2O 3The series pressure-sensitive ceramic medium.
Background technology
Improve ZnO-Bi 2O 3The conventional method of series pressure-sensitive ceramic electric potential gradient is the size that reduces ZnO crystal grain.If at ZnO-Bi 2O 3An amount of rare earth oxide mixes in the series pressure-sensitive ceramic, rare earth oxide or its formed grain boundaries that exists only in mutually, play significant " pinning " effect, obviously suppressed the growth of ZnO crystal grain, the ZnO crystallite dimension is dropped to about 5 μ m, thus corresponding electric potential gradient value can reach 400V/mm or more than.So doped with rare-earth oxide is to ZnO-Bi 2O 3Series pressure-sensitive ceramic carries out modification, is a kind of important method that improves the ceramic dielectric electric potential gradient.
At present, the emphasis about doped with rare-earth oxide mainly concentrates on the kind of additive to traditional Z nO-Bi 2O 3In the research of series pressure-sensitive ceramic microstructure impact, and for rare earth oxide doped and modified ZnO-Bi 2O 3The composition of series pressure-sensitive ceramic has had no open report.All can affect the raising of ceramic dielectric electric potential gradient and the improvement of comprehensive electrochemical properties if additive types is selected improper or addition is improper.
Summary of the invention
The objective of the invention is provides a kind of ZnO-Bi of doped with rare-earth oxide on the basis that the traditional pressure sensitive pottery forms 2O 3The composition of series pressure-sensitive ceramic prescription by conventional preparation method, can significantly improve the electric potential gradient of ceramic dielectric behind the sintering, improves the Universal electric performance.
For reaching above purpose, the present invention takes following technical scheme to be achieved:
A kind of ZnO-Bi of doped with rare-earth oxide 2O 3The series pressure-sensitive ceramic medium, by mole%, comprise that following component: ZnO is 91～98%; Bi 2O 3, Cr 2O 3, Co 2O 3, Ni 2O 3, MnCO 3And SiO 2Respectively be 0.1～1.0%; H 3BO 3Be 0.01～0.2%, Al (NO 3) 39H 2O is 0.001～0.01%; Sb 2O 3Be 0.5～2%; Rare earth oxide Ce 2O 3Or Gd 2O 3Content be 0.1～1.0%.
In the above-mentioned composition, component ZnO is preferably 94～97%; B component i 2O 3, Cr 2O 3, Co 2O 3, Ni 2O 3, MnCO 3And SiO 2Preferably respectively be 0.3～0.7%; Component H 3BO 3Be preferably 0.05～0.1%, component Al (NO 3) 39H 2O is preferably 0.002～0.006%; Component S b 2O 3Be preferably 0.7～1.2%; Rare earth oxide Ce 2O 3Or Gd 2O 3Be 0.3～0.7%; Preferably both have, and respectively be 0.3～0.7%.
Doped with rare-earth oxide ZnO-Bi provided by the present invention 2O 3The composition of series pressure-sensitive ceramic medium, by the adjustment to each additive component content, and to rare earth oxide Ce 2O 3, Gd 2O 3The single doping and the codope test, and the rational proportion of adjustment doping content, the series ceramic medium that obtains at 1100～1180 ℃ of sintering, electric potential gradient is mostly more than 450V/mm, reach as high as 520V/mm, leakage current and nonlinear exponent Universal electric performance indications are also fairly good simultaneously, and doping vario-property has obtained satisfied good effect.Pressure-sensitive ceramic dielectric of the present invention can be used for making the high-quality thunder arrester product of ultra-high/extra-high voltage power system.
Embodiment
The present invention is described in further detail below in conjunction with specific embodiment:
A kind of ZnO-Bi of doped with rare-earth oxide 2O 3The series pressure-sensitive ceramic medium, by mole%, comprise that following component: ZnO is 91～98%; Bi 2O 3, Cr 2O 3, Co 2O 3, Ni 2O 3, MnCO 3And SiO 2Respectively be 0.1～1.0%; H 3BO 3Be 0.01～0.2%, Al (NO 3) 39H 2O is 0.001～0.01%; Sb 2O 3Be 0.5～2%; Rare-earth oxide additives Ce 2O 3, Gd 2O 3Have at least a kind of; Described Ce 2O 3, Gd 2O 3Content respectively is 0.1～1.0%.List in table 1 concrete the composition, forms totally 18 of A～R.
