CN102167579B - ZnO-Bi2O3-B2O3 series voltage-sensitive material sintered at lower temperature and preparation method thereof - Google Patents
ZnO-Bi2O3-B2O3 series voltage-sensitive material sintered at lower temperature and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a ZnO-Bi2O3-B2O3 series voltage-sensitive material sintered at lower temperature, which is prepared from the following raw materials, such as ZnO, Bi2O3, TiO2, Co2O3, Cr2O3, MnCO3, NiO, Al2O3 and oxides of boron. In B2O3 terms, the additive amount of the oxides of boron is 2.2-20 parts by weight as comparison with 100 parts by weight of ZnO. The material contains no Sb2O3, has lower sintering temperature and favorable voltage-sensitive comprehensive properties. The invention also discloses a preparation method of the material, which is simple in process and easy to operate.
Description
Technical background
The invention belongs to the piezoresistive material technical field, be specifically related to a kind of low sintering ZnO-Bi
2O
3-B
2O
3It is piezoresistive material and preparation method thereof.
Background technology
Zinc-oxide piezoresistor has enjoyed investigator's attention always, and in the thunder arrester of countries in the world, is used widely owing to its excellent pressure-sensitive character since coming out.Common zinc oxide piezoresistive material all is to be staple with ZnO, through adding Bi
2O
3, Sb
2O
3, MnO
2, Co
2O
3, Cr
2O
3The sintered compact that forms by the manufacturing of ordinary electronic ceramic process Deng MOX (generally containing the 8-10 kind) (or pottery).These additives can be divided three classes by the mechanism of action: (1) promotes oxidn zinc voltage-sensitive ceramic forms the additive of grain boundary structure, like Bi
2O
3, BaO, SrO, PbO, Pr
2O
3Deng, their main influences is to promote liquid phase sintering and form trap and surface state and that zinc oxide piezoresistive material is had is non-linear; (2) improve the additive of zinc oxide pressure-sensitive ceramic electric property non-linear character, like MnO, Co
2O
3, Cr
2O
3, Al
2O
3Deng, their part is that the solid solution of donor impurity institute provides current carrier in ZnO crystal grain, rest part then forms trap and acceptor state and has improved the height of potential barrier on crystal boundary; (3) additive of raising safety is like Sb
2O
3, SiO
2, NiO, CeO
2With a small amount of frit, their main effect is to improve the stability of zinc oxide pressure-sensitive ceramic to the influence of voltage load and environment (like temperature and humidity).
According to the difference of additive, Zinc-oxide piezoresistor generally is divided into the material different system, and wherein most widely used is ZnO-Bi
2O
3-Sb
2O
3Be piezoresistive material, remove Bi in this material system
2O
3, Sb
2O
3As outside the additive, a spot of MnO, Co have also been added
2O
3, NiO, Cr
2O
3Deng transition metal oxide.Bismuth oxide (Bi in this material system
2O
3) mainly play the grain growing of promotes oxidn zinc and improve grain boundary resistance; Weisspiessglanz (Sb
2O
3) then be the growth that suppresses crystal grain through its characteristics that in sintering process, can be adsorbed in zinc oxide (ZnO) grain surface, improve the homogeneity of crystal grain.ZnO-Bi
2O
3-Sb
2O
3Be that piezoresistive material generally has the quick over-all properties of voltage preferably, but owing to have the Sb of a certain amount of inhibition grain growing
2O
3, its sintering temperature is higher, and generally between 1100 ℃-1300 ℃, high sintering temperature not only makes ceramic plate generation deformation easily, influences the coating quality of ceramic plate electrode, thereby has influence on ratio defective product, and makes low-melting component such as Bi easily
2O
3, Sb
2O
3Excessive volatilization causes the quick parameter of device voltage to descend.
Summary of the invention
The invention provides a kind of low sintering ZnO-Bi
2O
3-B
2O
3Be piezoresistive material, this material over-all properties is superior, with low cost.
