CN108863405B - ZnO pressure-sensitive ceramic additive and preparation method and application thereof - Google Patents
ZnO pressure-sensitive ceramic additive and preparation method and application thereof Download PDFInfo
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Abstract
The invention belongs to the field of pressure-sensitive materials, and provides a ZnO pressure-sensitive ceramic additive, and a preparation method and application thereofThe preparation method comprises the following steps: 1) adding ZnO and Sb2O3Ball milling with solvent as medium to obtain slurry, wherein ZnO and Sb2O3The molar ratio of (A) to (B) is 1-14: 1; 2) drying and calcining the slurry obtained in the step 1) to obtain the ZnO voltage-sensitive ceramic additive. The invention further provides the ZnO pressure sensitive ceramic additive and application thereof. The ZnO voltage-sensitive ceramic additive is added into a raw material for preparing ZnO voltage-sensitive ceramic, ZnO crystal grain growth is promoted, voltage-sensitive voltage is reduced, low-temperature sintering of a voltage-sensitive resistor is kept, the nonlinear coefficient of the voltage-sensitive ceramic can be increased, the sintering temperature of the ZnO voltage-sensitive ceramic is reduced to 850-900 ℃, the nonlinear coefficient alpha value of the material can reach 91, and the voltage-sensitive field strength is reduced to 500-760V/mm.
Description
Technical Field
The invention belongs to the field of pressure-sensitive materials, relates to a ZnO pressure-sensitive ceramic additive, a preparation method and application thereof, and particularly relates to a ZnO pressure-sensitive ceramic additive capable of reducing the ZnO pressure-sensitive voltage and the sintering temperature of a piezoresistor, and a preparation method and application thereof.
Background
The piezoresistor is a nonlinear volt-ampere characteristic electronic ceramic device with the resistance value sensitively changed along with the increase of the applied voltage, is widely applied to overvoltage protection of a power system, electrostatic protection in an electronic circuit, surge current absorption and the like, and is widely applied. Varistor material systems are numerous, e.g. SiC, TiO2、SnO2And ZnO pressure sensitive ceramics, and the like. Compared with other voltage dependent resistor materials, the ZnO semiconductor ceramic has better voltage dependent characteristics: its nonlinear coefficient is high, response speed to abnormal voltage is fast, leakage current under normal working state is small, influence by temperature is small and cost is low. ZnO varistor technology was pioneered since 1967 to date for over 50 years, and has been used as a protection from high voltage power systems to low voltage electronic circuitsThe sensitive resistor covers almost all electrical equipment and electronics.
With the development of communication technology and microelectronic technology, the volume of electronic equipment gradually develops towards miniaturization, and the integration degree of electronic equipment is higher and higher. This causes the driving voltage of the electronic components in the circuit to gradually decrease, and the voltage endurance of the electronic components also decreases, which can greatly increase the probability of the electronic circuit being damaged by electromagnetic pulse interference, operation overvoltage, and electrostatic discharge of human body. For this reason, low pressure and low power are required for the pressure-sensitive material.
At present: the Zn piezoresistor low-voltage method mainly comprises the following steps: (1) the thickness of the pressure-sensitive ceramic sheet is reduced by using a high-pressure formula. (2) The average grain size of ZnO is increased by a seed crystal method or a method of adding a grain growth promoter, increasing the sintering temperature, prolonging the heat preservation time and the like. The way (1) has high requirements on the preparation process and equipment thereof and is expensive in manufacturing cost. In the approach (2), the seed crystal method takes long time for preparing and screening seed crystals, the process is complex, and the uniformity of materials is poor. The performances of the zinc oxide, the additives of the zinc oxide, and the like, such as nonlinear coefficient, can be influenced by the fact that the sintering temperature is increased and the heat preservation time is prolonged. In contrast, the addition of grain growth promoting additives is currently the simplest and most effective method for low compaction. However, in general, oxide additives that promote grain growth will reduce the varistor nonlinear coefficient to varying degrees or increase its sintering temperature.