Additive B i during the present invention forms 2O 3, its average grain diameter is at 1～10 μ m, and content is preferably between 0.3～0.7mol% between 0.1～1mol%, and content is crossed to hang down and will be caused the increase of leakage current and the reduction of nonlinear exponent; And too high levels will produce a large amount of pores because of volatilization.Additive Sb during the present invention forms 2O 3, its average grain diameter is 0.5～3 μ m, content is adjusted in 0.5～2.0mol% scope, is preferably in 0.75～1.2 scope to adjust Sb 2O 3Can improve electric potential gradient, improve the distribution of other additives in porcelain body, Sb 2O 3Content is crossed to hang down the homodisperse effect of additive can not be brought into play; And the too high ZnO crystal grain that will cause is too little, and this will affect the through-current capability of big electric current.Addition of C r during the present invention forms 2O 3, Co 2O 3, MnCO 3, Ni 2O 3, its average grain diameter is between 1～10 μ m, and each constituent content is adjusted in 0.1～1mol% scope, is preferably in 0.3～0.7mol% scope to adjust.
Table 1
Form Bi 2O 3 Sb 2O 3 Cr 2O 3 Co 2O 3 Ni 2O 3 Ce 2O 3 Gd 2O 3 SiO 2 MnCO 3 H 3BO 3 Al(NO 3) 3·9H 2O
A 0.1 2.0 0.1 1.0 0.5 0.1 0 0.5 0.1 0.2 0.001
B 0.5 1.0 0.5 0.1 1.0 0 0.1 0.1 1.0 0.01 0.01
C 1.0 0.5 1.0 0.5 0.1 0.1 0.1 1.0 0.5 0.1 0.005
D 0.3 1.2 0.3 0.7 0.5 0.3 0 0.5 0.3 0.1 0.002
E 0.5 0.7 0.5 0.3 0.7 0.5 0 0.3 0.7 0.05 0.006
F 0.7 1.0 0.7 0.5 0.3 1.0 0 0.7 0.5 0.08 0.005
G 0.5 0.7 0.5 0.5 0.7 0 0.3 0.3 0.7 0.05 0.002
H 0.5 0.7 0.5 0.5 0.7 0 0.5 0.3 0.7 0.05 0.004
I 0.5 0.7 0.5 0.5 0.7 0 0.7 0.3 0.7 0.05 0.004
J 0.5 0.7 0.5 0.5 0.7 0.3 0.3 0.3 0.7 0.05 0.004
K 0.5 0.7 0.5 0.5 0.7 0.3 0.5 0.5 0.7 0.05 0.004
L 0.5 0.7 0.5 0.5 0.7 0.3 0.7 0.7 0.7 0.05 0.004
M 0.5 0.7 0.5 0.5 0.7 0.5 0.3 0.3 0.7 0.05 0.004
N 0.5 0.7 0.5 0.5 0.7 0.5 0.5 0.3 0.7 0.05 0.004
O 0.5 0.7 0.5 0.5 0.7 0.5 0.7 0.3 0.7 0.05 0.004
P 0.5 0.7 0.5 0.3 0.7 0.7 0.3 0.3 0.7 0.05 0.006
Q 0.5 0.7 0.5 0.3 0.7 0.7 0.5 0.3 0.7 0.05 0.006
R 0.5 0.7 0.5 0.3 0.7 0.7 1.0 0.3 0.7 0.05 0.006
Remarks Composition content is molar percentage (mol%), and surplus is ZnO
Additive SiO during the present invention forms 2, its average grain diameter is between 0.3～1 μ m, and content is adjusted in 0.1～1mol% scope, is preferably in 0.3～0.7mol% scope to adjust.Additive H 3BO 3Content in 0.01～0.2mol% scope, adjust, be preferably between 0.05～0.1mol% and adjust.Additive A l (NO 3) 39H 2The content of O is lower, adjusts in 0.001～0.01mol% scope, is preferably in 0.002～0.006mol% scope to adjust.The present invention also is doped with rare earth oxide Ce in forming 2O 3Or Gd 2O 3, its average grain diameter is between 0.5～3 μ m, and content is adjusted in 0.1～1mol% scope, preferably both has, and each adjusts content in 0.3～0.7mol% scope; Doping content is excessively low, can not play the effect that suppresses the ZnO grain growth; Doping content is too high will to cause the decline of nonlinear exponent and the increase of leakage current.
