CN113716952A - Low-gradient large-current impact-stability resistor material and preparation method thereof - Google Patents

Low-gradient large-current impact-stability resistor material and preparation method thereof Download PDF

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CN113716952A
CN113716952A CN202111061132.1A CN202111061132A CN113716952A CN 113716952 A CN113716952 A CN 113716952A CN 202111061132 A CN202111061132 A CN 202111061132A CN 113716952 A CN113716952 A CN 113716952A
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zno
powder
prepared
impact
blank
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叶雯
裴广强
王建斌
张鹏
尹阿利
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Xian Shendian Electronics Co Ltd
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Xian Shendian Electronics Co Ltd
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    • C04B35/453—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on zinc, tin, or bismuth oxides or solid solutions thereof with other oxides, e.g. zincates, stannates or bismuthates
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    • H01C7/00—Non-adjustable resistors formed as one or more layers or coatings; Non-adjustable resistors made from powdered conducting material or powdered semi-conducting material with or without insulating material
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Abstract

The invention belongs to the technical field of resistance electrical elements, and relates to a resistance card material with low gradient and large current impact stability and a preparation method thereof, which can improve the stability of a low gradient resistance card after large current impact. The resistor disc material comprises the following raw materials: ZnO: 80.0 to 93.0 wt.%, Bi2O3：2.0～6.0wt.％，Sb2O3：1.0～6.0wt.％，NiO：0～6.0wt.％，Cr2O3：0～2.0wt.％，Mn3O4：0.5～5.0wt.％，Co3O4：0.5～5.0wt.％，TiO2: 0.1-0.5 wt.%, glass frit (silver glass) containing Ag and B: 0.5-2.9 wt.%. By means of a corresponding method for the preparation,the preparation of the resistance sheet with low gradient, large flow and good stability is realized, and the degradation behavior of the zinc oxide piezoresistor caused by the influence of the existing large-current surge impact on the ZnO crystal boundary potential barrier is overcome.

Description

Low-gradient large-current impact-stability resistor material and preparation method thereof
Technical Field
The invention belongs to the technical field of resistance electrical elements, and relates to a resistance card material with low gradient and large current impact stability and a preparation method thereof, which can improve the stability of a low gradient resistance card after large current impact.
Background
The zinc oxide piezoresistor is a semiconductor ceramic resistor with nonlinear volt-ampere characteristics. Piezoresistors have a common voltage threshold, commonly referred to as the threshold voltage. When the applied voltage is lower than the critical voltage, the current passing through the piezoresistor is very small, the internal resistance of the piezoresistor is very large, when the applied voltage exceeds the critical voltage, the internal resistance is sharply reduced, and the current flowing through the piezoresistor is exponentially multiplied. Due to its special functionality, it has wide applications in the fields of high and low voltage power systems, semiconductor industry, etc.
The nonlinear volt-ampere characteristic of the zinc oxide piezoresistor is derived from the fact that crystal boundary layers around a large number of two adjacent ZnO crystal grains form back-to-back double Schottky barriers, and the zinc oxide piezoresistor obtains the voltage sensitive characteristic due to the double-side barriers. However, the barrier of the ZnO grain boundary is inevitably affected by the large current surge impact, and the degradation behavior of the zinc oxide varistor under the large current surge impact is an important factor restricting the development thereof.
Therefore, the improvement of the electrical performance of the zinc oxide varistor is especially important in the aspect of manufacturing the more miniaturized zinc oxide varistor with low gradient, large flow and high surge impact resistance stability, and becomes a technical problem to be solved urgently.
Disclosure of Invention
The invention aims to provide a resistor sheet material with low gradient and high through-current impact stability and a preparation method thereof, aiming at overcoming the degradation behavior of a zinc oxide piezoresistor caused by the influence of the existing high-current surge impact on ZnO crystal boundary potential barrier.
The technical scheme of the invention is to provide a resistance card material with low gradient and large through-flow impact stability, which is characterized by comprising the following raw materials in percentage by weight:
ZnO：80.0～93.0wt.％，Bi2O3：2.0～6.0wt.％，Sb2O3：1.0～6.0wt.％，NiO：0～6.0wt.％，Cr2O3：0～2.0wt.％，Mn3O4：0.5～5.0wt.％，Co3O4：0.5～5.0wt.％，TiO2: 0.1-0.5 wt.%, glass frit (silver glass) containing Ag and B: 0.5-2.9 wt.%.
Further, the composite material comprises the following raw materials in percentage by weight:
ZnO：89.1～92.3wt.％，Bi2O3：2.3～3.6wt.％，Sb2O3：1.5～1.8wt.％，NiO： 1.2～2.5wt.％，Cr2O3：0.2～0.7wt.％，Mn3O4：1.0～1.3wt.％，Co3O4：0.9～2.6wt.％， TiO2: 0.1-0.5 wt.%, glass frit containing Ag and B: 0.5 to 1.5 wt.%.
Further, the composite material comprises the following raw materials in percentage by weight:
ZnO：89.8wt.％，Bi2O3：2.5wt.％，Sb2O3：1.8wt.％，NiO：1.4wt.％，Cr2O3： 0.7wt.％，Mn3O4：1.1wt.％，Co3O4：1.0wt.％，TiO2: 0.4 wt.%, Ag and B containing glass frit: 1.3 wt.%.
Further, the composite material comprises the following raw materials in percentage by weight:
ZnO：89.9wt.％，Bi2O3：2.5wt.％，Sb2O3：1.8wt.％，NiO：1.4wt.％，Cr2O3：0.7wt.％，Mn3O4：1.1wt.％，Co3O4：1.0wt.％，TiO2: 0.3 wt.%, Ag and B containing glass frit: 1.3 wt.%.
Further, the composite material comprises the following raw materials in percentage by weight:
ZnO：92.3wt.％，Bi2O3：2.3wt.％，Sb2O3：1.5wt.％，NiO：0.8wt.％，Cr2O3： 0wt.％，Mn3O4：0.6wt.％，Co3O4：0.5wt.％，TiO2: 0.5 wt.%, Ag and B containing glass frit (silver glass): 1.5 wt.%.
Further, the composite material comprises the following raw materials in percentage by weight:
ZnO：89.5wt.％，Bi2O3：3.0wt.％，Sb2O3：1.6wt.％，NiO：1.5wt.％，Cr2O3： 0.5wt.％，Mn3O4：1.2wt.％，Co3O4：0.9wt.％，TiO2: 0.2 wt.%, Ag and B containing glass frit (silver glass): 1.6 wt.%.