Therefore, it is very significant for the low-voltage transformation development of ZnO piezoresistors to prepare a grain growth promoter which does not reduce the nonlinear coefficient or even increase the nonlinear coefficient, and has a lower sintering temperature.
Disclosure of Invention
In view of the defects of the prior art, the invention aims to provide a ZnO voltage-sensitive ceramic additive and a preparation method and application thereof, the additive is simple in preparation process and stable in chemical property, the ZnO voltage-sensitive ceramic additive is added into a raw material for preparing ZnO voltage-sensitive ceramic, ZnO crystal grain growth is promoted, voltage-sensitive voltage is reduced, low-temperature sintering of a piezoresistor is kept, the nonlinear coefficient of the voltage-sensitive ceramic can be increased, the sintering temperature of the ZnO voltage-sensitive ceramic is reduced to 850-900 ℃, the alpha value of the nonlinear coefficient of the material can reach 91, and the field intensity of the voltage-sensitive ceramic is reduced to 500-760V/mm.
In order to achieve the above objects and other related objects, a first aspect of the present invention provides a method for preparing a ZnO pressure sensitive ceramic additive, comprising the steps of:
1) adding ZnO and Sb2O3Ball milling with solvent as medium to obtain slurry, wherein ZnO and Sb2O3The molar ratio of (A) to (B) is 1-14: 1, as 1-6: 1 or 6 to 14: 1;
2) drying and calcining the slurry obtained in the step 1) to obtain the ZnO voltage-sensitive ceramic additive.
Preferably, in step 1), the solvent is selected from one or more of absolute ethyl alcohol and deionized water.
Preferably, in the step 1), the ball milling time is 1-5 hours, such as 1-3 hours, 3-4 hours or 4-5 hours.
Preferably, in the step 2), the drying temperature is 80-120 ℃.
Preferably, step 2) further comprises at least one of the following technical features:
1) the drying time is 5-15 h;
2) the calcination temperature is 700-900 deg.C, such as 700-750 deg.C, 750-800 deg.C, 800-850 deg.C or 850-900 deg.C;
3) the calcination time is 5-12 h, such as 5-10 h or 10-12 h.
Preferably, further comprising step 3): grinding and sieving the ZnO voltage-sensitive ceramic additive obtained in the step 2).
More preferably, the mesh number of the screen is 60 to 100 mesh.
The invention provides a ZnO pressure-sensitive ceramic additive which is obtained by adopting any one of the preparation methods.
The third aspect of the invention provides the use of the ZnO voltage-sensitive ceramic additive for adding into raw materials for preparing ZnO voltage-sensitive ceramic.
Preferably, the ZnO pressure sensitive ceramic additive is added in an amount of 0.1 to 0.6at%, such as 0.1 to 0.2 at%, 0.2 to 0.3 at%, 0.3 to 0.4 at%, 0.4 to 0.5 at%, or 0.5 to 0.6 at%.
The invention discloses a ZnO pressure sensitive ceramic additive and a preparation method and application thereof, wherein the chemical elements of the ZnO pressure sensitive ceramic additive comprise Zn, Sb and O, and the preparation method comprises the following steps: 1) adding ZnO and Sb2O3Ball milling with solvent as medium to obtain slurry, wherein ZnO and Sb2O3The molar ratio of (A) to (B) is 1-14: 1; 2) drying and calcining the slurry obtained in the step 1) to obtain the ZnO voltage-sensitive ceramic additive. The invention further provides the ZnO pressure sensitive ceramic additive and application thereof. The ZnO voltage-sensitive ceramic additive is added into a raw material for preparing ZnO voltage-sensitive ceramic, ZnO crystal grain growth is promoted, voltage-sensitive voltage is reduced, low-temperature sintering of a voltage-sensitive resistor is kept, the nonlinear coefficient of the voltage-sensitive ceramic can be increased, the sintering temperature of the ZnO voltage-sensitive ceramic is reduced to 850-900 ℃, the nonlinear coefficient alpha value of the material can reach 91, and the voltage-sensitive field strength is reduced to 500-760V/mm.
