CN113979740B - Pressure-sensitive ceramic additive, pressure-sensitive ceramic material, pressure-sensitive ceramic and preparation method thereof, piezoresistor and preparation method thereof, and resistor element - Google Patents

Pressure-sensitive ceramic additive, pressure-sensitive ceramic material, pressure-sensitive ceramic and preparation method thereof, piezoresistor and preparation method thereof, and resistor element Download PDF

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CN113979740B
CN113979740B CN202111183825.8A CN202111183825A CN113979740B CN 113979740 B CN113979740 B CN 113979740B CN 202111183825 A CN202111183825 A CN 202111183825A CN 113979740 B CN113979740 B CN 113979740B
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pressure
sensitive ceramic
sintering
sensitive
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CN113979740A (en
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郝留成
宋继光
陈蕊
徐仲勋
李凯
姜珊盼
赵新科
张琳
刘威
徐晨博
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State Grid Zhejiang Electric Power Co Ltd
Pinggao Group Co Ltd
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State Grid Zhejiang Electric Power Co Ltd
Pinggao Group Co Ltd
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Abstract

The invention relates to a pressure-sensitive ceramic additive, a pressure-sensitive ceramic material, pressure-sensitive ceramic and a preparation method thereof, a piezoresistor and a preparation method thereof, and a resistor element, and belongs to the technical field of piezoresistor materials. The additive for ZnO pressure-sensitive ceramics is mainly prepared by sintering the following raw materials: gd (Gd) 2 O 3 、Bi 2 O 3 And Sb (Sb) 2 O 3 . The microstructure and uniformity of the ZnO pressure-sensitive ceramic material can be optimized through the additive sintering process. The grain distribution effect of the ZnO varistor plays a dominant role in the energy absorbing capacity, and uneven grain distribution and high porosity can lead to uneven leakage current and heat concentration, thereby reducing the energy absorbing capacity. The energy absorption capacity of the ZnO varistor prepared by the additive for ZnO voltage-sensitive ceramics can reach 290J/cm 3 。