The invention also provides a preparation method of the low-gradient large-through-flow impact stability resistor disc, which is characterized by comprising the following steps of:
step 1, preparing a resistance card material;
weighing ZnO and Bi according to the weight percentage2O3、Sb2O3、NiO、Cr2O3、Mn3O4、Co3O4、 TiO2And glass powder containing Ag and B;
step 2, preparing slurry;
step 2.1, Bi weighed in the step 12O3，Sb2O3，NiO，Cr2O3，Mn3O4，Co3O4Mixing the glass powder of Ag and B with deionized water, adding the mixture into a ball mill, screening after ball milling for a set time, collecting mixed slurry, drying the mixed slurry at the temperature of 100-120 ℃, and crushing the dried mixed slurry into powder to obtain a mixed powder material I;
step 2.2, the ZnO and TiO weighed in the step 12Mixing with deionized water, adding into ball mill, ball milling, sieving, collecting mixed slurry, and mixing with deionized waterThe material is dried and then crushed into powder to obtain a mixed powder material II;
step 2.3, pre-calcining the mixed powder material II obtained in the step 2.2 at the temperature of 700-900 ℃ for 1-3h to ensure that part of Ti4+The ions permeate into ZnO crystal grains, and are crushed into powder after being cooled;
step 2.4, mixing the powder material I prepared in step 2.1, the powder prepared in step 2.3 and Al (NO)3)3·9H2Continuously mixing O, a dispersing agent, a binder and deionized water, adding the mixture into a ball mill, carrying out ball milling, and sieving the obtained slurry to obtain total slurry;
step 3, preparing a blank;
step 3.1, carrying out spray granulation on the total slurry prepared in the step 2 by adopting a spray dryer to obtain granules;
step 3.2, adding deionized water and a release agent into the granulated material prepared in the step 3.1, uniformly mixing, sieving, and then carrying out aging treatment on the powder collected by sieving for at least 24 hours to enable the mass percent water content of the powder to be a set value, so as to obtain blank making powder;
3.3, pressing and molding the blank making powder obtained in the step 3.2, and controlling the pressure to ensure that the density of the molded blank is 3.2-3.3g/cm3；
Step 4, sintering process;
step 4.1, pre-calcining the green body prepared in the step 3 at 450-550 ℃, and simultaneously finishing glue discharging treatment to discharge organic matters in the green body;
step 4.2, calcining the green body treated in the step 4.1 at the high temperature of 1100-1300 ℃ to obtain a sintered green body of the resistance card;
and 4.3, grinding and cleaning the resistance sheet blank processed in the step 4.2, and then preparing a silver electrode on the surface of the processed resistance sheet blank so as to obtain the finished ZnO piezoresistor.
Further, Al (NO) in step 2.43)3·9H2The weight of O is 0.01-0.05 wt% of the total weight of the mixed powder material I prepared in the step 2.1 and the powder prepared in the step 2.3. If it isAl(NO3)3·9H2If the amount of O exceeds this range, the leakage current increases, the aging performance increases, and the residual voltage ratio decreases.
Further, Al (NO) in step 2.43)3·9H2The weight of O is 0.0025 wt% of the total weight of the mixed powder material I prepared in step 2.1 and the powder prepared in step 2.3.
Further, in step 2.1, the set time is 48 hours, the slurry is sieved by a 120-mesh sieve, and the mixed slurry is collected;
in the step 2.2, ball milling time is 6 hours, sieving with a 120-mesh sieve, collecting mixed slurry, drying the mixed slurry at 120 ℃, and then crushing into powder to obtain a mixed powder material II;
in the step 2.4, the ball milling time is 24 hours, and the obtained slurry is sieved by a 120-mesh sieve to obtain total slurry;
step 3.2, adding deionized water and a release agent into the granulated material prepared in the step 3.1, uniformly mixing, sieving by a 30-mesh sieve, and then carrying out aging treatment on the sieved and collected powder for at least 24 hours to ensure that the mass percentage moisture content of the powder is about 1.5 percent, so as to obtain blank making powder;
step 3.3, pressing and molding the blank making powder obtained in the step 3.2, and controlling the pressure to ensure that the side length of the molded blank is 26-27mm and the thickness is 4.00-4.30 mm;
in step 4.1, pre-calcining the green body prepared in step 3 at 500 ℃;
and 4.2, calcining the blank treated in the step 4.1 at a high temperature of 1200 ℃ to obtain a sintered resistor disc blank.
Further, in step 3.3, the blank making powder obtained in step 3.2 is pressed and formed, and the pressure is controlled, so that the side length of the formed blank is 26mm, the thickness is 4.55mm, and the density is 3.25g/cm3。
Furthermore, in the step 4.3, the side length of the ZnO piezoresistor is 22-23mm, the thickness of the ZnO piezoresistor is 3.00-4.00mm, the gradient range of the piezopotential is 150-170V/mm, the nonlinear coefficient of the ZnO piezoresistor is 80-105, the residual voltage ratio of 10kA 8/20 mu s lightning wave is 2.3-2.5, and after 20X 10kA 8/20 mu s lightning wave impact, the difference between the forward piezovoltage and the reverse piezovoltage compared with the voltage before impact is not more than 5%.
The invention has the beneficial effects that:
1. according to the invention, the preparation of the resistance card with low gradient, large flow and good stability is realized by adjusting the specific proportion and the specific preparation process of each raw material in the resistance card material, and the degradation behavior of the zinc oxide piezoresistor caused by the influence of the existing large-current surge impact on the ZnO crystal boundary potential barrier is overcome;
2. in the preparation process, ZnO, deionized water and TiO are added2After mixing, pre-calcination is carried out to obtain partial Ti4+Ions can permeate into ZnO grains, so that the influence of large-current surge impact on ZnO grain boundary potential barrier is reduced;
3. the ZnO varistor with the side length of 22-23mm and the thickness of 3.00-4.00mm has the voltage-sensitive potential gradient range of 100-200V/mm, the nonlinear coefficient of 80-105, the residual voltage ratio of 10kA 8/20 mu s lightning wave of 2.3-2.5, and after 20 x 10kA 8/20 mu s lightning wave impact, the difference between the forward voltage-sensitive voltage and the reverse voltage-sensitive voltage is not more than 5% compared with the voltage-sensitive voltage before impact;
compared with the prior ZnO piezoresistor with the side length range of 22-23mm, the surge impact stability of the piezoresistor is effectively improved, and the piezoresistor can be suitable for small piezoresistors and piezochips of surge protectors.