The present invention also provides a kind of low sintering ZnO-Bi
2O
3-B
2O
3Be the preparation method of piezoresistive material, this method preparation technology is simple, sintering temperature is low, is suitable for suitability for industrialized production.
The present invention utilizes the oxide compound of boron to have lower fusing point on the one hand, and this low melting point oxide can effectively promote grain growing and reduce sintering temperature in the stupalith sintering process; Distinguish ability and ZnO-Bi on the other hand again
2O
3-B
2O
3Be ZnO and the Bi in the piezoresistive material
2O
3React (through the oxide compound and the Bi of boron
2O
3Between low temperature liquid phase reaction can promote additive material to improve the microtexture of voltage-sensitive ceramic at the uniform distribution of zinc oxide grain boundaries, the even growth that can control crystal grain in the reaction at interface through the oxide compound and the ZnO crystal grain of boron) characteristics.Oxide compound with right amount of boron replaces traditional grain growth inhibitor Sb in the ZnO voltage-sensitive ceramic
2O
3, realize both having reduced sintering temperature, further optimize the purpose of the quick over-all properties of voltage of material simultaneously again.
A kind of low sintering ZnO-Bi
2O
3-B
2O
3Be piezoresistive material, process: ZnO, Bi by following raw material
2O
3, TiO
2, Co
2O
3, Cr
2O
3, MnCO
3, NiO, Al
2O
3Oxide compound with boron;
Described ZnO, Bi
2O
3, TiO
2, Co
2O
3, Cr
2O
3, MnCO
3, NiO and Al
2O
3In the molar percentage of each raw material consist of:
ZnO 90.5％～96.5％；
Bi
2O
3 0.3％～5％；
TiO
2 0.1％～3％；
Co
2O
3 0.1％～2％；
Cr
2O
3 0.1％～1％；
MnCO
3 0.2％～2％；
NiO 0.1％～1％；
Al
2O
3 0.005％～0.05％；
With respect to 100 weight part ZnO, the addition of the oxide compound of described boron is with B
2O
32.2～20 weight parts are counted in conversion.
The present invention is at ZnO, Bi
2O
3, TiO
2, Co
2O
3, Cr
2O
3, MnCO
3, NiO, Al
2O
3The major ingredient of forming (is ZnO-Bi
2O
3Be piezoresistive material) in add the oxide compound of an amount of lower melting point boron, its mechanism of action is: with the oxide compound effectively growth of promotes oxidn zinc crystal grain in sintering process of lower melting point boron preferably of zinc oxide piezoresistive material compatibility, simultaneously through with Bi
2O
3Improve the voltage-sensitive ceramic microtexture with the reaction of ZnO, finally realize ZnO-Bi
2O
3Be that the piezoresistive material sintering temperature reduces, the quick over-all properties of voltage of material is further optimized simultaneously.
In order to reach better invention effect, the oxide compound of described boron is preferably boron trioxide or boric acid.
Described low sintering ZnO-Bi
2O
3-B
2O
3Be to contain boron bismuth glass and zinc borate in the microtexture of piezoresistive material mutually.
Described low sintering ZnO-Bi
2O
3-B
2O
3Be the preparation method of piezoresistive material, may further comprise the steps:
With ZnO, Bi
2O
3, TiO
2, Co
2O
3, Cr
2O
3, MnCO
3, NiO, Al
2O
3Through wet ball grinding, drying, extrusion forming and sintering, make low sintering zinc oxide piezoresistive material after mixing with the oxide compound of boron.
The condition optimization of described wet ball grinding is: with the deionized water solvent, and ball milling 2 hours～5 hours.
Described exsiccant condition optimization was: 80 ℃～95 ℃ dryings 10 hours～15 hours.
Described agglomerating condition optimization is: be warming up to 750 ℃～950 ℃ insulations 2 hours～5 hours with 120 ℃/hour～300 ℃/hour temperature rise rates.
The low sintering ZnO-Bi of the present invention
2O
3-B
2O
3Be that piezoresistive material has high voltage gradient (V
1mA>=230V/mm) with the good quick over-all properties of voltage.It particularly has crucial application potential aspect the high-voltage arrester in the line protection field.
