CN102167579A - 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 PDF

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CN102167579A
CN102167579A CN 201010609755 CN201010609755A CN102167579A CN 102167579 A CN102167579 A CN 102167579A CN 201010609755 CN201010609755 CN 201010609755 CN 201010609755 A CN201010609755 A CN 201010609755A CN 102167579 A CN102167579 A CN 102167579A
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piezoresistive material
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CN102167579B (en
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刘丰华
许高杰
段雷
李勇
崔平
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Ningbo Institute of Material Technology and Engineering of CAS
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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

A kind of low sintering ZnO-Bi 2O 3-B 2O 3It is piezoresistive material and preparation method thereof
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 researcher's attention always, and is used widely in the arrester of countries in the world owing to its excellent pressure-sensitive character since coming out.Common zinc oxide piezoresistive material all is take ZnO as main component, by adding Bi 2O 3, Sb 2O 3, MnO 2, Co 2O 3, Cr 2O 3The sintered body that forms by the manufacturing of ordinary electronic ceramic process Deng metal oxide (generally containing the 8-10 kind) (or pottery).These additives can be divided three classes by the mechanism of action: (1) accelerating oxidation zinc voltage-sensitive ceramic forms the additive of grain boundary structure, such as Bi 2O 3, BaO, SrO, PbO, Pr 2O 3To promote liquid-phase sintering and form trap and surface state and that zinc oxide piezoresistive material is had is non-linear Deng, their main impacts; (2) improve the additive of zinc oxide pressure-sensitive ceramic electric property nonlinear characteristic, such as MnO, Co 2O 3, Cr 2O 3, Al 2O 3Deng, their part provides carrier for the solid solution of donor impurity institute in ZnO crystal grain, and remainder then forms trap and acceptor state and has improved the height of potential barrier at crystal boundary; (3) additive of raising reliability is such as Sb 2O 3, SiO 2, NiO, CeO 2With a small amount of frit, their Main Function is to improve zinc oxide pressure-sensitive ceramic to the stability of the impact of voltage load and environment (such as temperature and humidity).
According to the difference of additive, Zinc-oxide piezoresistor generally is divided into different material systems, 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 small amount 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 growth of accelerating oxidation zinc and improve grain boundary resistance; Antimony oxide (Sb 2O 3) then be the growth that suppresses crystal grain by its characteristics that in sintering process, can be adsorbed in zinc oxide (ZnO) grain surface, improve the uniformity of crystal grain.ZnO-Bi 2O 3-Sb 2O 3Be that piezoresistive material generally has the preferably quick combination property of voltage, but owing to have the Sb of a certain amount of inhibition grain growth 2O 3, its sintering temperature is higher, and generally between 1100 ℃-1300 ℃, high sintering temperature not only makes potsherd generation deformation easily, affects the coating quality of potsherd electrode, thereby has influence on ratio defective product, and makes easily low-melting component such as Bi 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 combination property 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, the standby technology of the party's legal system is simple, sintering temperature is low, is suitable for suitability for industrialized production.
The present invention utilizes the oxide of boron to have on the one hand lower fusing point, and this low melting point oxide can effectively promote grain growth and reduce sintering temperature in the ceramic material sintering process; Distinguish again on the other hand energy and ZnO-Bi 2O 3-B 2O 3Be ZnO and the Bi in the piezoresistive material 2O 3React (by oxide and the Bi of boron 2O 3Between low temperature liquid phase reaction can promote additive material to improve the microstructure of voltage-sensitive ceramic in the even distribution of zinc oxide grain boundaries, the even growth that can control crystal grain in the reaction at interface by oxide and the ZnO crystal grain of boron) characteristics.Oxide with an 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 again the purpose of the quick combination property of voltage of material simultaneously.
A kind of low sintering ZnO-Bi 2O 3-B 2O 3Be piezoresistive material, made by following raw material: ZnO, Bi 2O 3, TiO 2, Co 2O 3, Cr 2O 3, MnCO 3, NiO, Al 2O 3Oxide 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 portion ZnO, the addition of the oxide of described boron is with B 2O 32.2～20 weight portions 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 that forms (is ZnO-Bi 2O 3Be piezoresistive material) the middle oxide that adds an amount of low melting point boron, its mechanism of action is: with the preferably oxide effectively growth of accelerating oxidation zinc crystal grain in sintering process of low melting point boron of zinc oxide piezoresistive material compatibility, simultaneously by with Bi 2O 3Improve microstructure with the reaction of ZnO, finally realize ZnO-Bi 2O 3Be that the piezoresistive material sintering temperature reduces, the quick combination property 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 Firebrake ZB in the microstructure 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 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) and the good quick combination property 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 combination property of good voltage: (1) this low sintering ZnO-Bi 2O 3-B 2O 3Be that piezoresistive material has suitable electric potential gradient, high nonlinear factor and low leakage current density: at this ZnO-Bi of 750 ℃ of-950 ℃ of sintering 2O 3-B 2O 3Be the electric potential gradient V of piezoresistive material 1mA=230～420V/mm, nonlinear factor α be greater than 50, leakage current 0.75V 1mALower to 0.5 μ A; Suitable electric potential gradient, high nonlinear factor and low leakage current density so that its not only power consumption is little in actual applications, power consumption is low, be difficult to simultaneously to 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 rate of change: at this ZnO-Bi of 750 ℃ of-950 ℃ of sintering 2O 3-B 2O 3Be that the electric current discharge capacity (twice pulse test of 8/20 μ S waveform of stipulating among the GB-10193) of zinc oxide piezoresistive material (take diameter 35mm disk as example) is greater than 1000A/cm 3, through-flow rear pressure sensitive voltage V 1mARate of change is ± (2.0～4.0) %.High discharge capacity and low pressure sensitive voltage rate of change are so that it significantly improves in surge absoption ability and the stability of processing lightning impulse, igniter shock, get rid of when bearing impact isopulse 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 this zinc oxide piezoresistive material of 750 ℃ of-950 ℃ of sintering less than 0.85.
