CN101823875A - Zinc oxide varistor material suitable for being used by electrical appliance working in high-tension inrush current and preparation method thereof - Google Patents

Zinc oxide varistor material suitable for being used by electrical appliance working in high-tension inrush current and preparation method thereof Download PDF

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CN101823875A
CN101823875A CN 201010150432 CN201010150432A CN101823875A CN 101823875 A CN101823875 A CN 101823875A CN 201010150432 CN201010150432 CN 201010150432 CN 201010150432 A CN201010150432 A CN 201010150432A CN 101823875 A CN101823875 A CN 101823875A
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zinc oxide
preparation
oxide
sintering
tension
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CN101823875B (en
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彭志坚
冯海
王成彪
付志强
岳�文
于翔
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China University of Geosciences
China University of Geosciences Beijing
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China University of Geosciences Beijing
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Abstract

The invention relates to a zinc oxide varistor material suitable for being used by an electrical appliance working in high-tension inrush current and a preparation method thereof and belongs to the field of the electronic ceramics preparation and application technology. The material comprises components according to the content: 70-98mol% of ZnO, 0.1-20mol% of Pr6011, 0.01-25mol% of cobalt oxide (Co3O4 or CoO), 0.01-25mol% of Cr2O3, 0.01-30mol% of ZrO2 and 0-5mol% of TiO2. The preparation method for the material comprises processing steps of mixing material, high-energy ball milling, drying, grinding, sieving, compression molding, sintering and silver-layer. In the zinc oxide piezoresistor slice prepared by the mateiral and the preparation method, the electric potential gradient E thereof (the corresponding electric potential gradient value when the current density is 1mA/cm<2>) is 500-2500V/mm, the nonlinear coeffieint alpha (being calculated accroding to the formula alpha which equals to 1/log(E10mA/E1mA)) is 10-15, the leakage current IL (the current density value which the 75% E corresponds to ) is 5-50mu A/cm<2>, the comprehensive property is excellent. The zinc oxide varistor material is particually suitable for being used by the electrical appliance such as a high-voltage arrester and the like working in high-tension inrush current. The invention also can be applied to fields such as household applicances and the like.