Compare with existing zinc oxide pressure-sensitive material, the present invention has the following advantages:
The low sintering ZnO-Bi of the present invention
2O
3-B
2O
3Be that piezoresistive material does not contain Sb
2O
3, having low firing temperature, it can burn till under 750 ℃～950 ℃ conditions.
The low sintering ZnO-Bi of the present invention
2O
3-B
2O
3Be that piezoresistive material has the quick over-all properties of good voltage: (1) this low sintering ZnO-Bi
2O
3-B
2O
3Be that piezoresistive material has proper voltage gradient, high nonlinear factor and low leakage current density: at 750 ℃ of-950 ℃ of these ZnO-Bi of agglomerating
2O
3-B
2O
3Be the potential gradient V of piezoresistive material
1mA=230～420V/mm, nonlinear factor α be greater than 50, leakage current 0.75V
1mADown less than 0.5 μ A; Proper voltage gradient, high nonlinear factor and low leakage current density make it not only power consumption are little in practical application, power consumption is low, are difficult to simultaneously take place destroyed by the heating that causes own out of control; (2) this low sintering ZnO-Bi
2O
3-B
2O
3Be that piezoresistive material has high electric current discharge capacity and low pressure sensitive voltage velocity of variation: at 750 ℃ of-950 ℃ of these ZnO-Bi of agglomerating
2O
3-B
2O
3The electric current discharge capacity (twice pulse test of 8/20 μ S waveform of stipulating among the GB-10193) that is zinc oxide piezoresistive material (is example with diameter 35mm disk) is greater than 1000A/cm
3, through-flow back pressure sensitive voltage V
1mAVelocity of variation is ± (2.0～4.0) %.High discharge capacity and low pressure sensitive voltage velocity of variation make it significantly improve in surge receptivity and the stability of handling lightning impulse, igniter shock, get rid of when bearing impact isopulse property heavy current impact.(3) this low sintering ZnO-Bi
2O
3-B
2O
3Be that piezoresistive material has good ageing-resistant performance: at the ageing-resistant coefficient of 750 ℃ of-950 ℃ of these zinc oxide piezoresistive materials of agglomerating less than 0.85.
The low sintering ZnO-Bi of the present invention
2O
3-B
2O
3Be that piezoresistive material only needs when preparing once sintered forming after all raw material uniform mixing, ball milling, the extrusion forming; The preparation method is simple, need not special devices and control, the cycle is short, easy to operate, and required raw material obtains very easily; With low cost, be suitable for suitability for industrialized production.
Description of drawings
Fig. 1 is the ZnO-Bi of embodiment 1 low temperature sintering
2O
3-B
2O
3It is the powder X-ray RD thing phase collection of illustrative plates of piezoresistive material; Wherein, X-coordinate is 2 θ angles, and ordinate zou is relative intensity (intensity).
Embodiment
The present invention mainly is at ZnO-Bi
2O
3-TiO
2-Co
2O
3-Cr
2O
3-MnCO
3-NiO-Al
2O
3Add the oxide compound of an amount of lower melting point boron in the principal constituent material, make and the oxide compound effectively growth of promotes oxidn zinc crystal grain in sintering process of lower melting point boron preferably of zinc oxide piezoresistive material compatibility, simultaneously through with Bi
2O
3Improve the voltage-sensitive ceramic microtexture with the reaction of ZnO.Below in conjunction with embodiment the present invention is further specified.
Embodiment 1
The principal constituent material is made up of the raw material of following molar percentage: 94.5%ZnO, 1.18%Bi
2O
3, 0.1%TiO
2, 2%Co
2O
3, 0.1%Cr
2O
3, 2%MnCO
3, 0.1%NiO and 0.02%Al
2O
3The oxide compound of boron is a boric acid, and the addition of boric acid is with respect to 100 part by weight of zinc oxide, with B
2O
33.0 weight parts are counted in conversion.