4. The method is simple and easy to implement, low in cost and suitable for popularization and application.
Detailed Description
In order to make the aforementioned objects, features and advantages of the present invention comprehensible, specific embodiments accompanied with the description are described in detail below, and it is apparent that the described embodiments are a part of the embodiments of the present invention, not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without making creative efforts based on the embodiments of the present invention, shall fall within the protection scope of the present invention.
In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention, but the present invention may be practiced in other ways than those specifically described and will be readily apparent to those of ordinary skill in the art without departing from the spirit of the present invention, and therefore the present invention is not limited to the specific embodiments disclosed below.
Example 1
The resistance card material with the low gradient and the large through-flow impact stability comprises the following raw materials in percentage by weight:
ZnO：89.9wt.％，Bi2O3：2.5wt.％，Sb2O3：1.8wt.％，NiO：1.4wt.％，Cr2O3： 0.7wt.％，Mn3O4：1.1wt.％，Co3O4：1.0wt.％，TiO2: 0.3 wt.%, Ag and B containing glass frit: 1.3 wt.%;
the preparation method comprises the following steps:
a. preparing raw materials of the resistor disc:
preparing raw materials according to the following raw material formula by weight percent:
ZnO：89.9wt.％，Bi2O3：2.5wt.％，Sb2O3：1.8wt.％，NiO：1.4wt.％，Cr2O3：0.7wt.％，Mn3O4：1.1wt.％，Co3O4：1.0wt.％，TiO2: 0.3 wt.%, Ag and B containing glass frit: 1.3 wt.%;
b. preparation of slurry:
b1. b, mixing the glass powder prepared in the step a and Bi2O3、Sb2O3、NiO、Cr2O3、Mn3O4、Co3O4、 TiO2Mixing with deionized water to enable the mixed solution to reach a solid content of 60% by mass, adding the mixed solution into a ball mill, carrying out ball milling for 48 hours, sieving with a 120-mesh sieve, collecting mixed slurry, drying the mixed slurry at 120 ℃, and then crushing the dried mixed slurry into powder to obtain a mixed powder material;
b2. mixing the ZnO prepared in the step a and the mixed powder material prepared in the step b1 with Al (NO)3)3·9H2Continuously feeding O, dispersant, binder and deionized waterMixing, adding into a ball mill, carrying out ball milling for 24h, and sieving the obtained slurry with a 120-mesh sieve to obtain total slurry; added Al (NO)3)3·9H2O is 0.025 wt% of the total amount of the powder prepared in the step b1 and the step b 2; the weight of the dispersant used in this example was determined based on the viscosity of the slurry, and the binder was a 4.5% PVR aqueous solution.
c. Preparing a blank body:
c1. b, performing spray granulation on the total slurry prepared in the step b by using a spray dryer to obtain granulated materials;
c2. adding deionized water and a release agent into the granulated material obtained in the step c1, uniformly mixing, sieving by a 30-mesh sieve, and then carrying out ageing treatment on the sieved and collected powder for 24 hours to enable the mass percentage moisture content of the powder to be 1.5%, so as to obtain blank making powder;
c3. c2, pressing and forming the blank making powder obtained in the step c, and controlling the pressure to ensure that the side length of the formed blank is 26mm, the thickness of the formed blank is 4.55mm, and the density of the formed blank is 3.25g/cm3；
d. The sintering process comprises the following steps:
d1. pre-calcining the green body prepared in the step c at 500 ℃, and simultaneously finishing glue discharging treatment to discharge organic matters in the green body;
d2. calcining the green body obtained through the pre-calcining treatment in the step d1 at the high temperature of 1200 ℃ for at least 2.5 hours to obtain a sintered green body of the resistance card;
d3. and d, grinding and cleaning the resistance card blank obtained in the step d2, and then preparing a metal electrode on the surface of the treated resistance card blank so as to obtain the finished ZnO piezoresistor.
Experimental test analysis:
the ZnO varistor prepared in this example was used as a test sample to conduct experimental tests.
The diameter of the finished ZnO varistor prepared by the method of the embodiment is 22mm, and the thickness of the finished ZnO varistor is 3 mm. The piezoresistor has a piezopotential gradient of 160V/mm, a nonlinear coefficient of 89 and a residual voltage ratio of 2.44 for 10kA 8/20 μ s lightning. After 20 lightning strikes of 10kA 8/20 mu s, the average difference between the forward voltage-dependent voltage and the comparison before the impacts is 8.26%, and the average difference between the reverse voltage-dependent voltage and the comparison before the impacts is 8.32%.
The potential gradient of the traditional ZnO resistor sample is 170V/mm, the nonlinear coefficient is 40, and after 20 times of 10kA 8/20 mu s lightning wave impact, the difference between the forward voltage-dependent voltage and the reverse voltage-dependent voltage is about 10 percent compared with that before impact.
The potential gradient of the ZnO varistor is lower than that of a traditional ZnO resistor sample, the ZnO varistor has a high nonlinear coefficient, the difference between the forward voltage-dependent voltage and the voltage-dependent voltage before impact is small after lightning wave impact, and the high-current impact stability of the ZnO varistor is effectively improved.
Example 2
This example is identical to the raw material formulation of example 1, except that the slurry of this example is prepared by pre-treating the slurry with TiO2The mixed powder material is pre-calcined, and the specific steps are as follows:
a. preparing raw materials for preparing the resistance card:
preparing raw materials according to the following raw material formula by weight percent:
ZnO：89.9wt.％，Bi2O3：2.5wt.％，Sb2O3：1.8wt.％，NiO：1.4wt.％，Cr2O3： 0.7wt.％，Mn3O4：1.1wt.％，Co3O4：1.0wt.％，TiO2: 0.3 wt.%, Ag and B containing glass frit: 1.3 wt.%.