Description

A kind of zinc oxide piezoresistive material of shoving high pressure down appliance working using and preparation method thereof that is applicable to
Technical field
The present invention relates to a kind of zinc oxide piezoresistive material of shoving high pressure down appliance working using and preparation method thereof that is applicable to, belong to electronic ceramics preparation and applied technical field.
Background technology
Since the seventies in 20th century, thunder arrester was succeeded in developing with znr, in the appliance working, it was voltage dependent resistor that Zinc-oxide piezoresistor has substituted silicon carbide gradually under high pressure shoves environment.From material prescription, the Zinc-oxide piezoresistor of producing both at home and abroad adopts with zinc oxide (ZnO) mostly and adds bismuth oxide (Bi at present 2O 3), weisspiessglanz (Sb 2O 3), manganese oxide (MnO 2), chromic oxide (Cr 2O 3) and cobalt oxide (CoO or Co 3O 4) prescription (is Zinc-oxide piezoresistor to call simple bismuth in the following text) that waits metal oxide to form.Bismuth is the requirement that the performance of Zinc-oxide piezoresistor can satisfy product design to a certain extent, but bismuth be zinc oxide varistor in sintering process because additive bismuth oxide (Bi 2O 3) high volatile volatile and violent in id reaction more than 1000 ℃, causing bismuth is that zinc oxide varistor is still having some deficits aspect microtexture and the electrical property.Although make volatilization obtain to a certain degree inhibition by adding relevant additive, fundamentally also it can't be eliminated.Bismuth is that zinc oxide varistor will obtain good performance and needs just can be achieved by adding the more additive of kind, has increased the complicacy of prescription control.In order to overcome bismuth is some problems that Zinc-oxide piezoresistor exists, and people are that Zinc-oxide piezoresistor is studied to praseodymium in recent years.Praseodymium is that the zinc oxide varistor prescription is formed based on zinc oxide, adds Praseodymium trioxide (Pr 6O 11), cobalt oxide (CoO or Co 3O 4), chromic oxide (Cr 2O 3) etc., it has overcome bismuth is the inherent defect that zinc oxide piezoresistive material exists, the additive kind is less relatively.Praseodymium is that the zinc oxide piezoresistive material microstructure comprises zinc oxide grain and the crystal boundary two-phase mutually that is principal constituent with the Praseodymium trioxide, and the useful area that it has increased the grain boundary layer has improved through-current capability, helps improving potential gradient and reduces leakage current.At praseodymium is the different metal oxide of interpolation in the zinc oxide piezoresistive material, and piezoresistive material that can obtained performance is different, purposes is different satisfies the demand of different field electrical equipment to Zinc-oxide piezoresistor.
Summary of the invention
The present invention proposes a kind of novel zinc oxide composite ceramic voltage dependent resistor material and preparation method.The ZnO varistor material component of making of this material is simple, volatile component is few, the easier realization of doped element is accurately controlled, material microstructure is more even, fine and close, the pressure sensitive voltage height, leakage current is less, non-linear behaviour is good, is particularly suitable for the high pressure appliance working (as super extra-high voltage electric transmission and transformation equipment) that shoves down and uses.
The material prescription that the present invention proposes is characterized in that, is principal phase with zinc oxide, and adopting Praseodymium trioxide is non-linear generation oxide compound, and adopt Co, Cr, Zr, Ti oxide compound more than one as non-linear toughener and stablizer.The molar content of its component and each component is:
Zinc oxide (ZnO) 65～98mol%
Praseodymium trioxide (Pr 6O 11) 0.1～20mol%
Cobalt oxide (Co 3O 4Or CoO) 0.01～25mol%
Chromic oxide (Cr 2O 3) 0.01～25mol%
Zirconium white (ZrO 2) 0.01～30mol%
Titanium oxide (TiO 2) 0～5mol%
Above-mentioned each component is carried out batch mixing according to corresponding content, mix after the oversintering densification promptly forms the zinc oxide piezoresistive material that shoves high pressure down appliance working uses that is applicable to proposed by the invention.
The corresponding preparation method of the described material that the present invention proposes is characterized in that, its technical process comprises " batch mixing, high-energy ball milling, oven dry, grinding are sieved, compression molding, sintering and by silver " operation successively.
In above-mentioned preparation method, the molar percentage of each component calculates the quality percentage composition of each component in the prescription that proposes according to the present invention, according to the quality percentage composition of each component each component is carried out weighing.Load weighted powder carries out batch mixing in proportion, adds the dispersion agent and the binding agent of 0～10% (massfraction) simultaneously.
In above-mentioned preparation method, described high-energy ball milling adopts the wet ball-milling method, promptly adds deionized water and zirconium oxide balls and be placed on and carry out ball milling on the high energy ball mill in mixed powder.Wherein the mass ratio of mixed powder, zirconium oxide balls, deionized water is 1: (2～10): (2～5), ball milling 12～72 hours.
In above-mentioned preparation method, the constant pressure and dry method is adopted in described oven dry, and the slurry that is about to the good mixed powder of ball milling is placed down in the baking oven at normal pressure dries.100～200 ℃ of temperature, time 12-96 hour.
In above-mentioned preparation method, described grinding is carried out in agate mortar, and the described back coacervate that sieves is less than 0.15mm.
In above-mentioned preparation method, adopt dry-pressing formed method to carry out compression molding.
