CN102020463B - Zinc oxide piezoresistor material and preparing method thereof - Google Patents
Zinc oxide piezoresistor material and preparing method thereof Download PDFInfo
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Abstract
The present invention discloses a zinc oxide piezoresistor material comprising the following raw materials: ZnO, Bi2O3, Sb2O3, Co2O3, Cr2O3, MnCO3, NiO, Al2O3 and oxides of boron, wherein, calculating according to B2O3, the weight ratio of the oxide of boron to ZnO is 2.1-20:100; the percentages by mole of ZnO, Bi2O3, Sb2O3, Co2O3, Cr2O3, MnCO3, NiO and Al2O3 are respectively 90.5%-96.5%, 0.3%-5%, 0.1%-3%, 0.1-2%, 0.1%-1%, 0.2%-2%, 0.1%-1% and 0.005%-0.05%; and voltage-dependent combination performance of the material is good. The present invention further discloses a preparing method of the material; the method has the advantages of simple technology and low cost, and the method is suitable for industrialized production.
Description
Technical field
The present invention relates to the piezoresistive material technical field, be specifically related to a kind of high non-linearity zinc oxide piezoresistive material and preparation method thereof.
Background technology
Zinc-oxide piezoresistor has enjoyed investigator's attention always, and is used widely in the thunder arrester of countries in the world due to its excellent pressure-sensitive character since coming out.Common zinc oxide piezoresistive material is all take ZnO as main component, by adding Bi
2O
3, Sb
2O
3, Mn
O2, Co
2O
3, Cr
2O
3The sintered compact 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, 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 non-linear character, as MnO, Co
2O
3, Cr
2O
3, Al
2O
3Provide current carrier Deng, their part for the solid solution of donor impurity institute in ZnO crystal grain, rest part forms trap and acceptor state and has improved the height of potential barrier on crystal boundary; (3) improve the additive of reliability, 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 (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 additive, a small amount of MnO, Co have also been added
2O
3, NiO, Cr
2O
3Deng transition metal oxide.ZnO-Bi
2O
3-Sb
2O
3The microtexture that is piezoresistive material is comprised of grain and grain boundary two portions, and wherein crystal grain is the zinc oxide phase mutually, and Grain-Boundary Phase generally comprises rich bismuth phase and zinc antimony Spinel; This material system has the quick over-all properties of voltage preferably, but sintering temperature is higher, and high sintering temperature easily makes ceramics generation deformation first, affects the coating quality of ceramics electrode, thereby has influence on ratio defective product, second easily makes low-melting component (Bi
2O
3, Sb
2O
3) excessive volatilization, cause the quick parameter of device voltage to descend.For appropriateness reduces sintering temperature, disclose in Chinese patent application CN02122851.5 in the zinc oxide pressure-sensitive material and to have added some and help the oxide compound of grain growing, be characterized in: add a small amount of titanium oxide or boron oxide, wherein the addition of titanium oxide is no more than 5% of zinc oxide weight, and the addition of boron oxide is no more than 1% of zinc oxide weight; Its mode that adds is modulated into powder for first titanium oxide or boron oxide and other additive being mixed together pre-burning, and then the powder that is modulated into and zinc oxide are mixed to reburn forms porcelain.The preparation process relative complex although the method sintering temperature lowers to some extent, and the optimization of its main quick parameter of several voltages (nonlinear factor, leakage current, electric current discharge capacity and through-flow rear pressure sensitive voltage velocity of variation) is also undesirable.
Summary of the invention
The invention provides a kind of over-all properties zinc oxide piezoresistive material superior, with low cost.
The present invention also provides a kind of preparation method of zinc oxide piezoresistive material, and the method preparation technology is simple, cost is low, is suitable for suitability for industrialized production.