The low sintering ZnO-Bi of the present invention 2O 3-B 2O 3Be that piezoresistive material only needs once sintered forming after the evenly mixing of all raw materials, ball milling, the extrusion forming when preparing, the preparation method is simple, need not special equipment and control, the cycle is short, easy to operate, and the very easy acquisition of required raw material, 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 phase collection of illustrative plates of piezoresistive material; Wherein, abscissa is 2 θ angles, and ordinate 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 of an amount of low melting point boron in the principal component material, make and the preferably oxide effectively growth of accelerating oxidation zinc crystal grain in sintering process of low melting point boron of zinc oxide piezoresistive material compatibility, simultaneously by with Bi 2O 3Improve microstructure with the reaction of ZnO.The present invention is further described below in conjunction with embodiment.
Embodiment 1
The principal component 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 of boron is 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 portions are counted in conversion.
By above-mentioned consumption boric acid and principal component material are mixed afterwards with deionized water and zirconium ball ball milling 3 hours in planetary ball mill, 90 ℃ obtained low sintering ZnO-Bi in lower dry 12 hours then 2O 3-B 2O 3It is the piezo-resistance powder.With low sintering ZnO-Bi 2O 3-B 2O 3Be that the piezo-resistance powder adds the formed body that is pressed into disc-shaped, place air atmosphere to be warmed up to 850 ℃ with 300 ℃ of/hour heating rates, be incubated after 2 hours and obtain low sintering ZnO-Bi with the stove cooling 2O 3-B 2O 3Be piezoresistive material (being sintered body).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 ultrasonic wave, obtain sample.After coating electrode silver plasm equably on the upper and lower surface of sample, put into resistance furnace, silver ink firing under 300 ℃ of conditions, be incubated 30 minutes, welding electrode lead-in wire on the electrode silver plasm face that burns till obtains zinc oxide varistor again, is used for measuring above-mentioned low sintering ZnO-Bi 2O 3-B 2O 3It is the electrical property of piezoresistive material.Relevant 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 rate of change 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 collection of illustrative plates 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 Firebrake ZB phase does not have Bi in this collection of illustrative plates simultaneously 2O 3The characteristic diffraction peak of phase, this illustrate in this pressure sensitive the low melting point boron oxide compound effectively the growth of accelerating oxidation zinc crystal grain reduce sintering temperature, and can by with Bi 2O 3Form boron bismuth glass and Firebrake ZB mutually with the reaction of ZnO at crystal boundary, thereby improve low sintering ZnO-Bi 2O 3-B 2O 3Be the microstructure of piezoresistive material, and optimize the combination property of material.
Embodiment 2
The principal component 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 of boron is diboron trioxide, and the addition of diboron trioxide is with respect to 100 part by weight of zinc oxide, with B 2O 32.2 weight portions are counted in conversion.
By above-mentioned consumption diboron trioxide and principal component material are mixed afterwards with deionized water and zirconium ball ball milling 5 hours in planetary ball mill, 80 ℃ obtained low sintering ZnO-Bi in lower dry 15 hours then 2O 3-B 2O 3It is the piezo-resistance powder.With low sintering ZnO-Bi 2O 3-B 2O 3Be that the piezo-resistance powder adds the formed body that is pressed into disc-shaped, place air atmosphere to be warmed up to 950 ℃ with 120 ℃ of/hour heating rates, be incubated after 3 hours and obtain low sintering ZnO-Bi with the stove cooling 2O 3-B 2O 3Be piezoresistive material (being sintered body).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 ultrasonic wave, obtain sample.After coating electrode silver plasm equably on the upper and lower surface of sample, put into resistance furnace, silver ink firing under 300 ℃ of conditions, be incubated 30 minutes, welding electrode lead-in wire on the electrode silver plasm face that burns till obtains zinc oxide varistor again, is used for measuring above-mentioned low sintering ZnO-Bi 2O 3-B 2O 3It is the electrical property of piezoresistive material.Relevant 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 rate of change and low ageing-resistant coefficient, the quick excellent of its integrated voltage.Simultaneously, the powder X-ray RD analysis result of this piezoresistive material illustrates and contains certain boron bismuth glass and Firebrake ZB in its microstructure mutually.