Evenly the back is with deionized water and zirconium ball ball milling 3 hours in planetary ball mill with boric acid and principal constituent material mixing by above-mentioned consumption, and drying obtained low sintering ZnO-Bi in 12 hours under 90 ℃ then
2O
3-B
2O
3It is the voltage dependent resistor powder.With low sintering ZnO-Bi
2O
3-B
2O
3Be that the voltage dependent resistor powder adds the molding that is pressed into the disk shape, place air atmosphere to be warmed up to 850 ℃, be incubated that furnace cooling obtains low sintering ZnO-Bi after 2 hours with 300 ℃ of/hour temperature rise rates
2O
3-B
2O
3Be piezoresistive material (being sintered compact).The test portion of sintered compact is of a size of thickness 10mm, and diameter is 35mm.
In order to measure the electrical property of sintered compact sample, sintered compact is polished on 1200 order SiC sand paper, then it is cleaned in alcohol with UW, obtain sample.After coating electrode silver plasm equably on the upper and lower surfaces of sample, put into resistance furnace, silver ink firing under 300 ℃ of conditions; Be incubated 30 minutes; Grid for welding lead-in wire on the electrode silver plasm face that burns till obtains zinc oxide varistor again, is used to measure above-mentioned low sintering ZnO-Bi
2O
3-B
2O
3It is the electrical property of piezoresistive material.Dependence test method among GB/T16528-1996 and the GB 11032-2000 is adopted in the test of electrical property.
The electric performance test result is: this low sintering ZnO-Bi
2O
3-B
2O
3Be piezoresistive material potential gradient V
1mABe 380V/mm, nonlinear factor α reaches 55, leakage current 0.75V
1mALess than 0.3 μ A, electric current discharge capacity (twice pulse test of 8/20 μ S waveform of stipulating among the GB-10193) is greater than 1050A/cm down
3, through-flow back pressure sensitive voltage V
1mAVelocity of variation is ± 2.0%; The ageing-resistant coefficient of material is less than 0.8.The electric performance test result shows this low sintering ZnO-Bi
2O
3-B
2O
3Be that piezoresistive material not only has high nonlinear factor and low leakage current density but also has high electric current discharge capacity, low pressure sensitive voltage velocity of variation and low ageing-resistant coefficient, the quick excellent of its integrated voltage.
Simultaneously, this low sintering ZnO-Bi
2O
3-B
2O
3The powder that is piezoresistive material gets the XRD figure spectrum through X-ray diffraction analysis (X-ray diffraction is called for short XRD), and as shown in Figure 1, the characteristic diffraction peak from Fig. 1 can obviously see the zinc borate phase does not have Bi in this collection of illustrative plates simultaneously
2O
3The characteristic diffraction peak of phase, the lower melting point boron oxide compound of this explanation in this pressure sensitive be the growth reduction sintering temperature of promotes oxidn zinc crystal grain effectively, and can through with Bi
2O
3Form boron bismuth glass and zinc borate mutually with the crystal boundary that is reflected at of ZnO, thereby improve low sintering ZnO-Bi
2O
3-B
2O
3Be the microtexture of piezoresistive material, and optimize the over-all properties of material.
Embodiment 2
The principal constituent material is made up of the raw material of following molar percentage: 96.5%ZnO, 0.3%Bi
2O
3, 0.895%TiO
2, 0.1%Co
2O
3, 1%Cr
2O
3, 0.2%MnCO
3, 1%NiO and 0.005%Al
2O
3The oxide compound of boron is a boron trioxide, and the addition of boron trioxide is with respect to 100 part by weight of zinc oxide, with B
2O
32.2 weight parts are counted in conversion.
Evenly the back is with deionized water and zirconium ball ball milling 5 hours in planetary ball mill with boron trioxide and principal constituent material mixing by above-mentioned consumption, and drying obtained low sintering ZnO-Bi in 15 hours under 80 ℃ then
2O
3-B
2O
3It is the voltage dependent resistor powder.With low sintering ZnO-Bi
2O
3-B
2O
3Be that the voltage dependent resistor powder adds the molding that is pressed into the disk shape, place air atmosphere to be warmed up to 950 ℃, be incubated that furnace cooling obtains low sintering ZnO-Bi after 3 hours with 120 ℃ of/hour temperature rise rates
2O
3-B
2O
3Be piezoresistive material (being sintered compact).The test portion of sintered compact is of a size of thickness 10mm, and diameter is 35mm.