b. Preparation of slurry:
b1. bi prepared in step a2O3，Sb2O3，NiO，Cr2O3，Mn3O4，Co3O4Mixing the glass powder and deionized water, adding the mixture into a ball mill, carrying out ball milling for 48 hours, sieving the mixture by a 120-mesh sieve, collecting mixed slurry, drying the mixed slurry at 120 ℃, and crushing the dried mixed slurry into powder to obtain a mixed powder material I. In other embodiments, the drying temperature can be 100-120 ℃;
b2. b, preparing ZnO, deionized water and TiO prepared in the step a2After the mixing, the mixture is mixed,adding the mixture into a ball mill, performing ball milling for 6 hours, sieving with a 120-mesh sieve, collecting mixed slurry, drying the mixed slurry at 120 ℃, and crushing the dried mixed slurry into powder to obtain a mixed powder material II;
b3. the obtained mixed powder material II is pre-calcined for 1-3h at the temperature of 700-900 ℃ to ensure that part of Ti4+Ion-permeating ZnO crystal grains; cooling and crushing into powder;
b4. mixing the powder prepared in the step b1 and the step b3 with Al (NO)3)3·9H2Continuously mixing O, a dispersing agent, a binder and deionized water, adding into a ball mill, carrying out ball milling for 24 hours, and sieving the obtained slurry with a 120-mesh sieve to obtain total slurry; added Al (NO)3)3·9H2O is 0.025 wt% of the total amount of the powder prepared in the step b2 and the step b 3; al (NO) added in other examples3)3·9H2And O is 0.01 to 0.05 weight percent of the total amount of the powder prepared in the step b2 and the step b3.
c. Preparing a blank body:
c1. b, performing spray granulation on the total slurry prepared in the step b by using a spray dryer to obtain granulated materials;
c2. adding deionized water and a release agent into the granulated material obtained in the step c1, uniformly mixing, sieving by a 30-mesh sieve, and then carrying out ageing treatment on the sieved and collected powder for 24 hours to enable the mass percentage water content of the powder to be 1.5%, so as to obtain blank making powder;
c3. c2, pressing and forming the blank powder obtained in the step c, and controlling the pressure so that the side length of the formed blank is 26mm, the thickness of the formed blank is 4.55mm, and the density of the formed blank is 3.25g/cm3。
d. The sintering process comprises the following steps:
d1. pre-calcining the green body prepared in the step c at 500 ℃, and simultaneously finishing glue discharging treatment to discharge organic matters in the green body;
d2. calcining the green body obtained through the pre-calcining treatment in the step d1 at a high temperature of 1200 ℃ for at least 2.5 hours to obtain a sintered green body of the resistor disc;
d3. and d2, grinding and cleaning the resistance card blank obtained in the step d2, and then preparing a metal electrode on the surface of the treated resistance card blank so as to obtain the finished ZnO piezoresistor.
Experimental test analysis:
the ZnO varistor prepared in this example was used as a test sample to conduct experimental tests.
The diameter of the finished ZnO varistor prepared by the method of the embodiment is 22mm, and the thickness of the finished ZnO varistor is 3 mm. The piezoresistor has a piezopotential gradient of 158V/mm, a nonlinear coefficient of 91 and a residual voltage ratio of 2.40 of 10kA 8/20 mus lightning wave. After 20 lightning strikes of 10kA 8/20 μ s, the forward voltage-dependent voltage varied by 4.15% from the control before the strike, and the reverse voltage-dependent voltage varied by 4.36% from the control before the strike.
Compared with the embodiment 1, the ZnO varistor has the advantages that the potential gradient is lower, the nonlinear coefficient is higher, the difference between the forward voltage-dependent voltage and the voltage-dependent voltage before impact is smaller after lightning wave impact, and the high-current impact stability of the ZnO varistor is improved more effectively.
Example 3
The preparation process of this example is completely the same as that of example 2, except that the raw material formula is adopted, and the low-gradient large-flux resistance card material with impact stability in this example comprises the following raw materials in percentage by weight:
ZnO：89.8wt.％，Bi2O3：2.5wt.％，Sb2O3：1.8wt.％，NiO：1.4wt.％，Cr2O3： 0.7wt.％，Mn3O4：1.1wt.％，Co3O4：1.0wt.％，TiO2: 0.4 wt.%, Ag and B containing glass frit: 1.3 wt.%.
Experimental test analysis:
the ZnO varistor prepared in this example was used as a test sample to conduct experimental tests.
The diameter of the finished ZnO varistor prepared by the method of the embodiment is 22mm, and the thickness of the finished ZnO varistor is 3 mm. The piezoresistor has a piezopotential gradient of 150V/mm, a nonlinear coefficient of 103 and a residual voltage ratio of 2.38 of 10kA 8/20 μ s. After 20 times of 10kA 8/20 mu s lightning wave impact, the average difference between the forward voltage-sensitive voltage and the comparison voltage before impact is 3.74 percent, and the average difference between the reverse voltage-sensitive voltage and the comparison voltage before impact is 0.85 percent; the maximum difference between the forward voltage-sensitive voltage and the comparison before impact is 4.16 percent, and the average difference between the reverse voltage-sensitive voltage and the comparison before impact is 1.19 percent; the difference between the forward voltage-sensitive voltage and the comparison before no impact is minimum 0.41%, and the difference between the reverse voltage-sensitive voltage and the comparison before no impact is average 0.36%.
Compared with the ZnO resistor sample in the embodiment 2, the ZnO varistor in the embodiment has lower varistor gradient, higher nonlinear coefficient and higher high-current impact stability.
Example 4
The preparation process of this example is the same as that of example 3, except that the raw material formula is adopted, and the low-gradient large-flux resistance card material with impact stability of this example comprises the following raw materials in percentage by weight:
ZnO：80.0wt.％，Bi2O3：6.0wt.％，Sb2O3：6.0wt.％，NiO：6.0wt.％，Cr2O3： 0wt.％，Mn3O4：1.0wt.％，Co3O4：0.5wt.％，TiO2: 0.1 wt.%, Ag and B containing glass frit (silver glass): 0.4 wt.%.
