CN104150900A - Low-voltage additive for ZnO varistor and preparation method thereof - Google Patents
Low-voltage additive for ZnO varistor and preparation method thereof Download PDFInfo
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- CN104150900A CN104150900A CN201410361166.6A CN201410361166A CN104150900A CN 104150900 A CN104150900 A CN 104150900A CN 201410361166 A CN201410361166 A CN 201410361166A CN 104150900 A CN104150900 A CN 104150900A
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- zno varistor
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- voltage
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Abstract
The invention discloses a low-voltage additive for a ZnO varistor and a preparation method thereof. The low-voltage additive comprises the chemical elements of Bi, Cr and O and the phase structure components of Bi2O3, Bi7.38Cr0.62O(12+x) and Bi14CrO24 and is prepared by calcining mixed powder of the Bi2O3 and Cr2O3. The mole ratio of the Bi2O3 and the Cr2O3 which are included in initial raw materials is 18:1, the calcination temperature is 750 DEG C, and the heat preserving time is 2-4 hours. The doped quantity of the additive is regulated between 3 percent by weight and 5 percent by weight according to different formulas of a ZnO varistor base body in a using process. The low-voltage additive disclosed by the invention has simple preparation process and can promote the crystal grain growth, reduce the varistor voltage of the ZnO varistor and enhance the nonlinear coefficient of the ZnO varistor to a certain degree in a sintering process.
Description
Technical field
The present invention relates to pressure sensitive, specifically a kind of additive that can reduce ZnO varistor pressure sensitive voltage and preparation method thereof.
Background technology
ZnO varistor is to take ZnO as main raw material, adds a small amount of Bi
2o
3, Co
2o
3, MnO
2, Cr
2o
3deng oxide compound, adopt traditional ceramic preparation technology's sintering to form.Because it has that nonlinear factor is high, fast response time, leakage current is little and the feature such as low cost of manufacture, has become one of most widely used piezoresistive material.Wherein low-voltage piezoresistor can be widely used in the protection of automotive industry, communication equipment, railway signal, micromachine and various electron devices; along with the miniaturization of electronic product, integrated development; to the increasing (Zhang Congchun of the demand of low voltage varistor; Zhou Dongxiang etc.; the research of low-voltage ZnO piezoresistive material and general situation of development [J] thereof, functional materials, 2001; 32(4), 343-347).
At present, ZnO varistor low pressure approach mainly contains: (1) utilizes high pressure formula, reduces the thickness of voltage-sensitive ceramic sheet.Mainly by press mold moulding, realize ceramic filming to be prepared into the lamination type piezoresistor that equivalent thickness is very little, but the method is higher to preparation technology and equipment requirements thereof, involves great expense.(2) increase the average grain size of ZnO, by seed crystal method or add the methods such as crystal grain growth substance to realize.In seed crystal method process, the preparation of seed crystal and screen length consuming time, complex process, material homogeneity is poor.Comparatively speaking, add to promote that the additive of grain growing is the effective means of current low pressureization.Yet, generally, promote that the oxide addition of grain growth can be at the nonlinear factor that reduces in varying degrees voltage dependent resistor.Therefore, prepare and a kind ofly can not reduce nonlinear factor, even increase the promotion grain growing agent of nonlinear factor, for ZnO varistor low pressureization, development is very significant.
Summary of the invention
The object of this invention is to provide a kind of additive that can reduce ZnO varistor pressure sensitive voltage.Preparation technology is simple for this additive, stable chemical nature.To adding a certain amount of this material in the initial powder of ZnO voltage-sensitive ceramic, can promote ZnO grain growth, reduce pressure sensitive voltage, and can increase to a certain extent the nonlinear factor of voltage-sensitive ceramic.
ZnO varistor low pressure additive provided by the invention, chemical element consists of Bi, Cr and O, and phase structure component is Bi
2o
3, Bi
7.38cr
0.62o
12+x(0 ﹤ x ﹤ 0.93) and Bi
14crO
24.
The preparation method of described ZnO varistor low pressure additive, its step is as follows:
(1) be in molar ratio Bi
2o
3: Cr
2o
3=18:1 weighs configuration raw material;
(2) take dehydrated alcohol or deionized water as solvent, by the Bi weighing up
2o
3and Cr
2o
3raw material mixes, ball milling 0.5-2 h;
(3) after the raw material stoving after ball milling, powder is put into crucible, or be pressed into sheet and at 750 ℃, calcine 2-4 h;
(4) powder after calcining is pulverized, ball milling, after being dried, crosses 50-100 mesh sieve, obtains ZnO varistor low pressure additive.