Drawings
Fig. 1 shows that the molar ratio of ZnO pressure sensitive ceramic additive is ZnO: sb2O314: 1 XRD analysis pattern of sintering at 750 ℃.
Fig. 2 shows the molar ratio of ZnO pressure sensitive ceramic additive to ZnO: sb2O314: 1 XRD analysis pattern of sintering at 850 ℃.
Detailed Description
The present invention is further illustrated below with reference to specific examples, which are intended to be illustrative only and not to limit the scope of the invention.
The embodiments of the present invention are described below with reference to specific embodiments, and other advantages and effects of the present invention will be easily understood by those skilled in the art from the disclosure of the present specification. The invention is capable of other and different embodiments and of being practiced or of being carried out in various ways, and its several details are capable of modification in various respects, all without departing from the spirit and scope of the present invention.
It should be understood that the processing equipment or devices not specifically mentioned in the following examples are conventional in the art; all pressure values and ranges are relative pressures and the starting materials used are those conventionally used in the art.
Furthermore, it is to be understood that one or more method steps mentioned in the present invention does not exclude that other method steps may also be present before or after the combined steps or that other method steps may also be inserted between these explicitly mentioned steps, unless otherwise indicated; it is also to be understood that a combined connection between one or more devices/apparatus as referred to in the present application does not exclude that further devices/apparatus may be present before or after the combined device/apparatus or that further devices/apparatus may be interposed between two devices/apparatus explicitly referred to, unless otherwise indicated. Moreover, unless otherwise indicated, the numbering of the various method steps is merely a convenient tool for identifying the various method steps, and is not intended to limit the order in which the method steps are arranged or the scope of the invention in which the invention may be practiced, and changes or modifications in the relative relationship may be made without substantially changing the technical content.
Example 1 ZnO and Sb2O3In a molar ratio of 14: 1
1) Adding ZnO and Sb2O3Ball milling for 4h by taking absolute ethyl alcohol as a medium to obtain slurry, wherein ZnO and Sb2O3In a molar ratio of 14: 1;
2) drying the slurry obtained in the step 1), grinding, putting into a crucible, and calcining, wherein the drying temperature is 80 ℃, the drying time is 8 hours, the calcining temperature is 750 ℃, and the calcining time is 10 hours;
3) and grinding the calcined powder, and sieving the powder by a 60-mesh sieve to obtain the ZnO voltage-sensitive ceramic additive.
To (97at% -x) ZnO- (1at%) Bi2O3-(0.5at％)Sb2O3-(0.5at％)MnO2-(0.5at％)Co2O3-(0.5at％)Cr2O3ZnO pressure sensitive ceramic additives in the amount of x (x ═ 0 at%, 0.1 at%, 0.3 at%, 0.5 at%) are added to the initial powder of the system pressure sensitive resistor ceramic. According to the stoichiometric ratio in the formulaTaking raw materials: ZnO and Bi2O3、Sb2O3、MnO2、Co2O3、Cr2O3And an additive; ball-milling the weighed raw material powder for 4 hours by using absolute ethyl alcohol as a medium, preserving the heat of slurry obtained by ball-milling for 8 hours at the temperature of 80 ℃, fully grinding the powder, and dropwise adding polyvinyl alcohol (PVA) with the weight of 10 wt% of the powder for granulation. Then, the obtained powder is pressed and molded under the relative pressure of 100MPa to obtain a wafer with the diameter of 10mm and the thickness of 1.5 mm; and fully removing the adhesive of the ceramic plates, and sintering the ceramic plates in air at 850,880,900,920 ℃ for 2h to obtain the ZBSSMCC pressure-sensitive ceramic.
The obtained ZBSSMCC pressure sensitive ceramic is finely ground, cleaned by ultrasonic waves and then tested by a silver electrode for electrical properties. Among these, the properties of the samples obtained at a sintering temperature of 900 ℃ are the best, as shown in table 1.