In order to measure the electrical property of sintered compact sample, sintered compact is polished on 1200 order SiC sand paper, then it is cleaned in alcohol with UW, obtain sample.After coating electrode silver plasm equably on the upper and lower surfaces of sample, put into resistance furnace, silver ink firing under 300 ℃ of conditions; Be incubated 30 minutes; Grid for welding lead-in wire on the electrode silver plasm face that burns till obtains zinc oxide varistor again, is used to measure above-mentioned low sintering ZnO-Bi
2O
3-B
2O
3It is the electrical property of piezoresistive material.Dependence test method among GB/T16528-1996 and the GB 11032-2000 is adopted in the test of electrical property.
The electric performance test result is: this low sintering ZnO-Bi
2O
3-B
2O
3Be piezoresistive material potential gradient V
1mABe 230V/mm, nonlinear factor α reaches 52, leakage current 0.75V
1mALess than 0.4-, electric current discharge capacity (twice pulse test of 8/20 μ S waveform of stipulating among the GB-10193) is greater than 1000A/cm down
3, through-flow back pressure sensitive voltage V
1mAVelocity of variation is ± 3.0%; The ageing-resistant coefficient of material is less than 0.8.The electric performance test result shows this low sintering ZnO-Bi
2O
3-B
2O
3Be that piezoresistive material not only has high nonlinear factor and low leakage current density, but also have high electric current discharge capacity, low pressure sensitive voltage velocity of variation and low ageing-resistant coefficient, the quick excellent of its integrated voltage.Simultaneously, contain certain boron bismuth glass and zinc borate in its microtexture of the powder X-ray RD analytical results of this piezoresistive material explanation mutually.
Embodiment 3
The principal constituent material is made up of the raw material of following molar percentage: 92.5%ZnO, 5%Bi
2O
3, 0.55%TiO
2, 0.5%Co
2O
3, 0.5%Cr
2O
3, 0.5%MnCO
3, 0.4%NiO and 0.05%Al
2O
3Boron oxide compound is a boric acid, and the addition of boric acid is with respect to 100 part by weight of zinc oxide, with B
2O
310 weight parts are counted in conversion.
Evenly the back is with deionized water and zirconium ball ball milling 3 hours in planetary ball mill with boric acid and principal constituent material mixing by above-mentioned consumption, and drying obtained low sintering ZnO-Bi in 10 hours under 95 ℃ then
2O
3-B
2O
3It is the voltage dependent resistor powder.With low sintering ZnO-Bi
2O
3-B
2O
3Be that the voltage dependent resistor powder adds the molding that is pressed into the disk shape, place air atmosphere to be warmed up to 900 ℃, be incubated that furnace cooling obtains low sintering ZnO-Bi after 3 hours with 180 ℃ of/hour temperature rise rates
2O
3-B
2O
3Be piezoresistive material (being sintered compact).The test portion of sintered compact is of a size of thickness 10mm, and diameter is 35mm.
In order to measure the electrical property of sintered compact sample, sintered compact is polished on 1200 order SiC sand paper, then it is cleaned in alcohol with UW, obtain sample.After coating electrode silver plasm equably on the upper and lower surfaces of sample, put into resistance furnace, silver ink firing under 300 ℃ of conditions; Be incubated 30 minutes; Grid for welding lead-in wire on the electrode silver plasm face that burns till obtains zinc oxide varistor again, is used to measure above-mentioned low sintering ZnO-Bi
2O
3-B
2O
3It is the electrical property of piezoresistive material.Dependence test method among GB/T16528-1996 and the GB 11032-2000 is adopted in the test of electrical property.