Foregoing preparation method, preferred scheme is: step (1) is Bi in molar ratio
2o
3: Cr
2o
3=18:1 weighs configuration raw material.
Foregoing preparation method, preferred scheme is: step (2) ball milling 0.6-1.5 h(is preferred, ball milling 1.2 h).
Foregoing preparation method, preferred scheme is: step (3) calcining 2.5-3.5 h(is preferred, 3.0h);
The application of described ZnO varistor low pressure additive, is characterized in that: consumption is that 3-5 wt%(is preferred, and consumption is 5 wt%).
ZnO varistor low pressure additive provided by the invention is by Bi, Cr, tri-kinds of elementary composition compounds of O, by Bi
2o
3phase and two kinds of green stone phase composites of Jiao, the chemical composition of its burnt green stone phase is respectively Bi
7.38cr
0.62o
12+xand Bi
14crO
24.According to the difference of ZnO varistor matrix formulation, in initial powder, add this additive of 3-5 wt%, then prepare voltage-sensitive ceramic according to traditional method, can reduce the pressure sensitive voltage of ZnO varistor.
The invention discloses a kind of ZnO varistor low pressure additive and preparation method thereof.The chemical element of this additive consists of Bi, Cr and O, and phase structure component is Bi
2o
3, Bi
7.38cr
0.62o
12+xand Bi
14crO
24.It is by Bi
2o
3and Cr
2o
3mixed powder calcining be prepared from.Bi in initial feed
2o
3and Cr
2o
3mol ratio is 18:1, and calcining temperature is 750
oc, soaking time 2-4 h.Different according to the formula of ZnO varistor matrix in use procedure, the doping of this additive is adjusted between 3-5 wt%.Advantage of the present invention is: (1) preparation technology is simple.(2) in sintering process, this additive can promote grain growth, reduces the pressure sensitive voltage of ZnO varistor, can increase to a certain extent the nonlinear factor of voltage dependent resistor simultaneously.
Accompanying drawing explanation
Fig. 1 is the XRD analysis collection of illustrative plates of ZnO varistor low pressure additive.
Embodiment
Below in conjunction with embodiment and accompanying drawing, the present invention program is described further, but protection domain is not by this restriction.
Embodiment 1: a kind of ZnO varistor low pressure additive and preparation method thereof.
1) Bi
2o
3and Cr
2o
318:1 carries out weigh batching in molar ratio, uses dehydrated alcohol as solvent, ball milling 30 min.
2) after powder is dried, grind and put into crucible, 750
oc calcines 4 h.
3) powder obtaining after calcining, through pulverizing, after ball milling is dried, regrinds and carefully crosses 50 mesh sieves, obtains additive.
4) to ZnO-Bi
2o
3-MnO
2this additive that adds respectively 0 wt%, 3wt%, 5 wt% in the initial powder of system based varistor.According to traditional voltage-sensitive ceramic preparation method, through ball milling, dry, moulding, sintering, after top electrode, the electric parameters of test voltage-sensitive ceramic sample is in Table one.
The electric property of table one: embodiment 1 sample
Fig. 1 is the XRD analysis collection of illustrative plates of ZnO varistor low pressure additive.This additive is by Bi as seen from Figure 1
2o
3, Bi
7.38cr
0.62o
12+xand Bi
14crO
24three kinds of phase composites.By table one, can find out that this additive can reduce ZnO-Bi when addition is 3wt% and 5wt%
2o
3-MnO
2the pressure-sensitive field intensity of system voltage dependent resistor has improved the nonlinear factor of voltage dependent resistor simultaneously.
Embodiment 2: a kind of ZnO varistor low pressure additive and preparation method thereof.
1) Bi
2o
3and Cr
2o
318:1 carries out weigh batching in molar ratio, uses deionized water as solvent, ball milling 1.2 h.
2), after powder is dried, become thickness to be less than the sheet of 2 mm, 750 powder pressing
oc calcines 3 h.
3) powder obtaining after calcining, through pulverizing, after ball milling is dried, regrinds and carefully crosses 100 mesh sieves, obtains additive.
4) to ZnO-Bi
2o
3-Co
2o
3this additive that adds respectively 0 wt%, 3 wt%, 5 wt% in the initial powder of system based varistor.According to traditional voltage-sensitive ceramic preparation method, through ball milling, dry, moulding, sintering, after top electrode, the electric parameters of test voltage-sensitive ceramic sample is in Table two.