The preparation process comprises the following steps:
a. preparing raw materials for preparing the resistance card:
preparing raw materials according to the following raw material formula by weight percent:
ZnO：80.0wt.％，Bi2O3：6.0wt.％，Sb2O3：6.0wt.％，NiO：6.0wt.％，Cr2O3： 0wt.％，Mn3O4：1.0wt.％，Co3O4：0.5wt.％，TiO2: 0 wt.%, Ag and B containing glass frit (silver glass): 0.5 wt.%.
b. Preparation of slurry:
b1. bi prepared in step a2O3，Sb2O3，NiO，Mn3O4，Co3O4Glass powder andmixing deionized water, adding the mixture into a ball mill, performing ball milling for 48 hours, sieving the mixture through a 120-mesh sieve, collecting mixed slurry, drying the mixed slurry at 120 ℃, and crushing the dried mixed slurry into powder to obtain a mixed powder material;
b2. b, mixing the ZnO prepared in the step a with deionized water, adding the mixture into a ball mill, carrying out ball milling for 6 hours, sieving the mixture through a 120-mesh sieve, collecting mixed slurry, drying the mixed slurry at 120 ℃, and then crushing the dried mixed slurry into powder to obtain a mixed powder material;
b3. pre-calcining the obtained mixed powder material at the temperature of 700-900 ℃ for 1-3 h; cooling and crushing into powder;
b4. mixing the powder prepared in the step b1 and the step b3 with Al (NO)3)3·9H2Continuously mixing O, a dispersing agent, a binder and deionized water, adding into a ball mill, carrying out ball milling for 24 hours, and sieving the obtained slurry with a 120-mesh sieve to obtain total slurry; added Al (NO)3)3·9H2O is 0.025 wt% of the total amount of the powder prepared in the step b2 and the step b 3;
c. preparing a blank body:
c1. b, performing spray granulation on the total slurry prepared in the step b by using a spray dryer to obtain granulated materials;
c2. adding deionized water and a release agent into the granulated material obtained in the step c1, uniformly mixing, sieving by a 30-mesh sieve, and then carrying out ageing treatment on the sieved and collected powder for 24 hours to enable the mass percentage water content of the powder to be 1.5%, so as to obtain blank making powder;
c3. c2, pressing and forming the blank powder obtained in the step c, and controlling the pressure so that the side length of the formed blank is 26mm, the thickness of the formed blank is 4.55mm, and the density of the formed blank is 3.25g/cm3；
d. The sintering process comprises the following steps:
d1. pre-calcining the green body prepared in the step c at 500 ℃, and simultaneously finishing glue discharging treatment to discharge organic matters in the green body;
d2. calcining the green body obtained through the pre-calcining treatment in the step d1 at a high temperature of 1200 ℃ for at least 2.5 hours to obtain a sintered green body of the resistor disc;
d3. and d2, grinding and cleaning the resistance card blank obtained in the step d2, and then preparing a metal electrode on the surface of the treated resistance card blank so as to obtain the finished ZnO piezoresistor.
Experimental test analysis:
the ZnO varistor prepared in this example was used as a test sample to conduct experimental tests.
The diameter of the finished ZnO varistor prepared by the method of the embodiment is 22mm, and the thickness of the finished ZnO varistor is 3 mm. The piezoresistor has a piezopotential gradient of 168V/mm, a nonlinear coefficient of 85 and a residual voltage ratio of 2.43 of 10kA 8/20 mus. After 20 lightning strikes of 10kA 8/20 μ s, the forward voltage-dependent voltage varied by 4.89% from the comparison before the strike, and the reverse voltage-dependent voltage varied by 4.97% from the comparison before the strike.
Compared with the ZnO resistor samples in the embodiments 3 and 2, the ZnO varistor of the present embodiment has poor performance such as varistor gradient, nonlinear coefficient, and high current impact stability, but has lower varistor gradient, higher nonlinear coefficient, and higher high current impact stability compared with the conventional ZnO resistor sample.
Example 5
The difference between the present embodiment and embodiment 3 is the raw material formula, and the resistance card material with low gradient and large flow impact stability of the present embodiment comprises the following raw materials by weight percent:
ZnO：83.5wt.％，Bi2O3：4.5wt.％，Sb2O3：5.0wt.％，NiO：0.5wt.％，Cr2O3： 2.0wt.％，Mn3O4：1.3wt.％，Co3O4：2.6wt.％，TiO2: 0.1 wt.%, Ag and B containing glass frit (silver glass): 0.5 wt.%.
The preparation is exactly the same as in example 3.
Experimental test analysis:
the ZnO varistor prepared in this example was used as a test sample to conduct experimental tests.
The diameter of the finished ZnO varistor prepared by the method of the embodiment is 22mm, and the thickness of the finished ZnO varistor is 3 mm. The piezoresistor has a piezopotential gradient of 160V/mm, a nonlinear coefficient of 90 and a residual voltage ratio of 2.40 of 10kA 8/20 mus lightning wave. After 20 lightning strikes of 10kA 8/20 μ s, the forward voltage-dependent voltage varied by 4.18% from the control before the strike, and the reverse voltage-dependent voltage varied by 4.40% from the control before the strike.
Compared with the ZnO resistor sample in example 3, the ZnO varistor of this embodiment has poorer performance such as varistor gradient, nonlinear coefficient, and high current impact stability, but has comparable performance to the ZnO resistor sample in example 2, and compared with the conventional ZnO resistor sample and the ZnO resistor sample in example 4, the ZnO varistor of this embodiment also has lower varistor gradient, higher nonlinear coefficient, and higher high current impact stability.
Example 6
The difference between the present embodiment and embodiment 3 is the raw material formula, and the resistance card material with low gradient and large flow impact stability of the present embodiment comprises the following raw materials by weight percent:
ZnO：86.6wt.％，Bi2O3：3.6wt.％，Sb2O3：1.0wt.％，NiO：2.5wt.％，Cr2O3： 0.2wt.％，Mn3O4：0.5wt.％，Co3O4：5.0wt.％，TiO2: 0.1 wt.%, Ag and B containing glass frit (silver glass): 0.5 wt.%.
The preparation is exactly the same as in example 4.
Experimental test analysis:
the ZnO varistor prepared in this example was used as a test sample to conduct experimental tests.
The diameter of the finished ZnO varistor prepared by the method of the embodiment is 22mm, and the thickness of the finished ZnO varistor is 3 mm. The piezoresistor has a piezopotential gradient of 166V/mm, a nonlinear coefficient of 87 and a residual voltage ratio of 2.43 for 10kA 8/20 μ s lightning. After 20 lightning strikes of 10kA 8/20 μ s, the forward voltage-dependent voltage varied by 4.87% from the control before the strike, and the reverse voltage-dependent voltage varied by 4.95% from the control before the strike.
Compared with the ZnO resistor samples in the embodiments 3 and 2, the ZnO varistor of the present embodiment has poorer performance such as varistor gradient, nonlinear coefficient, and high current impact stability, but has comparable performance to the ZnO resistor sample in the embodiment 4, and has lower varistor gradient, higher nonlinear coefficient and higher high current impact stability compared with the conventional ZnO resistor sample.