Table 1 electrical properties of the samples of example 1
FIG. 1 shows ZnO voltage sensitive ceramic additive with ZnO and Sb2O3In a molar ratio of 14: 1 XRD analysis pattern of sintering at 750 ℃. As can be seen from FIG. 1, the additive is composed of ZnO and ZnSb2+5O6、Zn2.33Sb0.67O4And Zn7Sb2O12Four phases. It can be seen from the table one that the addition of the additive can reduce the voltage-sensitive field intensity of the ZBSSMCC system voltage-sensitive resistor, and the voltage-sensitive field intensity gradually decreases with the increase of the addition amount, and meanwhile, when 0.3 at% of ZnO voltage-sensitive ceramic additive is added, the nonlinear coefficient reaches 77, and the sintering temperature is as low as 900 ℃.
Example 2 ZnO and Sb2O3In a molar ratio of 14: 1
1) Adding ZnO and Sb2O3Ball milling for 4h by taking absolute ethyl alcohol as a medium to obtain slurry, wherein ZnO and Sb2O3In a molar ratio of 14: 1;
2) drying the slurry obtained in the step 1), grinding, pressing the powder into a large sheet, putting the large sheet into a crucible, and calcining for 12 hours, wherein the drying temperature is 120 ℃, the drying time is 8 hours, the calcining temperature is 850 ℃, and the calcining time is 12 hours;
3) and grinding the calcined powder, and sieving the powder by a 60-mesh sieve to obtain the ZnO voltage-sensitive ceramic additive.
To (97.5at% -x) ZnO- (1at%) Bi2O3-(0.5at％)Sb2O3-(0.5at％)MnO2-(0.5at％)Co2O3ZnO pressure sensitive ceramic additives in the amount of x (x ═ 0 at%, 0.2 at%, 0.4 at%, 0.6 at%) are added to the initial powder of the system pressure sensitive resistor ceramic. Weighing the raw materials according to the stoichiometric ratio in the formula: ZnO and Bi2O3、Sb2O3、MnO2、Co2O3And an additive; ball-milling the weighed raw material powder for 4h by taking deionized water as a medium, preserving the heat of slurry obtained by ball-milling for 8h at 120 ℃, fully grinding the powder, and dropwise adding polyvinyl alcohol (PVA) with the weight of 10 wt% for granulation. Then, the obtained powder is pressed and molded under the relative pressure of 100MPa to obtain a wafer with the diameter of 10mm and the thickness of 1.5 mm; and fully removing the adhesive of the ceramic plates, and sintering the ceramic plates in air at 830,850,880,900 ℃ for 2 hours to obtain the ZBSMC series pressure sensitive ceramic.
The obtained ZBSMC pressure-sensitive ceramic is finely ground, ultrasonically cleaned and then subjected to silver electrode testing to test the electrical properties. Among these, the properties of the samples obtained at a sintering temperature of 880 ℃ are the best, see table 2.
Table 2 electrical properties of the samples of example 2
FIG. 2 is a graph of ZnO varistor ceramic additives with ZnO and Sb2O3In a molar ratio of 14: 1 XRD analysis pattern of sintering at 850 ℃. It can be seen from FIG. 2 that the additive reacts with Zn7Sb2O12The diffraction peaks of the phases fit better. As can be seen from Table 2, the ZBTMC-based pressure sensitive ceramics showed a decrease in the pressure sensitive field strength after addition of the additive, and when 0.4 at% of the ZnO-based pressure sensitive ceramics was addedWhen the additive is used, the pressure-sensitive performance is optimal, the nonlinear coefficient is 91, the leakage current is 0, and the sintering temperature is lower and is 880 ℃.
Example 3 ZnO and Sb2O3In a molar ratio of 6: 1
1) Adding ZnO and Sb2O3Ball milling for 4h by taking absolute ethyl alcohol as a medium to obtain slurry, wherein ZnO and Sb2O3In a molar ratio of 6: 1;
2) drying the slurry obtained in the step 1), grinding, putting into a crucible, and calcining, wherein the drying temperature is 80 ℃, the drying time is 8 hours, the calcining temperature is 700 ℃, and the calcining time is 10 hours;
3) grinding the calcined powder, and sieving with a 60-mesh sieve to obtain the ZnO voltage-sensitive ceramic additive mainly comprising ZnO and Sb2O3、Sb2O4、ZnSb2+5O6、Zn2.33Sb0.67O4Phase composition, wherein ZnO is taken as a main crystal phase.