The electric property of table two: embodiment 2 samples
By table two, can find out that this additive can reduce ZnO-Bi
2o
3-Co
2o
3the pressure-sensitive field intensity of system voltage dependent resistor, the while is improved the nonlinear factor of voltage dependent resistor to a certain extent.
Embodiment 3: a kind of ZnO varistor low pressure additive and preparation method thereof.
1) Bi
2o
3and Cr
2o
318:1 carries out weigh batching in molar ratio, uses dehydrated alcohol as solvent, ball milling 30 min.
2) after powder is dried, grind and put into crucible, 750
oc calcines 4 h.
3) powder obtaining after calcining, through pulverizing, after ball milling is dried, regrinds and carefully crosses 50 mesh sieves, obtains additive.
4) to ZnO-Bi
2o
3-B
2o
3this additive that adds respectively 0 wt%, 3 wt%, 4wt%, 5 wt% in initial powder etc. system based varistor.According to traditional voltage-sensitive ceramic preparation method, through ball milling, dry, moulding, sintering, after top electrode, the electric parameters of test voltage-sensitive ceramic sample is in Table three.
The electric property of table three: embodiment 3 samples
By table three, can find out that this additive, when addition is 3-5wt%, can reduce ZnO-Bi
2o
3-B
2o
3the pressure-sensitive field intensity of system voltage dependent resistor, the while is improved the nonlinear factor of voltage dependent resistor to a certain extent.
The present invention obtains the subsidy of national " 863 " plan (2013AA030801), state natural sciences fund (No.51372110, No.51302124), Shandong Province's Natural Science Fund In The Light (ZR2012EMM004).
Claims (7)
1. a ZnO varistor low pressure additive, is characterized in that: the chemical element of this additive consists of Bi, Cr and O, and phase structure component is Bi
2o
3, Bi
7.38cr
0.62o
12+xand Bi
14crO
24.
2. the preparation method of ZnO varistor low pressure additive according to claim 1, is characterized in that: step is as follows:
(1) Bi in molar ratio
2o
3: Cr
2o
3=18:1 weighs configuration raw material;
(2) take dehydrated alcohol or deionized water as solvent, by the Bi weighing up
2o
3and Cr
2o
3raw material mixes, ball milling 0.5-2 h;
(3) after the raw material stoving after ball milling, powder is put into crucible, or be pressed into sheet and at 750 ℃, calcine 2-4 h;
(4) powder after calcining is pulverized, ball milling, after being dried, crosses 50-100 mesh sieve, obtains ZnO varistor low pressure additive.
3. preparation method according to claim 2, is characterized in that: step (1) is Bi in molar ratio
2o
3: Cr
2o
3=18:1 weighs configuration raw material.
4. preparation method according to claim 2, is characterized in that: step (2) ball milling 0.6-1.5 h(is preferred, ball milling 1.2 h).
5. preparation method according to claim 2, is characterized in that: step (3) calcining 2.5-3.5 h(is preferred, 3.0h).
6. the application of ZnO varistor low pressure additive according to claim 1, is characterized in that: consumption is 3-5wt%.
7. the application of ZnO varistor low pressure additive according to claim 1, is characterized in that: consumption is that 3-5 wt%(is preferred, and consumption is 5 wt%).
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Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN108863405A (en) * | 2018-07-26 | 2018-11-23 | 聊城大学 | A kind of ZnO voltage-sensitive ceramic additive and its preparation method and application |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH10308302A (en) * | 1997-05-06 | 1998-11-17 | Osaka Prefecture | Zinc oxide-based porcelain composition and its production and zinc oxide varistor |
CN103073302A (en) * | 2013-01-21 | 2013-05-01 | 聊城大学 | Low-temperature sintering method of high potential gradient voltage-sensitive ceramic material |
-
2014
- 2014-07-28 CN CN201410361166.6A patent/CN104150900B/en not_active Expired - Fee Related
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH10308302A (en) * | 1997-05-06 | 1998-11-17 | Osaka Prefecture | Zinc oxide-based porcelain composition and its production and zinc oxide varistor |
CN103073302A (en) * | 2013-01-21 | 2013-05-01 | 聊城大学 | Low-temperature sintering method of high potential gradient voltage-sensitive ceramic material |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN108863405A (en) * | 2018-07-26 | 2018-11-23 | 聊城大学 | A kind of ZnO voltage-sensitive ceramic additive and its preparation method and application |
CN108863405B (en) * | 2018-07-26 | 2021-04-20 | 聊城大学 | ZnO pressure-sensitive ceramic additive and preparation method and application thereof |
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