In above-mentioned preparation method, described agglomerating system is: sintering in electric furnace and under the air recycle to extinction environment, and 1～10 ℃/min of heat-up rate, 300～500 ℃ are incubated binder removal 1～5 hour, 1000-1500 ℃ is incubated 0.5～5 hour down under top temperature, then furnace cooling.
In above-mentioned preparation method, described is sample the two poles of the earth evenly are coated with spread special silver slurry, and insulation to be dried in 1～4 hour under 400～800 ℃ by silver process.
With the zinc oxide varistor that material prescription provided by the invention and preparation method make, (current density is 1mA/cm to its potential gradient E 2The time correspondence the potential gradient value) be 500～2500V/mm, nonlinear factor α is [according to formula α=1/log (E 10mA/ E 1mA) calculate] be＞10～50, leakage current I L(the pairing current density value of 75%E) is 5～50 μ A/cm 2, high comprehensive performance.Be specially adapted to the high pressure appliance working that shoves down and use,, also can be used for fields such as household electrical appliance as high-tension power transmission and transformation equipment etc.
Description of drawings
Fig. 1 is the x-ray diffraction pattern of the embodiment of the invention 1 obtained zinc oxide piezoresistive material;
Fig. 2 is the stereoscan photograph of the embodiment of the invention 1 obtained zinc oxide piezoresistive material;
Fig. 3 is the x-ray diffraction pattern of the embodiment of the invention 2 obtained zinc oxide piezoresistive materials;
Fig. 4 is the stereoscan photograph of the embodiment of the invention 2 obtained zinc oxide piezoresistive materials.
Embodiment
Below in conjunction with embodiment technical scheme of the present invention is described further.
The present invention proposes a kind of zinc oxide piezoresistive material and preparation method of shoving high pressure down appliance working using that be applicable to, it is characterized in that, described zinc oxide piezoresistive material is principal phase with zinc oxide, adopting Praseodymium trioxide is non-linear generation oxide compound, and adopt Co, Cr, Zr, Ti oxide compound more than one as non-linear toughener and stablizer, form through mixed sintering.Described principal phase ZnO molar content is 65～98%, Pr 6O 11Non-linear generation oxide molar percentage composition is 0.1～20%, cobalt oxide (Co 3O 4Or CoO) molar content is 0.01～25%, Cr 2O 3Molar content 0.01～25%, ZrO 2Molar content 0.01～30%, TiO 2 Molar content 0～5mol%.
Described preparation method comprises following processing step and content:
1) the design composition according to described zinc oxide piezoresistive material takes by weighing raw material, and adds the dispersion agent and the caking agent of 0～10% (massfraction).
2) alleged powder, dispersion agent and caking agent and zirconia ball, deionized water are mixed levigate on high energy ball mill, mixing in the urethane ball grinder.
3) in loft drier, the mixed powder slurry of levigate mixing was dried in 100～200 ℃ of following insulations of temperature in 12～96 hours.
4) mixed powder after will drying grinds, and selects for use the sieve of suitable order number to sieve.
5) dry-pressing formed in the mould of specifying specification and shape to the powder after grinding.
6) according to predefined sintering schedule described Zinc-oxide piezoresistor biscuit of ceramics is carried out sintering.
7) described Zinc-oxide piezoresistor ceramic sintered bodies is carried out by silver, make electrode.
8) weldering making line on silver electrode.
Resultant Zinc-oxide piezoresistor is the lividity solid.
Embodiment 1:
With commercially available analytical pure ZnO, Pr 6O 11, Co 3O 4, Cr 2O 3And ZrO 2Carry out batch mixing with mol ratio, wherein ZnO 96.5mol%, Pr 6O 111.5mol%, Co 3O 40.8mol%, Cr 2O 30.7mol%, ZrO 20.5mol%, and add 5% (massfraction) polyvinyl alcohol and 3% (massfraction) Davon C, powder by 1: 4: 2: zirconium ball: the mass ratio of deionized water drops in the Polyurethane ball grinder, at ball milling on the high energy ball mill after 48 hours, 120 ℃ of oven dry in following 72 hours are after the grinding, dry-pressing formed in air, in the loft drier, 1350 ℃ of following sintering 4 hours, 700 ℃ down insulation made electrode by silvery in 2 hours.This example gained Zinc-oxide piezoresistor is typical two phase structure by analysis, comprise ZnO mutually with based on the intergranular of praseodymium, zirconium (as Fig. 1) mutually, homogeneous grain size (as Fig. 2).The zinc oxide varistor of this example made, (current density is 1mA/cm to its potential gradient E 2The time correspondence the potential gradient value) be 1040V/mm, nonlinear factor α is [according to formula α=1/log (E 10mA/ E 1mA) calculate] be 27, leakage current I L(the pairing current density value of 75%E) is 35 μ A/cm 2
Embodiment 2:
With commercially available analytical pure ZnO, Pr 6O 11, Co 3O 4, Cr 2O 3, ZrO 2And TiO 2Carry out batch mixing with mol ratio, wherein ZnO95.0mol%, Pr 6O 112.0mol%, Co 3O 41.7mol%, Cr 2O 30.9mol%, ZrO 20.3mol%, TiO 20.1mol%, and add 5% (massfraction) polyvinyl alcohol and 3% (massfraction) Davon C, powder by 1: 4: 2: zirconium ball: the mass ratio of deionized water drops in the Polyurethane ball grinder, at ball milling on the high energy ball mill after 48 hours, 120 ℃ of oven dry in following 72 hours are after the grinding, dry-pressing formed in air, in the loft drier, 1300 ℃ of following sintering 5 hours, 700 ℃ down insulation made electrode by silvery in 2 hours.This example gained Zinc-oxide piezoresistor is typical two phase structure by analysis, comprise ZnO mutually with based on the intergranular of praseodymium, zirconium (as Fig. 3) mutually, homogeneous grain size (as Fig. 4).The zinc oxide varistor of this example made, (current density is 1mA/cm to its potential gradient E 2The time correspondence the potential gradient value) be 500V/mm, nonlinear factor α is [according to formula α=1/log (E 10mA/ E 1mA) calculate] be 47, leakage current I L(the pairing current density value of 75%E) is 12 μ A/cm 2