The electric performance test result is: this low sintering ZnO-Bi
2O
3-B
2O
3Be piezoresistive material potential gradient V
1mABe 280V/mm, nonlinear factor α reaches 58, leakage current 0.75V
1mALess than 0.3-, electric current discharge capacity (twice pulse test of 8/20 μ S waveform of stipulating among the GB-10193) is greater than 1000A/cm down
3, through-flow back pressure sensitive voltage V
1mAVelocity of variation is ± 2.5%; The ageing-resistant coefficient of material is less than 0.8.The electric performance test result shows this low sintering ZnO-Bi
2O
3-B
2O
3Be that piezoresistive material not only has high nonlinear factor and low leakage current density, but also have high electric current discharge capacity, low pressure sensitive voltage velocity of variation and low ageing-resistant coefficient, the quick excellent of its integrated voltage.Simultaneously, contain certain boron bismuth glass and zinc borate in its microtexture of the powder X-ray RD analytical results of this piezoresistive material explanation mutually.
Embodiment 4
The principal constituent material is made up of the raw material of following molar percentage: 90.5%ZnO, 4.5%Bi
2O
3, 3.0%TiO
2, 0.5%Co
2O
3, 0.5%Cr
2O
3, 0.5%MnCO
3, 0.48%NiO and 0.02%Al
2O
3Boron oxide compound is a boron trioxide, and the addition of boron trioxide is with respect to 100 part by weight of zinc oxide, with B
2O
320 weight parts are counted in conversion.
Evenly the back is with deionized water and zirconium ball ball milling 2 hours in planetary ball mill with boron trioxide and principal constituent material mixing by above-mentioned consumption, and drying obtained low sintering ZnO-Bi in 15 hours under 90 ℃ then
2O
3-B
2O
3It is the voltage dependent resistor powder.With low sintering ZnO-Bi
2O
3-B
2O
3Be that the voltage dependent resistor powder adds the molding that is pressed into the disk shape, place air atmosphere to be warmed up to 750 ℃, be incubated that furnace cooling obtains low sintering ZnO-Bi after 5 hours with 240 ℃ of/hour temperature rise rates
2O
3-B
2O
3Be piezoresistive material (being sintered compact).The test portion of sintered compact is of a size of thickness 10mm, and diameter is 35mm.
In order to measure the electrical property of sintered compact sample, sintered compact is polished on 1200 order SiC sand paper, then it is cleaned in alcohol with UW, obtain sample.After coating electrode silver plasm equably on the upper and lower surfaces of sample, put into resistance furnace, silver ink firing under 300 ℃ of conditions; Be incubated 30 minutes; Grid for welding lead-in wire on the electrode silver plasm face that burns till obtains zinc oxide varistor again, is used to measure above-mentioned low sintering ZnO-Bi
2O
3-B
2O
3It is the electrical property of piezoresistive material.Dependence test method among GB/T16528-1996 and the GB 11032-2000 is adopted in the test of electrical property.
The electric performance test result is: this low sintering ZnO-Bi
2O
3-B
2O
3Be piezoresistive material potential gradient V
1mABe 420V/mm, nonlinear factor α reaches 50, leakage current 0.75V
1mALess than 0.5 μ A, electric current discharge capacity (twice pulse test of 8/20 μ S waveform of stipulating among the GB-10193) is greater than 1000A/cm down
3, through-flow back pressure sensitive voltage V
1mAVelocity of variation is ± 4.0%; The ageing-resistant coefficient of material is less than 0.85.The electric performance test result shows this low sintering ZnO-Bi
2O
3-B
2O
3Be that piezoresistive material not only has high nonlinear factor and low leakage current density, but also have high electric current discharge capacity, low pressure sensitive voltage velocity of variation and low ageing-resistant coefficient, the quick excellent of its integrated voltage.Simultaneously, contain certain boron bismuth glass and zinc borate in its microtexture of the powder X-ray RD analytical results of this piezoresistive material explanation mutually.