Example 7
The difference between the present embodiment and embodiment 3 is the raw material formula, and the resistance card material with low gradient and large flow impact stability of the present embodiment comprises the following raw materials by weight percent:
ZnO：89.1wt.％，Bi2O3：2.6wt.％，Sb2O3：1.0wt.％，NiO：1.2wt.％，Cr2O3： 0wt.％，Mn3O4：5.0wt.％，Co3O4：0.5wt.％，TiO2: 0.1 wt.%, Ag and B containing glass frit (silver glass): 0.5 wt.%.
The preparation is exactly the same as in example 4.
Experimental test analysis:
the ZnO varistor prepared in this example was used as a test sample to conduct experimental tests.
The diameter of the finished ZnO varistor prepared by the method of the embodiment is 22mm, and the thickness of the finished ZnO varistor is 3 mm. The varistor has a varistor potential gradient of 163V/mm, a nonlinear coefficient of 89 and a 10kA 8/20 mu s residual voltage ratio of 2.40. After 20 lightning strikes of 10kA 8/20 μ s, the forward voltage-dependent voltage varied by 4.66% from the control before the strike, and the reverse voltage-dependent voltage varied by 4.82% from the control before the strike.
Compared with the ZnO resistor samples in the embodiments 3 and 2, the ZnO varistor of the present embodiment has poorer performance such as varistor gradient, nonlinear coefficient, and high current impact stability, but is better than the ZnO resistor samples in the embodiments 4 and 6, and has lower varistor gradient, higher nonlinear coefficient and higher high current impact stability compared with the conventional ZnO resistor samples.
Example 8
The difference between the present embodiment and embodiment 3 is the raw material formula, and the resistance card material with low gradient and large flow impact stability of the present embodiment comprises the following raw materials by weight percent:
ZnO：92.3wt.％，Bi2O3：2.3wt.％，Sb2O3：1.5wt.％，NiO：0.8wt.％，Cr2O3： 0wt.％，Mn3O4：0.6wt.％，Co3O4：0.5wt.％，TiO2: 0.5 wt.%, Ag and B containing glass frit (silver glass): 1.5 wt.%.
The preparation is exactly the same as in example 3.
Experimental test analysis:
the ZnO varistor prepared in this example was used as a test sample to conduct experimental tests.
The diameter of the finished ZnO varistor prepared by the method of the embodiment is 22mm, and the thickness of the finished ZnO varistor is 3 mm. The piezoresistor has a piezopotential gradient of 159V/mm, a nonlinear coefficient of 92 and a residual voltage ratio of 2.39 of 10kA 8/20 mus lightning wave. After 20 lightning strikes of 10kA 8/20 μ s, the forward voltage-dependent voltage varied by 4.09% from the comparison before the strikes, and the reverse voltage-dependent voltage varied by 4.85% from the comparison before the strikes.
Compared with the ZnO resistor sample in example 3, the ZnO varistor of this embodiment has poorer performance such as varistor gradient, nonlinear coefficient, and high current impact stability, but has comparable performance to the ZnO resistor sample in example 2, and compared with the conventional ZnO resistor sample and the ZnO resistor sample in example 4, the ZnO varistor of this embodiment also has lower varistor gradient, higher nonlinear coefficient, and higher high current impact stability.
Example 9
The preparation process of this example is the same as that of example 3, except that the raw material formula is adopted, and the low-gradient large-flux resistance card material with impact stability of this example comprises the following raw materials in percentage by weight:
ZnO：93.0wt.％，Bi2O3：2.0wt.％，Sb2O3：1.0wt.％，NiO：0wt.％，Cr2O3： 0wt.％，Mn3O4：0.5wt.％，Co3O4：0.5wt.％，TiO2: 0.1 wt.%, Ag and B containing glass frit (silver glass): 2.9 wt.%.
The preparation is exactly the same as in example 3.
Experimental test analysis:
the ZnO varistor prepared in this example was used as a test sample to conduct experimental tests.
The diameter of the finished ZnO varistor prepared by the method of the embodiment is 22mm, and the thickness of the finished ZnO varistor is 3 mm. The piezoresistor has a piezopotential gradient of 169V/mm, a nonlinear coefficient of 80 and a residual voltage ratio of 2.44 for 10kA 8/20 μ s lightning wave. After 20 lightning strikes of 10kA 8/20 μ s, the forward voltage-dependent voltage varied by 4.63% from the control before the strike, and the reverse voltage-dependent voltage varied by 4.76% from the control before the strike.
Compared with the ZnO resistor samples in the embodiments 3 and 2, the ZnO varistor of the present embodiment has poor performance such as varistor gradient, nonlinear coefficient, and high current impact stability, but has lower varistor gradient, higher nonlinear coefficient, and higher high current impact stability compared with the conventional ZnO resistor sample.
Example 10
The preparation process of this example is the same as that of example 3, except that the raw material formula is adopted, and the low-gradient large-flux resistance card material with impact stability of this example comprises the following raw materials in percentage by weight:
ZnO：89.5wt.％，Bi2O3：3.0wt.％，Sb2O3：1.6wt.％，NiO：1.5wt.％，Cr2O3： 0.5wt.％，Mn3O4：1.2wt.％，Co3O4：0.9wt.％，TiO2: 0.2 wt.%, Ag and B containing glass frit (silver glass): 1.6 wt.%.
The preparation is exactly the same as in example 3.
Experimental test analysis:
the ZnO varistor prepared in this example was used as a test sample to conduct experimental tests.
The diameter of the finished ZnO varistor prepared by the method of the embodiment is 22mm, and the thickness of the finished ZnO varistor is 3 mm. The piezoresistor has a piezopotential gradient of 151V/mm, a nonlinear coefficient of 99, and a residual voltage ratio of 2.39 of 10kA 8/20 μ s. After 20 lightning strikes of 10kA 8/20 μ s, the forward voltage-dependent voltage varied by 3.78% from the comparison before the strikes, and the reverse voltage-dependent voltage varied by 1.07% from the comparison before the strikes.
The performances of the varistor gradient, the nonlinear coefficient, the large-current impact stability and the like of the ZnO varistor in the embodiment are equivalent to those of the ZnO varistor in the embodiment 3, and compared with the traditional ZnO varistor sample, the ZnO varistor also has the advantages of lower varistor gradient, higher nonlinear coefficient and higher large-current impact stability.