A kind of zinc oxide piezoresistive material is made by following raw material: ZnO, Bi
2O
3, Sb
2O
3, Co
2O
3, Cr
2O
3, MnCO
3, NiO, Al
2O
3Oxide compound with boron;
Wherein, the oxide compound of boron is with B
2O
3The weight ratio of counting with ZnO that converts is 2.1~20: 100;
ZnO, Bi
2O
3, Sb
2O
3, Co
2O
3, Cr
2O
3, MnCO
3, NiO and Al
2O
3In the molar percentage of each raw material consist of: 90.5%~96.5%ZnO, 0.3%~5%Bi
2O
3, 0.1%~3%Sb
2O
3, 0.1%~2%Co
2O
3, 0.1%~1%Cr
2O
3, 0.2%~2%MnCO
3, 0.1%~1%NiO and 0.005%~0.05%Al
2O
3
The present invention is at ZnO-Bi
2O
3-Sb
2O
3Be that the piezoresistive material major ingredient (is ZnO, Bi
2O
3, Sb
2O
3, Co
2O
3, Cr
2O
3, MnCO
3, NiO and Al
2O
3) in to add appropriate low melting component be the oxide compound of boron, its mechanism of action is: the oxide compound of boron is not only better compatible with the raw material of other zinc oxide piezoresistive material, and the effectively growth of accelerating oxidation zinc crystal grain in sintering process of the oxide compound of the boron of low melting point, simultaneously by with Bi
2O
3Improve the microtexture of zinc oxide piezoresistive material with the reaction of ZnO, obtain containing in microtexture boron bismuth glass and zinc borate mutually and the good zinc oxide piezoresistive material of the quick over-all properties of voltage.
Contain boron bismuth glass and zinc borate in the microtexture of described zinc oxide piezoresistive material mutually.
In order to reach better invention effect, the preferred boron trioxide of the oxide compound of described boron or boric acid.
The preparation method of described zinc oxide piezoresistive material comprises step:
With ZnO, Bi
2O
3, Sb
2O
3, Co
2O
3, Cr
2O
3, MnCO
3, NiO, Al
2O
3Through wet ball grinding, drying, extrusion forming and sintering, make zinc oxide piezoresistive material after mixing with the oxide compound of boron.
The condition optimization of described wet ball grinding is: take deionized water as solvent, and ball milling 2.5 hours~5 hours.
The condition optimization of described drying was: 80 ℃~95 ℃ dryings 10 hours~15 hours.
The condition optimization of described sintering is: be warming up to 800 ℃~1100 ℃ insulations 2.5 hours~5 hours with the temperature rise rates of 120 ℃/hour~160 ℃/hour.
Zinc oxide piezoresistive material of the present invention has high voltage gradient (V
1mA〉=250V/mm) and the good quick over-all properties of voltage.It particularly has very important application potential aspect high-voltage arrester in the line protection field.
Compared with prior art, the present invention has following advantage:
Zinc oxide piezoresistive material of the present invention has the quick over-all properties of good voltage, and (1) this zinc oxide piezoresistive material has suitable potential gradient, high nonlinear factor and low leakage current density: at the potential gradient V of this zinc oxide piezoresistive material of 800 ℃ of-1100 ℃ of sintering
1mA=250~380V/mm, nonlinear factor α be greater than 60, leakage current 0.75V
1mAUnder less than 0.3 μ A; Suitable potential gradient, high nonlinear factor and low leakage current density make it not only power consumption are little in actual applications, power consumption is low, are difficult to simultaneously occur destroyed by the heating that causes own out of control.(2) this zinc oxide piezoresistive material has high electric current discharge capacity and low pressure sensitive voltage velocity of variation: at the electric current discharge capacity (twice pulse test of 8/20 μ S waveform of stipulating in GB-10193) of this zinc oxide piezoresistive materials (take diameter 35mm disk as example) of 800 ℃ of-1100 ℃ of sintering greater than 950A/cm
3, through-flow rear 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 absoption ability and the stability of processing lightning impulse, igniter shock, get rid of when bearing impact isopulse heavy current impact.(3) this zinc oxide piezoresistive material has good ageing-resistant performance: at the ageing-resistant coefficient of this zinc oxide piezoresistive material of 800 ℃ of-1100 ℃ of sintering less than 0.85.