The ZnO-Bi of above-mentioned doped with rare-earth oxide 2O 3The preparation method of series pressure-sensitive ceramic medium comprises the steps:
1) form A～R by table 1 and carry out the proportioning weighing, it is pure that the binder component that is adopted is reagent, and major ingredient ZnO is the technical pure of piezoresistor special use, and its median size is about 0.5 μ m.
2) after each composition and ratio weighing, respectively will be except ZnO, Al (NO 3) 39H 2All components mixing and ball milling beyond the O 20 hours is warming up to 900 ℃ of pre-burnings 30 minutes after 120 ℃ of oven dry.
3) component after the pre-burning is through pulverizing and ZnO, Al (NO again 3) 39H 2O mixes, and the polyvinyl alcohol water solution ball milling that adds 1wt% concentration was made slurry in 20 hours, then spray-dried one-tenth granulation material;
4) use the single-column press, be pressed into the disk shape green compact that are of a size of φ 26 * 9mm, form to press 6 for every kind, totally 108 of 18 compositions, binder removal under 450 ℃ ± 20 ℃ temperature together with 50 tons forming pressures.
5) be one group with per two of every kind behind binder removal composition (6), each is at 1100 ℃, and sintering is 4 hours under 1150 ℃ and 1180 ℃ of three temperature, and heating rate is 200 ℃/hour, is cooled to room temperature with 100 ℃/hour speed then; Obtain altogether 54 groups of dense sintering bodies of φ 20 * 8mm size, i.e. 18 embodiment of every kind of corresponding three different sintering temperatures of prescription, totally 54 embodiment by the aluminizing electrode, carry out electric performance test, and get its mean value after the end face polishing.
Table 2 has provided the electric performance test result of 1100 ℃ of agglomerating embodiment 1～18:
Table 2
Sample Form Potential gradient (V/mm) Leakage current (μ A) Nonlinear exponent
Embodiment 1 A 280 0.5 35
Embodiment 2 B 278 0.2 36
Embodiment 3 C 277 0.2 35
Embodiment 4 D 315 55 8
Embodiment 5 E 360 45 10
Embodiment 6 F 346 27 9
Embodiment 7 G 460 15 15
Embodiment 8 H 480 13 14
Embodiment 9 I 482 13 12
Embodiment 10 J 490 16 12
Embodiment 11 K 500 18 13
Embodiment 12 L 508 17 12
Embodiment 13 M 500 18 12
Embodiment 14 N 510 20 11
Embodiment 15 O 520 20 11
Embodiment 16 P 479 21 9
Embodiment 17 Q 465 21 9
Embodiment 18 R 470 23 8
Table 3 has provided the electric performance test result of 1150 ℃ of agglomerating embodiment 19～36:
Table 3
Sample Form Potential gradient (V/mm) Leakage current (μ A) Nonlinear exponent
Embodiment 19 A 250 0.3 40
Embodiment 20 B 246 0.2 42
Embodiment 21 C 245 0.2 39
Embodiment 22 D 316 45 12
Embodiment 23 E 335 35 14
Embodiment 24 F 341 35 13
Embodiment 25 G 456 12 19
Embodiment 26 H 476 11 18
Embodiment 27 I 478 11 16
Embodiment 28 J 487 12 16
Embodiment 29 K 450 13 17
Embodiment 30 L 455 12 16
Embodiment 31 M 485 13 16
Embodiment 32 N 486 15 15
Embodiment 33 O 486 15 15
Embodiment 34 P 435 16 13
Embodiment 35 Q 432 16 13
Embodiment 36 R 436 18 12
Table 4 has provided the electric performance test result of 1180 ℃ of agglomerating embodiment 37～54:
Table 4
Sample Form Potential gradient (V/mm) Leakage current (μ A) Nonlinear exponent
Embodiment 37 A 200 0.3 45
Embodiment 38 B 198 0.2 45
Embodiment 39 C 198 0.3 44
Embodiment 40 D 257 45 15
Embodiment 41 E 258 35 16
Embodiment 42 F 271 35 16
Embodiment 43 G 445 12 25
Embodiment 44 H 450 11 24
Embodiment 45 I 451 11 24
Embodiment 46 J 450 12 22
Embodiment 47 K 452 13 23
Embodiment 48 L 455 12 22
Embodiment 49 M 455 13 22
Embodiment 50 N 460 13 22
Embodiment 51 O 460 15 21
Embodiment 52 P 410 16 19
Embodiment 53 Q 406 16 19
Embodiment 54 R 405 18 18
Can find out from table 2, table 3, table 4 test result, form G～O at 1100 ℃ of agglomerating embodiment 7～15, at 1150 ℃ of agglomerating embodiment 25～33, at 1180 ℃ of agglomerating embodiment 43～51, all more than 450V/mm, embodiment 15 is up to 520V/mm for potential gradient; All below 20 μ A, nonlinear exponent is all more than 11 for leakage current, and embodiment 43 is up to 25; Integrated performance index is fairly good.