Claims (4)
1. low sintering ZnO-Bi
2O
3-B
2O
3Be piezoresistive material, process: ZnO, Bi by following raw material
2O
3, TiO
2, Co
2O
3, Cr
2O
3, MnCO
3, NiO, Al
2O
3Oxide compound with boron;
Described ZnO, Bi
2O
3, TiO
2, Co
2O
3, Cr
2O
3, MnCO
3, NiO and Al
2O
3In the molar percentage of each raw material consist of:
With respect to 100 weight part ZnO, the addition of the oxide compound of described boron is with B
2O
32.2～20 weight parts are counted in conversion.
2. low sintering ZnO-Bi according to claim 1
2O
3-B
2O
3Be piezoresistive material, it is characterized in that the oxide compound of described boron is a boron trioxide.
3. low sintering ZnO-Bi according to claim 1
2O
3-B
2O
3Be piezoresistive material, it is characterized in that, described low sintering ZnO-Bi
2O
3-B
2O
3Be to contain boron bismuth glass and zinc borate in the microtexture of piezoresistive material mutually.
4. according to each described low sintering ZnO-Bi of claim 1～3
2O
3-B
2O
3Be the preparation method of piezoresistive material, may further comprise the steps:
With ZnO, Bi
2O
3, TiO
2, Co
2O
3, Cr
2O
3, MnCO
3, NiO, Al
2O
3Through wet ball grinding, drying, extrusion forming and sintering, make low sintering zinc oxide piezoresistive material after mixing with the oxide compound of boron;
The condition of described wet ball grinding is: with the deionized water solvent, and ball milling 2 hours～5 hours;
Described exsiccant condition was: 80 ℃～95 ℃ dryings 10 hours～15 hours;
Described agglomerating condition is: be warming up to 750 ℃～950 ℃ insulations 2 hours～5 hours with 120 ℃/hour～300 ℃/hour temperature rise rates.
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| CN102584206A (en) * | 2012-01-19 | 2012-07-18 | 深圳顺络电子股份有限公司 | Zinc oxide pressure-sensitive resistor raw material |
| CN102603284B (en) * | 2012-02-13 | 2014-09-03 | 深圳顺络电子股份有限公司 | Bi-based zinc oxide voltage dependent resistor material |
| CN102617126B (en) * | 2012-03-31 | 2013-09-11 | 中国科学院上海硅酸盐研究所 | Low-temperature sintered zinc oxide voltage dependent resistance material and preparation method thereof |
| CN106458761B (en) * | 2014-03-19 | 2019-08-06 | 日本碍子株式会社 | Ceramic matrix and its manufacturing method |
| CN107021749A (en) * | 2017-03-24 | 2017-08-08 | 合肥羿振电力设备有限公司 | A kind of zinc oxide piezoresistive material and preparation method thereof |
| CN112225554A (en) * | 2020-10-08 | 2021-01-15 | 烟台大学 | ZnO-Bi capable of being sintered at low temperature2O3Base low-voltage pressure-sensitive ceramic and preparation method thereof |
| CN112341186A (en) * | 2020-10-27 | 2021-02-09 | 国网电力科学研究院武汉南瑞有限责任公司 | Preparation method of zinc oxide piezoresistor with rare earth oxide additive subjected to pre-solid solution treatment |
| CN115512916A (en) * | 2022-10-20 | 2022-12-23 | 东莞易力禾电子有限公司 | Zinc oxide piezoresistor material suitable for low-temperature sintering and preparation method thereof |
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| JPS52136386A (en) * | 1976-05-10 | 1977-11-15 | Marukon Denshi Kk | Method of manufacturing ceramic varistor |
| US5770113A (en) * | 1995-03-06 | 1998-06-23 | Matsushita Electric Industrial Co., Ltd. | Zinc oxide ceramics and method for producing the same |
| CN100468582C (en) * | 2004-12-03 | 2009-03-11 | 广西新未来信息产业股份有限公司 | Nanometer doped composite low-voltage zinc oxide pressure sensitive resistor and its manufacture |
| CN100527290C (en) * | 2006-11-21 | 2009-08-12 | 广西新未来信息产业股份有限公司 | A method for microwave sintering zinc oxide pressure-sensitive resistor |
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