To (97.5at% -x) ZnO- (1at%) Bi2O3-(0.5at％)Sb2O3-(0.5at％)MnO2-(0.5at％)Co2O3The ZnO voltage sensitive ceramic additive with the amount of x (x is 0 at%, 0.2 at%, 0.4 at%, 0.6 at%) is added into the initial powder of the voltage sensitive resistor ceramic. Weighing the raw materials according to the stoichiometric ratio in the formula: ZnO and Bi2O3、Sb2O3、MnO2、Co2O3And an additive; ball-milling the weighed raw material powder for 4 hours by using absolute ethyl alcohol as a medium, preserving the heat of slurry obtained by ball-milling for 8 hours at the temperature of 80 ℃, fully grinding the powder, and dropwise adding polyvinyl alcohol (PVA) with the weight of 10 wt% of the powder for granulation. Then, the obtained powder is pressed and molded under the relative pressure of 100MPa to obtain a wafer with the diameter of 10mm and the thickness of 1.5 mm; and fully removing the adhesive of the ceramic plates, and sintering the ceramic plates in air at 880,900,920,950 ℃ for 2 hours to obtain the ZBSMC series pressure sensitive ceramic.
The obtained ZBSMC pressure-sensitive ceramic is finely ground, ultrasonically cleaned and then subjected to silver electrode testing to test the electrical properties. Among them, the properties of the samples obtained at a sintering temperature of 920 ℃ are the best, see table 3.
Table 3 electrical properties of the samples of example 3
It can be seen from table three that the addition of the additive can reduce the voltage-sensitive field strength of the varistor of the ZBTSC system, and when 0.4 at% of ZnO voltage-sensitive ceramic additive is added, the nonlinear coefficient of the sample is at most 61, and the preferred sintering temperature is as low as 920 ℃.
Example 4 ZnO and Sb2O3In a molar ratio of 6: 1
1) Adding ZnO and Sb2O3Ball milling for 3h by taking deionized water as a medium to obtain slurry, wherein ZnO and Sb2O3In a molar ratio of 6: 1;
2) drying the slurry obtained in the step 1), grinding, pressing the powder into a large sheet, putting the large sheet into a crucible, and calcining for 12 hours, wherein the drying temperature is 120 ℃, the drying time is 8 hours, the calcining temperature is 900 ℃, and the calcining time is 12 hours;
3) grinding the calcined powder, and sieving with a 60-mesh sieve to obtain the ZnO voltage-sensitive ceramic additive mainly comprising ZnO and Sb2O3、Sb2O4、Zn7Sb2O12Phase composition, wherein ZnO is taken as a main crystal phase.
To (97.5at% -x) ZnO- (1at%) Bi2O3-(0.5at％)Sb2O3-(0.5at％)MnO2-(0.5at％)Cr2O3The ZnO varistor ceramic additive of x (x is 0 at%, 0.2 at%, 0.4 at%, 0.6 at%) is added into the initial powder of the varistor ceramic. Weighing the raw materials according to the stoichiometric ratio in the formula: ZnO and Bi2O3、Sb2O3、MnO2、Cr2O3And an additive; ball-milling the weighed raw material powder for 4h by taking deionized water as a medium, preserving the heat of slurry obtained by ball-milling for 8h at 120 ℃, fully grinding the powder, and dropwise adding polyvinyl alcohol (PVA) with the weight of 10 wt% for granulation. Then will obtainPressing and molding the powder under the relative pressure of 100MPa to obtain a wafer with the diameter of 10mm and the thickness of 1.5 mm; and fully removing the adhesive of the ceramic plates, and sintering the ceramic plates in air at 880,900,920,950 ℃ for 2 hours to obtain the ZBSMC series pressure sensitive ceramic.