Embodiment 3
The principal component 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 boric acid, and the addition of boric acid is with respect to 100 part by weight of zinc oxide, with B 2O 310 weight portions are counted in conversion.
By above-mentioned consumption boric acid and principal component material are mixed afterwards with deionized water and zirconium ball ball milling 3 hours in planetary ball mill, 95 ℃ obtained low sintering ZnO-Bi in lower dry 10 hours then 2O 3-B 2O 3It is the piezo-resistance powder.With low sintering ZnO-Bi 2O 3-B 2O 3Be that the piezo-resistance powder adds the formed body that is pressed into disc-shaped, place air atmosphere to be warmed up to 900 ℃ with 180 ℃ of/hour heating rates, be incubated after 3 hours and obtain low sintering ZnO-Bi with the stove cooling 2O 3-B 2O 3Be piezoresistive material (being sintered body).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 ultrasonic wave, obtain sample.After coating electrode silver plasm equably on the upper and lower surface of sample, put into resistance furnace, silver ink firing under 300 ℃ of conditions, be incubated 30 minutes, welding electrode lead-in wire on the electrode silver plasm face that burns till obtains zinc oxide varistor again, is used for measuring above-mentioned low sintering ZnO-Bi 2O 3-B 2O 3It is the electrical property of piezoresistive material.Relevant 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 rate of change and low ageing-resistant coefficient, the quick excellent of its integrated voltage.Simultaneously, the powder X-ray RD analysis result of this piezoresistive material illustrates and contains certain boron bismuth glass and Firebrake ZB in its microstructure mutually.
Embodiment 4
The principal component 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 diboron trioxide, and the addition of diboron trioxide is with respect to 100 part by weight of zinc oxide, with B 2O 320 weight portions are counted in conversion.
By above-mentioned consumption diboron trioxide and principal component material are mixed afterwards with deionized water and zirconium ball ball milling 2 hours in planetary ball mill, 90 ℃ obtained low sintering ZnO-Bi in lower dry 15 hours then 2O 3-B 2O 3It is the piezo-resistance powder.With low sintering ZnO-Bi 2O 3-B 2O 3Be that the piezo-resistance powder adds the formed body that is pressed into disc-shaped, place air atmosphere to be warmed up to 750 ℃ with 240 ℃ of/hour heating rates, be incubated after 5 hours and obtain low sintering ZnO-Bi with the stove cooling 2O 3-B 2O 3Be piezoresistive material (being sintered body).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 ultrasonic wave, obtain sample.After coating electrode silver plasm equably on the upper and lower surface of sample, put into resistance furnace, silver ink firing under 300 ℃ of conditions, be incubated 30 minutes, welding electrode lead-in wire on the electrode silver plasm face that burns till obtains zinc oxide varistor again, is used for measuring above-mentioned low sintering ZnO-Bi 2O 3-B 2O 3It is the electrical property of piezoresistive material.Relevant 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 rate of change and low ageing-resistant coefficient, the quick excellent of its integrated voltage.Simultaneously, the powder X-ray RD analysis result of this piezoresistive material illustrates and contains certain boron bismuth glass and Firebrake ZB in its microstructure mutually.

Claims (7)

1. low sintering ZnO-Bi 2O 3-B 2O 3Be piezoresistive material, made by following raw material: ZnO, Bi 2O 3, TiO 2, Co 2O 3, Cr 2O 3, MnCO 3, NiO, Al 2O 3Oxide 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 portion ZnO, the addition of the oxide of described boron is with B 2O 32.2～20 weight portions 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 of described boron is diboron trioxide or boric acid.
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 Firebrake ZB in the microstructure 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 of boron.
5. low sintering ZnO-Bi according to claim 4 2O 3-B 2O 3Be the preparation method of piezoresistive material, it is characterized in that the condition of described wet ball grinding is: take deionized water as solvent, ball milling 2 hours～5 hours.
6. low sintering ZnO-Bi according to claim 4 2O 3-B 2O 3Be the preparation method of piezoresistive material, it is characterized in that the condition of described drying is: 80 ℃～95 ℃ dryings 10 hours～15 hours.
7. low sintering ZnO-Bi according to claim 4 2O 3-B 2O 3Be the preparation method of piezoresistive material, it is characterized in that the condition of described sintering is: be warming up to 750 ℃～950 ℃ insulations 2 hours～5 hours with 120 ℃/hour～300 ℃/hour heating 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
CN102603284A (en) * 2012-02-13 2012-07-25 深圳顺络电子股份有限公司 Bi-based zinc oxide voltage dependent resistor material
CN102617126A (en) * 2012-03-31 2012-08-01 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
CN106458761A (en) * 2014-03-19 2017-02-22 日本碍子株式会社 Ceramic body and method for producing same
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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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
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CN102617126A (en) * 2012-03-31 2012-08-01 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
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CN106458761B (en) * 2014-03-19 2019-08-06 日本碍子株式会社 Ceramic matrix and its manufacturing method
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