Claims (3)

1. the ZnO-Bi of a doped with rare-earth oxide 2O 3The series pressure-sensitive ceramic medium is characterized in that, by mole%, comprise that following component: ZnO is 91～98%; Bi 2O 3, Cr 2O 3, Co 2O 3, Ni 2O 3, MnCO 3And SiO 2Respectively be 0.1～1.0%; H 3BO 3Be 0.01～0.2%, Al (NO 3) 39H 2O is 0.001～0.01%; Sb 2O 3Be 0.5～2%; Rare earth oxide Ce 2O 3, Gd 2O 3One or both, its content respectively is 0.1～1.0%.
2. the ZnO-Bi of doped with rare-earth oxide according to claim 1 2O 3The series pressure-sensitive ceramic medium is characterized in that, by mole%, comprise that following component: ZnO is 94～97%; Bi 2O 3, Cr 2O 3, Co 2O 3, Ni 2O 3, MnCO 3And SiO 2Respectively be 0.3～0.7%H 3BO 3Be 0.05～0.1%, Al (NO 3) 39H 2O is 0.002～0.006%; Sb 2O 3Be 0.7～1.2%; Rare earth oxide Ce 2O 3, Gd 2O 3One or both, its content respectively is 0.3～0.7%.
3. the ZnO-Bi of doped with rare-earth oxide according to claim 2 2O 3The series pressure-sensitive ceramic medium is characterized in that, described rare earth oxide is Ce 2O 3And Gd 2O 3Two kinds, its content respectively is 0.3～0.7%.
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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102030522A (en) * 2010-11-17 2011-04-27 西安交通大学 Low-equilibrium temperature ZnO-Bi2O3 series voltage-sensitive ceramic dielectric
CN102557612A (en) * 2012-01-11 2012-07-11 深圳顺络电子股份有限公司 Low-dielectric-constant pressure-sensitive resistor material and preparation method thereof
WO2014101030A1 (en) * 2012-12-27 2014-07-03 Littelfuse, Inc. Zinc oxide based varistor and fabrication method
CN113979740A (en) * 2021-10-11 2022-01-28 平高集团有限公司 Pressure-sensitive ceramic additive, pressure-sensitive ceramic material, pressure-sensitive ceramic and preparation method thereof, pressure-sensitive resistor and preparation method thereof, and resistor element

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102030522A (en) * 2010-11-17 2011-04-27 西安交通大学 Low-equilibrium temperature ZnO-Bi2O3 series voltage-sensitive ceramic dielectric
CN102557612A (en) * 2012-01-11 2012-07-11 深圳顺络电子股份有限公司 Low-dielectric-constant pressure-sensitive resistor material and preparation method thereof
WO2014101030A1 (en) * 2012-12-27 2014-07-03 Littelfuse, Inc. Zinc oxide based varistor and fabrication method
TWI551568B (en) * 2012-12-27 2016-10-01 力特福斯股份有限公司 Zinc oxide based varistor and fabrication method
US9601244B2 (en) 2012-12-27 2017-03-21 Littelfuse, Inc. Zinc oxide based varistor and fabrication method
CN113979740A (en) * 2021-10-11 2022-01-28 平高集团有限公司 Pressure-sensitive ceramic additive, pressure-sensitive ceramic material, pressure-sensitive ceramic and preparation method thereof, pressure-sensitive resistor and preparation method thereof, and resistor element
CN113979740B (en) * 2021-10-11 2023-12-15 平高集团有限公司 Pressure-sensitive ceramic additive, pressure-sensitive ceramic material, pressure-sensitive ceramic and preparation method thereof, piezoresistor and preparation method thereof, and resistor element

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