Comparative example
The resistance card material in the comparative example comprises the following raw materials in percentage by weight:
ZnO：75.6wt.％，Bi2O3：7.3wt.％，Sb2O3：1.6wt.％，NiO：1.4wt.％，Cr2O3： 2.6wt.％，Mn3O4：5.6wt.％，Co3O4：4.1wt.％，TiO2: 0 wt.%, Ag and B containing glass frit: 1.8 wt.%;
the preparation method comprises the following steps:
a. preparing raw materials of the resistor disc:
preparing raw materials according to the following raw material formula by weight percent:
ZnO：75.6wt.％，Bi2O3：7.3wt.％，Sb2O3：1.6wt.％，NiO：1.4wt.％，Cr2O3： 2.6wt.％，Mn3O4：5.6wt.％，Co3O4：4.1wt.％，TiO2: 0 wt.%, Ag and B containing glass frit: 1.8 wt.%;
b. preparation of slurry:
b1. b, mixing the glass powder prepared in the step a and Bi2O3、Sb2O3、NiO、Cr2O3、Mn3O4、Co3O4Mixing with deionized water to make the mixed solution reach a solid content of 60% by mass,adding the mixed solution into a ball mill, carrying out ball milling for 48h, sieving with a 120-mesh sieve, collecting mixed slurry, drying the mixed slurry at 120 ℃, and crushing into powder to obtain a mixed powder material;
b2. mixing the ZnO prepared in the step a and the mixed powder material prepared in the step b1 with Al (NO)3)3·9H2Continuously mixing O, a dispersing agent, a binder and deionized water, adding into a ball mill, carrying out ball milling for 24 hours, and sieving the obtained slurry with a 120-mesh sieve to obtain total slurry; added Al (NO)3)3·9H2O is 0.025 wt% of the total amount of the powder prepared in the step b1 and the step b 2;
c. preparing a blank body:
c1. b, performing spray granulation on the total slurry prepared in the step b by using a spray dryer to obtain granulated materials;
c2. adding deionized water and a release agent into the granulated material obtained in the step c1, uniformly mixing, sieving by a 30-mesh sieve, and then carrying out ageing treatment on the sieved and collected powder for 24 hours to enable the mass percentage moisture content of the powder to be 1.5%, so as to obtain blank making powder;
c3. c2, pressing and forming the blank making powder obtained in the step c, and controlling the pressure to ensure that the side length of the formed blank is 26mm, the thickness of the formed blank is 4.55mm, and the density of the formed blank is 3.25g/cm3；
d. The sintering process comprises the following steps:
d1. pre-calcining the green body prepared in the step c at 500 ℃, and simultaneously finishing glue discharging treatment to discharge organic matters in the green body;
d2. calcining the green body obtained through the pre-calcining treatment in the step d1 at the high temperature of 1200 ℃ for at least 2.5 hours to obtain a sintered green body of the resistance card;
d3. and d, grinding and cleaning the resistance card blank obtained in the step d2, and then preparing a metal electrode on the surface of the treated resistance card blank so as to obtain the finished ZnO piezoresistor.
Experimental test analysis:
and (3) taking the ZnO piezoresistor prepared by the comparison as a test sample to carry out experimental inspection.
The diameter of the finished ZnO varistor prepared by the method of the embodiment is 22mm, and the thickness of the finished ZnO varistor is 3 mm. The varistor has a varistor potential gradient of 172V/mm and a nonlinear coefficient of 43, and after 20 times of 10kA 8/20 mus lightning wave impact, the difference between the forward varistor voltage and the voltage before impact is 35 percent, and the difference between the reverse varistor voltage and the voltage before impact is 36 percent.
In conclusion, compared with the traditional ZnO piezoresistor, the ZnO piezoresistor has low piezoresistor gradient and high nonlinear coefficient, and after the prepared ZnO piezoresistor is subjected to large-current pulse surge impact, the forward and reverse piezovoltages have small difference compared with those before impact, and the prepared ZnO piezoresistor has good stability, so that the ZnO piezoresistor can meet the application requirements of photovoltaic, wind power, lightning arrester counters, communication equipment and other occasions.

Claims (12)

1. The low-gradient high-through-current impact-stability resistor material is characterized by comprising the following raw materials in percentage by weight:
ZnO：80.0～93.0wt.％，Bi2O3：2.0～6.0wt.％，Sb2O3：1.0～6.0wt.％，NiO：0～6.0wt.％，Cr2O3：0～2.0wt.％，Mn3O4：0.5～5.0wt.％，Co3O4：0.5～5.0wt.％，TiO2: 0.1-0.5 wt.%, glass frit containing Ag and B: 0.5-2.9 wt.%.
2. The low-gradient large-flux impact-stable electrical resistance sheet material according to claim 1, comprising the following raw materials in percentage by weight:
ZnO：89.1～92.3wt.％，Bi2O3：2.3～3.6wt.％，Sb2O3：1.5～1.8wt.％，NiO：1.2～2.5wt.％，Cr2O3：0.2～0.7wt.％，Mn3O4：1.0～1.3wt.％，Co3O4：0.9～2.6wt.％，TiO2: 0.1-0.5 wt.%, glass frit containing Ag and B: 0.5 to 1.5 wt.%.
3. The low-gradient large-flux impact-stable electrical resistance sheet material according to claim 2, comprising the following raw materials in percentage by weight:
ZnO：89.8wt.％，Bi2O3：2.5wt.％，Sb2O3：1.8wt.％，NiO：1.4wt.％，Cr2O3：0.7wt.％，Mn3O4：1.1wt.％，Co3O4：1.0wt.％，TiO2: 0.4 wt.%, Ag and B containing glass frit: 1.3 wt.%.
4. The low-gradient large-flux impact-stable electrical resistance sheet material according to claim 2, comprising the following raw materials in percentage by weight:
ZnO：89.9wt.％，Bi2O3：2.5wt.％，Sb2O3：1.8wt.％，NiO：1.4wt.％，Cr2O3：0.7wt.％，Mn3O4：1.1wt.％，Co3O4：1.0wt.％，TiO2: 0.3 wt.%, Ag and B containing glass frit: 1.3 wt.%.