Description

Pressure-sensitive ceramic additive, pressure-sensitive ceramic material, pressure-sensitive ceramic and preparation method thereof, piezoresistor and preparation method thereof, and resistor element
Technical Field
The invention relates to a pressure-sensitive ceramic additive, a pressure-sensitive ceramic material, pressure-sensitive ceramic and a preparation method thereof, a piezoresistor and a preparation method thereof, and a resistor element, and belongs to the technical field of piezoresistor materials.
Background
The nonlinear ohmic characteristic of the zinc oxide varistor valve plate is a crystal boundary effect, the formation mechanism of the pressure-sensitive performance of the zinc oxide varistor valve plate is closely related to the crystal boundary structure, such as the number of crystal boundaries, donor concentration, interface state density, schottky barrier height and the like, on the electrical parameters (nonlinear coefficient alpha, pressure-sensitive voltage gradient E) 1mA Leakage current I L Etc.) produces a direct effect. The grain boundary characteristic of the ZnO varistor depends on the formula components and the preparation process of the sample. The zinc oxide pressure sensitive ceramic is prepared by adding multiple oxides (Bi 2 O 3 、Sb 2 O 3 、Co 2 O 3 、MnO 2 Etc.), the new type of multifunctional semiconductor ceramic element sintered by traditional ceramic process, changing the kind of additive and optimizing technological parameters becomes the main means for regulating and controlling the microstructure and grain boundary property of ZnO pressure sensitive ceramic and raising its electrical performance.
The zinc oxide pressure-sensitive valve plate has the advantages of excellent nonlinear ohmic characteristic, high energy absorption capacity, short response time and the like, so that the zinc oxide pressure-sensitive valve plate is applied to a surge absorber for protecting a lightning arrester valve core of a power line from voltage surge, wherein the pressure-sensitive voltage gradient and the energy absorption capacity are main characteristic parameters of the ZnO varistor valve plate. The voltage-sensitive voltage gradient of the current ZnO varistor valve plate is low, and the miniaturization of the volume of the arrester product prepared by the ZnO varistor valve plate is limited.
Disclosure of Invention
The invention aims to provide an additive for ZnO pressure-sensitive ceramics, and ZnO pressure-sensitive ceramics prepared by using the additive have high voltage gradient.
The second object of the invention is to provide a ZnO pressure-sensitive ceramic material.
The third object of the invention is to provide a ZnO pressure sensitive ceramic.
The fourth object of the invention is to provide a preparation method of ZnO pressure-sensitive ceramic.
A fifth object of the present invention is to provide a ZnO varistor.
The sixth object of the invention is to provide a method for preparing ZnO varistor.
A seventh object of the present invention is to provide a varistor element.
In order to achieve the above purpose, the technical scheme of the additive for ZnO pressure-sensitive ceramics of the invention is as follows:
an additive for ZnO pressure-sensitive ceramics is mainly prepared by sintering the following raw materials: gd (Gd) 2 O 3 、Bi 2 O 3 And Sb (Sb) 2 O 3 。
When the additive for ZnO pressure-sensitive ceramics is used for preparing ZnO pressure-sensitive ceramics, znO and Sb 2 O 3 Reacting to generate Zn 7 Sb 2 O 12 Spinel phase, rare earth oxide Gd 2 O 3 With Bi 2 O 3 、Sb 2 O 3 Reacting to generate Bi 6 Gd 2 O 12 、Gd 3 Sb 5 O 12 The phases, the second phases gather at the grain boundaries to play a role of 'pinning', and inhibit the growth of ZnO main grains. The voltage-sensitive voltage gradient is mainly affected by the grain size and breakdown voltage of each grain boundary, and equation E can be used 1mA ＝V gb And (5) calculating the x d. Wherein E is 1mA Is a voltage-sensitive voltage gradient, d is the number of grain boundaries, V gb Is the breakdown voltage of each grain boundary. Smaller ZnO grains and higher V gb Resulting in a higher breakdown voltage. Taking into account V of the sample gb Relatively small variation, thus grain size vs. Conditioning E 1mA Plays a main role. The second phase generated in the sintering process reduces the average grain size of ZnO through the pinning effect, so that the voltage-sensitive potential gradient of the ZnO varistor is obviously improved. The voltage-sensitive voltage gradient of the ZnO varistor prepared by the method can reach 480-600V/mm.
Preferably, the Gd 2 O 3 、Bi 2 O 3 And Sb (Sb) 2 O 3 The molar ratio of (2) is 0.25-1.00:0.50-0.80:0.80-1.20.
Preferably, the raw material further comprises Co 2 O 3 、MnO 2 、NiO、SiO 2 And Cr (V) 2 O 3 。