When preparing, zinc oxide piezoresistive material of the present invention only needs once sintered forming after the evenly mixing of all raw materials, ball milling, extrusion forming, preparation method's technique is simple, need not special equipment and control, the cycle is short, sintering temperature is lower, easy to operate, and required raw material very easily obtains, with low cost, be suitable for suitability for industrialized production.
Description of drawings
Fig. 1 is the powder X-ray RD phase collection of illustrative plates of zinc oxide piezoresistive material in embodiment 1; Wherein, X-coordinate is 2 θ angles, and ordinate zou is relative intensity (intensity);
Fig. 2 is the powder X-ray RD phase collection of illustrative plates of Comparative Examples material (being the made sample of implementation column 4 in Chinese patent application CN02122851.5); Wherein, X-coordinate is 2 θ angles, and ordinate zou is relative intensity (intensity).
Embodiment
The present invention is mainly at ZnO-Bi
2O
3-Sb
2O
3-Co
2O
3-Cr
2O
3-MnCO
3-NiO-Al
2O
3Add appropriate low melting point boron oxide compound in major ingredient, make and the low melting point boron oxide compound effectively growth of accelerating oxidation zinc crystal grain in sintering process preferably 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 constituent material is comprised of the raw material of following molar percentage: 94.5mol%ZnO, 1.18mol%Bi
2O
3, 0.1mol%Sb
2O
3, 2mol%Co
2O
3, 0.1mol%Cr
2O
3, 2mol%MnCO
3, 0.1mol%NiO and 0.02mol%Al
2O
3Boron oxide compound is boric acid, and the consumption of boric acid is with B
2O
3In conversion meter and principal constituent material, the weight ratio of zinc oxide is 3: 100.
By above-mentioned consumption with boric acid and principal constituent material mixing evenly after with deionized water and zirconium ball ball milling 3 hours in planetary ball mill, then drying obtained the Zinc-oxide piezoresistor powder in 12 hours under 90 ℃.The Zinc-oxide piezoresistor powder is added the molding that is pressed into disc-shaped, be placed in air atmosphere and be warming up to 1050 ℃ with the temperature rise rate of 150 ℃/hour, be incubated that after 3 hours, furnace cooling obtains zinc oxide piezoresistive material (being sintered compact), the test portion of this zinc oxide piezoresistive material is of a size of thickness 10mm, diameter 35mm.
Above-mentioned zinc oxide piezoresistive material 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, grid for welding lead-in wire on the electrode silver plasm face that burns till, obtain zinc oxide varistor again, is used for measuring the electrical property of above-mentioned zinc oxide piezoresistive material.Relevant test method in GB/T16528-1996 and GB 11032-2000 is adopted in the test of electrical property.
The electric performance test result is: this zinc oxide piezoresistive material potential gradient V
1mABe 280V/mm, nonlinear factor α reaches 70, leakage current 0.75V
1mAUnder less than 0.1 μ A, greater than 1000A/cm3, through-flow rear pressure sensitive voltage V1mA velocity of variation is ± 2.0% to electric current discharge capacity (twice pulse test of 8/20 μ S waveform of stipulating in GB-10193); The ageing-resistant coefficient of material is less than 0.8.
The electric performance test result shows that this zinc oxide 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, the powder X-ray RD analytical results of this zinc oxide pressure-sensitive material shows that this zinc oxide pressure-sensitive material compares it and also exist obviously different from Zinc oxide pressure sensitive (as: the made sample of implementation column 4 in Chinese patent application CN02122851.5) in the past on the microcosmic phase forms.
The powder X-ray RD analytical results of this zinc oxide piezoresistive material and Comparative Examples material (the made sample of implementation column 4 in Chinese patent application CN02122851.5) as depicted in figs. 1 and 2.