The obtained ZBSMC pressure-sensitive ceramic is finely ground, ultrasonically cleaned and then subjected to silver electrode testing to test the electrical properties. Among them, the properties of the samples obtained at a sintering temperature of 920 ℃ are the best, see table 4.
Table 4 electrical properties of the samples of example 4
As can be seen from Table 4, the addition of the additive can reduce the varistor strength of the ZBTMC system, and when 0.4 at% of ZnO varistor ceramic additive is added, the nonlinear coefficient is at most 77, and the preferred sintering temperature is 920 ℃.
Example 5 ZnO and Sb2O3In a molar ratio of 1: 1
1) Adding ZnO and Sb2O3Ball milling for 4h by taking absolute ethyl alcohol as a medium to obtain slurry, wherein ZnO and Sb2O3In a molar ratio of 1: 1;
2) drying and grinding the slurry obtained in the step 1), and putting the powder into a crucible for calcination, wherein the drying temperature is 80 ℃, the drying time is 8 hours, the calcination temperature is 800 ℃, and the calcination time is 10 hours;
3) grinding the calcined powder, and sieving with a 60-mesh sieve to obtain the ZnO voltage-sensitive ceramic additive, wherein the ZnO voltage-sensitive ceramic additive mainly comprises Sb2O3、Sb2O4、Sb2O5、Zn7Sb2O12Phase composition in which Sb is2O5Is a main crystal phase.
To (97at% -x) ZnO- (1at%) Bi2O3-(0.5at％)Sb2O3-(0.5at％)MnO2-(0.5at％)Co2O3-(0.5at％)Cr2O3Adding x (0 at%,0.1 at%, 0.3 at%, 0.5 at%) of ZnO pressure sensitive ceramic additive. Weighing the raw materials according to the stoichiometric ratio in the formula: ZnO and Bi2O3、Sb2O3、MnO2、Co2O3、Cr2O3And an additive; ball-milling the weighed raw material powder for 4 hours by using absolute ethyl alcohol as a medium, preserving the heat of slurry obtained by ball-milling for 8 hours at the temperature of 80 ℃, fully grinding the powder, and dropwise adding polyvinyl alcohol (PVA) with the weight of 10 wt% of the powder for granulation. Then, the obtained powder is pressed and molded under the relative pressure of 100MPa to obtain a wafer with the diameter of 10mm and the thickness of 1.5 mm; and fully removing the adhesive of the ceramic plates, and sintering the ceramic plates in air at 880,900,920,950 ℃ for 2h to obtain the ZBSSMCC pressure-sensitive ceramic.
The obtained ZBSSMCC pressure sensitive ceramic is finely ground, cleaned by ultrasonic waves and then tested by a silver electrode for electrical properties. Among them, the properties of the samples obtained at a sintering temperature of 920 ℃ are the best, see table 5.
Table 5 electrical properties of the samples of example 5
As can be seen from Table 5, the addition of the additive can reduce the varistor strength of the ZBSSMCC system varistor, and when 0.1 at% of ZnO varistor ceramic additive is added, the nonlinear coefficient is at most 64, and the preferred sintering temperature is 920 ℃.
Example 6 ZnO and Sb2O3In a molar ratio of 1: 1
1) Adding ZnO and Sb2O3Ball milling for 4h by taking absolute ethyl alcohol as a medium to obtain slurry, wherein ZnO and Sb2O3In a molar ratio of 1: 1;
2) drying the slurry obtained in the step 1), grinding, pressing the powder into a large sheet, putting the large sheet into a crucible, and calcining for 12 hours, wherein the drying temperature is 120 ℃, the drying time is 8 hours, the calcining temperature is 900 ℃, and the calcining time is 12 hours;
3) grinding the calcined powder, and sieving with a 60-mesh sieve to obtain the ZnO voltage-sensitive ceramic additive, wherein the ZnO voltage-sensitive ceramic additive mainly comprises Sb2O3、Sb2O4、Sb2O5、Zn7Sb2O12Phase composition in which Sb is2O5Is a main crystal phase.