5. The low-gradient large-flux impact-stable electrical resistance sheet material according to claim 1, comprising the following raw materials in percentage by weight:
ZnO：92.3wt.％，Bi2O3：2.3wt.％，Sb2O3：1.5wt.％，NiO：0.8wt.％，Cr2O3：0wt.％，Mn3O4：0.6wt.％，Co3O4：0.5wt.％，TiO2: 0.5 wt.%, Ag and B containing glass frit (silver glass): 1.5 wt.%.
6. The low-gradient large-flux impact-stable electrical resistance sheet material according to claim 1, comprising the following raw materials in percentage by weight:
ZnO：89.5wt.％，Bi2O3：3.0wt.％，Sb2O3：1.6wt.％，NiO：1.5wt.％，Cr2O3：0.5wt.％，Mn3O4：1.2wt.％，Co3O4：0.9wt.％，TiO2: 0.2 wt.%, Ag and B containing glass frit: 1.6 wt.%.
7. A preparation method of a low-gradient large-flux impact-stability resistor disc is characterized by comprising the following steps:
step 1, preparing a resistance card material;
weighing ZnO and Bi according to the weight percentage of any one of claims 1 to 62O3、Sb2O3、NiO、Cr2O3、Mn3O4、Co3O4、TiO2And glass powder containing Ag and B;
step 2, preparing slurry;
step 2.1, Bi weighed in the step 12O3，Sb2O3，NiO，Cr2O3，Mn3O4，Co3O4Mixing the glass powder of Ag and B with deionized water, adding the mixture into a ball mill, screening after ball milling for a set time, collecting mixed slurry, drying the mixed slurry at the temperature of 100-120 ℃, and crushing the dried mixed slurry into powder to obtain a mixed powder material I;
step 2.2, the ZnO and TiO weighed in the step 12Mixing with deionized water, adding into a ball mill, ball-milling, sieving, collecting mixed slurry, drying the mixed slurry, and pulverizing into powder to obtain a mixed powder material II;
step 2.3, pre-calcining the mixed powder material II obtained in the step 2.2 at the temperature of 700-900 ℃ for 1-3h to ensure that part of Ti4 +The ions permeate into ZnO crystal grains, and are crushed into powder after being cooled;
step 2.4, mixing the powder material I prepared in step 2.1, the powder prepared in step 2.3 and Al (NO)3)3·9H2Continuously mixing O, dispersant, binder and deionized water, adding into a ball mill, ball-milling, and sieving the obtained slurryObtaining total slurry;
step 3, preparing a blank;
step 3.1, carrying out spray granulation on the total slurry prepared in the step 2 by adopting a spray dryer to obtain granules;
step 3.2, adding deionized water and a release agent into the granulated material prepared in the step 3.1, uniformly mixing, sieving, and then carrying out aging treatment on the powder collected by sieving for at least 24 hours to enable the mass percent water content of the powder to be a set value, so as to obtain blank making powder;
3.3, pressing and molding the blank making powder obtained in the step 3.2, and controlling the pressure to ensure that the density of the molded blank is 3.2-3.3g/cm3；
Step 4, sintering process;
step 4.1, pre-calcining the green body prepared in the step 3 at 450-550 ℃, and simultaneously finishing glue discharging treatment to discharge organic matters in the green body;
step 4.2, calcining the green body treated in the step 4.1 at the high temperature of 1100-1300 ℃ to obtain a sintered green body of the resistance card;
and 4.3, grinding and cleaning the resistance sheet blank processed in the step 4.2, and then preparing a silver electrode on the surface of the processed resistance sheet blank so as to obtain the finished ZnO piezoresistor.
8. The method for preparing the low-gradient large-flux impact-stability resistor disc as claimed in claim 7, wherein the method comprises the following steps: step 2.4 Al (NO)3)3·9H2The weight of O is 0.01-0.05 wt% of the total weight of the mixed powder material I prepared in the step 2.1 and the powder prepared in the step 2.3.
9. The method for preparing the low-gradient large-flux impact-stability resistor disc according to claim 8, wherein the method comprises the following steps: step 2.4 Al (NO)3)3·9H2The weight of O is 0.0025 wt% of the total weight of the mixed powder material I prepared in step 2.1 and the powder prepared in step 2.3.
10. The method for preparing the low-gradient large-flux impact-stability resistor disc according to claim 8, wherein the method comprises the following steps:
in step 2.1, the set time is 48 hours, sieving the slurry by a 120-mesh sieve, and collecting the mixed slurry;
in the step 2.2, ball milling time is 6 hours, sieving with a 120-mesh sieve, collecting mixed slurry, drying the mixed slurry at 120 ℃, and then crushing into powder to obtain a mixed powder material II;
in the step 2.4, the ball milling time is 24 hours, and the obtained slurry is sieved by a 120-mesh sieve to obtain total slurry;
step 3.2, adding deionized water and a release agent into the granulated material prepared in the step 3.1, uniformly mixing, sieving by a 30-mesh sieve, and then carrying out aging treatment on the sieved and collected powder for at least 24 hours to ensure that the mass percentage moisture content of the powder is about 1.5 percent, so as to obtain blank making powder;
step 3.3, pressing and molding the blank making powder obtained in the step 3.2, and controlling the pressure to ensure that the side length of the molded blank is 26-27mm and the thickness is 4.00-4.30 mm;
in step 4.1, pre-calcining the green body prepared in step 3 at 500 ℃;
and 4.2, calcining the blank treated in the step 4.1 at a high temperature of 1200 ℃ to obtain a sintered resistor disc blank.
11. The method for preparing the low-gradient large-flux impact-stability resistor disc as claimed in claim 10, wherein the method comprises the following steps: step 3.3, pressing and molding the blank making powder obtained in the step 3.2, and controlling the pressure to ensure that the side length of the molded blank is 26mm, the thickness is 4.55mm, and the density is 3.25g/cm3。
12. The method for preparing the low-gradient large-flux impact-stability resistor disc as claimed in claim 10, wherein the method comprises the following steps: in the step 4.3, the side length of the ZnO piezoresistor is 22-23mm, the thickness of the ZnO piezoresistor is 3.00-4.00mm, the range of the piezopotential gradient is 150-170V/mm, the nonlinear coefficient is 80-105, the residual voltage ratio of 10kA 8/20 mus lightning wave is 2.3-2.5, and after 20 x 10kA 8/20 mus lightning wave impact, the difference between the positive and negative piezovoltages is not more than 5% compared with that before impact.
CN202111061132.1A 2021-09-10 2021-09-10 Low-gradient large-current impact-stability resistor material and preparation method thereof Pending CN113716952A (en)

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