Comparison diagram 1 and Fig. 2, as can be known: the zinc oxide pressure-sensitive material in Chinese patent application CN02122851.5 has different microtextures from zinc oxide pressure-sensitive material of the present invention, there is no the zinc borate phase in the microtexture of the zinc oxide pressure-sensitive material in Chinese patent application CN02122851.5, and zinc oxide pressure-sensitive material of the present invention contains certain zinc borate phase.Contain certain bismuth oxide phase in the microtexture of the zinc oxide pressure-sensitive material in Chinese patent application CN02122851.5 simultaneously, and there is no the bismuth oxide phase in the microtexture of zinc oxide pressure-sensitive material of the present invention, the bismuth oxide that adds in this material has reacted with the oxide compound of the boron that adds in preparation process and has formed the boron bismuth glass.The performance of zinc oxide pressure-sensitive material of the present invention and microtexture presentation of results: the oxide compound of the low melting point boron that adds in the present invention effectively growth of accelerating oxidation zinc crystal grain reduces sintering temperature, and can by with Bi
2O
3Improve the microtexture of zinc oxide piezoresistive material with the reaction of ZnO, obtain containing in microtexture boron bismuth glass and zinc borate mutually and the good zinc oxide piezoresistive material of the quick over-all properties of voltage.
The principal constituent material is comprised of the raw material of following molar percentage: 96.5mol%ZnO, 0.3mol%Bi
2O
3, 0.895mol%Sb
2O
3, 0.1mol%Co
2O
3, 1mol%Cr
2O
3, 0.2mol%MnCO
3, 1mol%NiO and 0.005mol%Al
2O
3Boron oxide compound is boron trioxide, and the consumption of boron trioxide is with B
2O
3In conversion meter and principal constituent material, the weight ratio of zinc oxide is 2.1: 100.
By above-mentioned consumption with boron trioxide and principal constituent material mixing evenly after with deionized water and zirconium ball ball milling 3 hours in planetary ball mill, then drying obtained the Zinc-oxide piezoresistor powder in 12 hours under 95 ℃.The Zinc-oxide piezoresistor powder is added the molding that is pressed into disc-shaped, be placed in air atmosphere and be warming up to 1100 ℃ with the temperature rise rate of 120 ℃/hour, be incubated that after 3 hours, furnace cooling obtains zinc oxide piezoresistive material (being sintered compact), the test portion of this zinc oxide piezoresistive material is of a size of thickness 10mm, diameter 35mm.
The preparation of zinc oxide varistor is with embodiment 1.Measure the electrical property of above-mentioned zinc oxide piezoresistive material.Relevant test method in GB/T16528-1996 and GB 11032-2000 is adopted in the test of electrical property.
The electric performance test result is: this zinc oxide piezoresistive material potential gradient V
1mABe 250V/mm, nonlinear factor α reaches 62, leakage current 0.75V
1mAUnder less than 0.3 μ A, electric current discharge capacity (twice pulse test of 8/20 μ S waveform of stipulating in GB-10193) is greater than 950A/cm
3, through-flow rear pressure sensitive voltage V
1mAVelocity of variation is ± 3.0%; The ageing-resistant coefficient of material is less than 0.85.The electric performance test result shows that this zinc oxide 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, the powder X-ray RD analytical results of this zinc oxide piezoresistive material illustrates and contains certain boron bismuth glass and zinc borate in its microtexture mutually.
Embodiment 3
The principal constituent material is comprised of the raw material of following molar percentage: 92.5mol%ZnO, 5mol%Bi
2O
3, 0.55mol%Sb
2O
3, 0.5mol%Co
2O
3, 0.5mol%Cr
2O
3, 0.5mol%MnCO
3, 0.4mol%NiO and 0.05mol%Al
2O
3Boron oxide compound is boric acid, and the consumption of boric acid is with B
2O
3In conversion meter and principal constituent material, the weight ratio of zinc oxide is 10: 100.