To (97.5at% -x) ZnO- (1at%) Bi2O3-(0.5at％)Sb2O3-(0.5at％)MnO2-(0.5at％)Cr2O3The ZnO varistor ceramic additive of x (x is 0 at%, 0.2 at%, 0.4 at%, 0.6 at%) is added into the initial powder of the varistor ceramic. Weighing the raw materials according to the stoichiometric ratio in the formula: ZnO and Bi2O3、Sb2O3、MnO2、Cr2O3And an additive; ball-milling the weighed raw material powder for 4h by taking deionized water as a medium, preserving the heat of slurry obtained by ball-milling for 8h at 120 ℃, fully grinding the powder, and dropwise adding polyvinyl alcohol (PVA) with the weight of 10 wt% for granulation. Then, the obtained powder is pressed and molded under the relative pressure of 100MPa to obtain a wafer with the diameter of 10mm and the thickness of 1.5 mm; and fully removing the adhesive of the ceramic plates, and sintering the ceramic plates in air at 880,900,920,950 ℃ for 2 hours to obtain the ZBSMC series pressure sensitive ceramic.
The obtained ZBSMC pressure-sensitive ceramic is finely ground, ultrasonically cleaned and then subjected to silver electrode testing to test the electrical properties. Among them, the properties of the samples obtained at a sintering temperature of 920 ℃ are the best, see table 6.
Table 6 electrical properties of the samples of example 6
As can be seen from Table 6, the addition of the additive can reduce the varistor strength of the ZBTMC system, and when 0.2 at% of ZnO varistor ceramic additive is added, the nonlinear coefficient is at most 67, and the preferred sintering temperature is 920 ℃.
The foregoing embodiments are merely illustrative of the principles and utilities of the present invention and are not intended to limit the invention. Any person skilled in the art can modify or change the above-mentioned embodiments without departing from the spirit and scope of the present invention. Accordingly, it is intended that all equivalent modifications or changes which can be made by those skilled in the art without departing from the spirit and technical spirit of the present invention be covered by the claims of the present invention.
Claims (8)
1. The application of the ZnO voltage-sensitive ceramic additive is characterized in that the ZnO voltage-sensitive ceramic additive is used for promoting the growth of ZnO crystal grains, reducing the voltage-sensitive voltage and increasing the nonlinear coefficient of the voltage-sensitive ceramic, and the ZnO voltage-sensitive ceramic is (97at%) ZnO- (1at%) Bi2O3-(0.5at%)Sb2O3-(0.5at%)MnO2-(0.5at%)Co2O3-(0.5at%)Cr2O3Or (97.5at%) ZnO- (1at%) Bi2O3-(0.5at%)Sb2O3-(0.5at%)MnO2-(0.5at%)Co2O3Or (97.5at%) ZnO- (1at%) Bi2O3-(0.5at%)Sb2O3-(0.5at%)MnO2-(0.5at%)Cr2O3，
The ZnO pressure-sensitive ceramic additive is obtained by adopting a preparation method comprising the following steps:
1) adding ZnO and Sb2O3Ball milling with solvent as medium to obtain slurry, wherein ZnO and Sb2O3The molar ratio of (A) to (B) is 1-14: 1;
2) drying and calcining the slurry obtained in the step 1), wherein the calcining temperature is 700-900 ℃, and the ZnO pressure-sensitive ceramic additive is obtained.
2. The use according to claim 1, wherein the ZnO pressure sensitive ceramic additive is added in an amount of 0.1 to 0.6 at%.
3. The use according to claim 1, wherein in step 1), the solvent is selected from one or more of absolute ethanol and deionized water.
4. The use according to claim 1, wherein in step 1), the ball milling time is 1-5 h.
5. The use according to claim 1, wherein in step 2), the drying temperature is 80-120 ℃.
6. The use according to claim 1, wherein in step 2), the drying time is 5 to 15 hours and/or the calcination time is 5 to 12 hours.
7. The use according to claim 1, further comprising step 3): grinding and sieving the ZnO voltage-sensitive ceramic additive obtained in the step 2).
8. Use according to claim 7, wherein the mesh size of the screen is 60 to 100 mesh.
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