Claims (2)

1. one kind is applicable to the zinc oxide piezoresistive material that shoves high pressure down appliance working uses, it is characterized in that, with zinc oxide is principal phase, adopting Praseodymium trioxide is non-linear generation oxide compound, and adopt Co, Cr, Zr, Ti oxide compound more than one as non-linear toughener and stablizer, form through mixed sintering.The component of described material and content comprise ZnO 70～98mol%, Pr 6O 110.1～20mol%, cobalt oxide (Co 3O 4Or CoO) 0.01～25mol%, Cr 2O 30.01～25mol%, ZrO 20.01～30mol%, TiO 20～5mol%.
2. according to the preparation method of the described zinc oxide piezoresistive material of claim 1, it is characterized in that described material preparation method comprises " batch mixing, high-energy ball milling, oven dry, grinding are sieved, compression molding, sintering and by silver " processing step successively; Described ceramic powder adds the dispersion agent and the binding agent of 0～10% (massfraction) simultaneously in the batching when carrying out batch mixing; In the described high-energy ball milling, mixed powder: zirconium oxide balls: deionized water quality ratio is 1: (2～10): (2～5), ball milling 12～72 hours; Baking oven, 100～200 ℃ of temperature, 12～96 hours time are adopted in described oven dry; Described grinding is carried out in agate mortar; Described sieve finish after, the powder coacervate is less than 0.15mm; Described agglomerating system is: sintering in electric furnace and under the air recycle to extinction environment, 1～10 ℃/min of heat-up rate, 300～500 ℃ are incubated binder removal 1～5 hour, and 1000～1500 ℃ are incubated 0.5～5 hour down under top temperature, furnace cooling promptly gets described zinc oxide piezoresistive material then.
CN2010101504322A 2010-04-20 2010-04-20 Zinc oxide varistor material suitable for being used by electrical appliance working in high-tension inrush current and preparation method thereof Expired - Fee Related CN101823875B (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102584207A (en) * 2012-02-09 2012-07-18 江苏大学 Negative resistance temperature coefficient zinc oxide linear resistance ceramic material and preparation method
CN102584209A (en) * 2012-02-23 2012-07-18 江苏大学 ZnO-Pr6O11-base linear resistance material and preparation method thereof
CN113716952A (en) * 2021-09-10 2021-11-30 西安神电电器有限公司 Low-gradient large-current impact-stability resistor material and preparation method thereof

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101604566A (en) * 2009-07-21 2009-12-16 中国地质大学（北京） Zinc oxide piezoresistive material and preparation method that a kind of suitable electrical appliances with low surge voltage uses

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101604566A (en) * 2009-07-21 2009-12-16 中国地质大学（北京） Zinc oxide piezoresistive material and preparation method that a kind of suitable electrical appliances with low surge voltage uses

Non-Patent Citations (1)

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Title
《Journal of the European Ceramic Society》 20041231 Chul-Hong Kim et al. Microstructure and electrical properties of ZnO-ZrO2-Bi2O3-M3O4 (M=Co, Mn) varistors 2537-2546 1-2 第24卷, 2 *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102584207A (en) * 2012-02-09 2012-07-18 江苏大学 Negative resistance temperature coefficient zinc oxide linear resistance ceramic material and preparation method
CN102584209A (en) * 2012-02-23 2012-07-18 江苏大学 ZnO-Pr6O11-base linear resistance material and preparation method thereof
CN102584209B (en) * 2012-02-23 2013-10-23 江苏大学 ZnO-Pr6O11-base linear resistance material and preparation method thereof
CN113716952A (en) * 2021-09-10 2021-11-30 西安神电电器有限公司 Low-gradient large-current impact-stability resistor material and preparation method thereof

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