By above-mentioned consumption with boric acid and principal constituent material mixing evenly after with deionized water and zirconium ball ball milling 3 hours in planetary ball mill, then drying obtained the Zinc-oxide piezoresistor powder in 12 hours under 85 ℃.The Zinc-oxide piezoresistor powder is added the molding that is pressed into disc-shaped, be placed in air atmosphere and be warming up to 800 ℃ with the temperature rise rate of 160 ℃/hour, be incubated that after 5 hours, furnace cooling obtains zinc oxide piezoresistive material (being sintered compact), the test portion of this zinc oxide piezoresistive material is of a size of thickness 10mm, diameter 35mm.
The preparation of zinc oxide varistor is with embodiment 1.Measure the electrical property of above-mentioned zinc oxide piezoresistive material.Relevant test method in GB/T16528-1996 and GB 11032-2000 is adopted in the test of electrical property.
The electric performance test result is: this zinc oxide piezoresistive material potential gradient V
1mABe 380V/mm, nonlinear factor α reaches 68, leakage current 0.75V
1mAUnder less than 0.2 μ A, electric current discharge capacity (twice pulse test of 8/20 μ S waveform of stipulating in GB-10193) is greater than 950A/cm
3, through-flow rear 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 that this zinc oxide 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, the powder X-ray RD analytical results of this zinc oxide piezoresistive material illustrates and contains certain boron bismuth glass and zinc borate in its microtexture mutually.
Embodiment 4
The principal constituent material is comprised of the raw material of following molar percentage: 90.5mol%ZnO, 4.5mol%Bi
2O
3, 3.0mol%Sb
2O
3, 0.5mol%Co
2O
3, 0.5mol%Cr
2O
3, 0.5mol%MnCO
3, 0.48mol%NiO and 0.02mol%Al
2O
3Boron oxide compound is boron trioxide, and the consumption of boron trioxide is with B
2O
3In conversion meter and principal constituent material, the weight ratio of zinc oxide is 20: 100.
By above-mentioned consumption with boron trioxide and principal constituent material mixing evenly after with deionized water and zirconium ball ball milling 3 hours in planetary ball mill, then drying obtained the Zinc-oxide piezoresistor powder in 12 hours under 90 ℃.The Zinc-oxide piezoresistor powder is added the molding that is pressed into disc-shaped, be placed in air atmosphere and be warming up to 900 ℃ with the temperature rise rate of 150 ℃/hour, be incubated that after 5 hours, furnace cooling obtains zinc oxide piezoresistive material (being sintered compact), the test portion of this zinc oxide piezoresistive material is of a size of thickness 10mm, diameter 35mm.
The preparation of zinc oxide varistor is with embodiment 1.Measure the electrical property of above-mentioned zinc oxide piezoresistive material.Relevant test method in GB/T16528-1996 and GB 11032-2000 is adopted in the test of electrical property.
The electric performance test result is: this zinc oxide piezoresistive material potential gradient V
1mABe 350V/mm, nonlinear factor α reaches 65, leakage current 0.75V
1mAUnder less than 0.2 μ A, electric current discharge capacity (twice pulse test of 8/20 μ S waveform of stipulating in GB-10193) is greater than 950A/cm
3, through-flow rear pressure sensitive voltage V
1mAVelocity of variation is ± 2.0%; The ageing-resistant coefficient of material is less than 0.85.The electric performance test result shows that this zinc oxide 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, the powder X-ray RD analytical results of this zinc oxide piezoresistive material illustrates and contains certain boron bismuth glass and zinc borate in its microtexture mutually.
Claims (13)
1. a zinc oxide piezoresistive material, made by following raw material: ZnO, Bi
2O
3, Sb
2O
3, Co
2O
3, Cr
2O
3, MnCO
3, NiO, Al
2O
3Oxide compound with boron;
Wherein, the oxide compound of boron is with B
2O
3The weight ratio of counting with ZnO that converts is 2.1~20:100;
ZnO, Bi
2O
3, Sb
2O
3, Co
2O
3, Cr
2O
3, MnCO
3, NiO and Al
2O
3In the molar percentage of each raw material consist of: 90.5%~96.5%ZnO, 0.3%~5%Bi
2O
3, 0.1%~3%Sb
2O
3, 0.1%~2%Co
2O
3, 0.1%~1%Cr
2O
3, 0.2%~2%MnCO
3, 0.1%~1%NiO and 0.02%~0.05%Al
2O
3
2. zinc oxide piezoresistive material as claimed in claim 1, is characterized in that, the oxide compound of described boron is boron trioxide.
3. zinc oxide piezoresistive material as claimed in claim 1, is characterized in that, contains boron bismuth glass and zinc borate in the microtexture of described zinc oxide piezoresistive material mutually.
4. as the preparation method of the described zinc oxide piezoresistive material of claim 1~3 any one, comprise step:
With ZnO, Bi
2O
3, Sb
2O
3, Co
2O
3, Cr
2O
3, MnCO
3, NiO, Al
2O
3Through wet ball grinding, drying, extrusion forming and sintering, make zinc oxide piezoresistive material after mixing with the oxide compound of boron.
5. the preparation method of zinc oxide piezoresistive material as claimed in claim 4, is characterized in that, the condition of described wet ball grinding is: take deionized water as solvent, and ball milling 2.5 hours~5 hours.
6. the preparation method of zinc oxide piezoresistive material as claimed in claim 4, is characterized in that, the condition of described drying is: 80 ℃~95 ℃ dryings 10 hours~15 hours.
7. the preparation method of zinc oxide piezoresistive material as claimed in claim 4, is characterized in that, the condition of described sintering is: be warming up to 800 ℃~1100 ℃ insulations 2.5 hours~5 hours with the temperature rise rates of 120 ℃/hour~160 ℃/hour.
8. a zinc oxide piezoresistive material, made by following raw material: ZnO, Bi
2O
3, Sb
2O
3, Co
2O
3, Cr
2O
3, MnCO
3, NiO, Al
2O
3And boric acid;
Wherein, boric acid is with B
2O
3The weight ratio of counting with ZnO that converts is 2.1~20:100;
ZnO, Bi
2O
3, Sb
2O
3, Co
2O
3, Cr
2O
3, MnCO
3, NiO and Al
2O
3In the molar percentage of each raw material consist of: 90.5%~96.5%ZnO, 0.3%~5%Bi
2O
3, 0.1%~3%Sb
2O
3, 0.1%~2%Co
2O
3, 0.1%~1%Cr
2O
3, 0.2%~2%MnCO
3, 0.1%~1%NiO and 0.02%~0.05%Al
2O
3
9. zinc oxide piezoresistive material as claimed in claim 8, is characterized in that, contains boron bismuth glass and zinc borate in the microtexture of described zinc oxide piezoresistive material mutually.
10. the preparation method of zinc oxide piezoresistive material as claimed in claim 8 or 9 comprises step:
With ZnO, Bi
2O
3, Sb
2O
3, Co
2O
3, Cr
2O
3, MnCO
3, NiO, Al
2O
3Through wet ball grinding, drying, extrusion forming and sintering, make zinc oxide piezoresistive material after mixing with boric acid.
11. the preparation method of zinc oxide piezoresistive material as claimed in claim 10 is characterized in that, the condition of described wet ball grinding is: take deionized water as solvent, and ball milling 2.5 hours~5 hours.
12. the preparation method of zinc oxide piezoresistive material as claimed in claim 10 is characterized in that, the condition of described drying was: 80 ℃~95 ℃ dryings 10 hours~15 hours.
13. the preparation method of zinc oxide piezoresistive material as claimed in claim 10 is characterized in that, the condition of described sintering is: be warming up to 800 ℃~1100 ℃ insulations 2.5 hours~5 hours with the temperature rise rates of 120 ℃/hour~160 ℃/hour.
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