Preferably, the Gd 2 O 3 、Bi 2 O 3 、Sb 2 O 3 、Co 2 O 3 、MnO 2 、NiO、SiO 2 And Cr (V) 2 O 3 The molar ratio of the (C) to the (B) is 0.25-1.00:0.50-0.80:0.80-1.20:0.60-0.90:0.50-0.90:0.30-0.80:1.30-1.60:0.10-0.50.
Preferably, the sintering temperature is 700 ℃ to 900 ℃.
Preferably, the sintering time is 2 to 4 hours.
Preferably, the temperature rising rate of the sintering temperature is 3 ℃/min to 5 ℃/min.
Preferably, the raw materials are mixed and ground prior to sintering.
Preferably, the grinding is ball milling.
Preferably, the ball milling medium is absolute ethanol.
Preferably, the amount of the absolute ethyl alcohol added is 1.0 mL-1.5 mL per g of the powder.
More preferably, the amount of the absolute ethyl alcohol added is 1.2mL per g of powder.
Preferably, the ball milling rate is 400r/min to 600r/min.
More preferably, the ball milling rate is 400r/min.
Preferably, the ball milling time is 5-12 hours.
More preferably, the ball milling time is 5 hours.
The ZnO pressure-sensitive ceramic material has the technical scheme that:
a ZnO pressure-sensitive ceramic material comprises ZnO and the additive for ZnO pressure-sensitive ceramic.
According to the ZnO pressure-sensitive ceramic material, the sintering additives are added, so that on one hand, the mixing uniformity among the additives can be improved, and on the other hand, the sintering activity of the additives can be effectively reduced. Both functions can improve the microscopic uniformity of the ZnO voltage-sensitive ceramic material, thereby improving the energy absorption capacity of the ZnO varistor.
Preferably, the ZnO pressure-sensitive ceramic material is composed of ZnO and an additive for ZnO pressure-sensitive ceramic. Preferably, the additive for ZnO pressure-sensitive ceramics is prepared by sintering the following raw materials: gd (Gd) 2 O 3 、Bi 2 O 3 、Sb 2 O 3 、Co 2 O 3 、MnO 2 、NiO、SiO 2 And Cr (V) 2 O 3 。
Preferably, the additive for ZnO pressure-sensitive ceramics is prepared by sintering the following raw materials in mole percent based on 100 parts of total mole of ZnO and the additive for ZnO pressure-sensitive ceramics:
Gd 2 O 3 0.25～1.00，Sb 2 O 3 0.80～1.20，Co 2 O 3 0.60～0.90，MnO 2 0.50～0.90，Bi 2 O 3 0.50～0.80，NiO 0.30～0.80，SiO 2 1.30～1.60，Cr 2 O 3 0.10～0.50。
preferably, the ZnO pressure-sensitive ceramic material is obtained by a preparation method comprising the following steps: znO and the additive for ZnO pressure-sensitive ceramics are mixed.
Preferably, the mixing comprises a ball milling process.
Preferably, the ball milling medium is absolute ethanol.
Preferably, the ball milling rate is 400r/min.
Preferably, the ball milling time is 5 hours.
Preferably, the preparation method further comprises the following steps: and mixing and sieving.
Preferably, the mesh number of the sieve is 100.
The ZnO pressure-sensitive ceramic has the technical scheme that:
the ZnO voltage-sensitive ceramic material is obtained by sintering treatment.
The ZnO pressure-sensitive ceramic material of the invention mainly comprises ZnO and Gd 2 O 3 ，Sb 2 O 3 And Bi (Bi) 2 O 3 ZnO and Sb are used as raw materials in the sintering process 2 O 3 Reacting to generate Zn 7 Sb 2 O 12 Spinel phase, rare earth oxide Gd 2 O 3 With Bi 2 O 3 、Sb 2 O 3 Reacting to generate Bi 6 Gd 2 O 12 、Gd 3 Sb 5 O 12 The phases, the second phases gather at the grain boundaries to play a role of 'pinning', and inhibit the growth of ZnO main grains. Thus, by optimizing Gd 2 O 3 And other additives, can further enhance the voltage-dependent voltage gradient. The voltage-sensitive voltage gradient of the ZnO varistor prepared by the method can reach 480-600V/mm. In addition, the microstructure and uniformity of the ZnO pressure-sensitive ceramic material can be optimized through the additive sintering process. The grain distribution effect of the ZnO varistor plays a dominant role in the energy absorbing capacity, and uneven grain distribution and high porosity can lead to uneven leakage current and heat concentration, thereby reducing the energy absorbing capacity. The energy absorption capacity of the ZnO varistor prepared by the additive for ZnO voltage-sensitive ceramics can reach 290J/cm 3 。
The technical scheme of the preparation method of the ZnO pressure-sensitive ceramic is as follows:
a preparation method of ZnO pressure-sensitive ceramic comprises the following steps: and sintering the ZnO pressure-sensitive ceramic material to obtain the ZnO pressure-sensitive ceramic material.
The preparation method of the ZnO voltage-sensitive ceramic is simple to operate, and the voltage-sensitive voltage gradient and the energy absorption capacity of the piezoresistor can be improved by utilizing the ZnO voltage-sensitive ceramic prepared by the preparation method.
Preferably, the particle size of the ZnO pressure-sensitive ceramic material is not more than 0.15mm.
Preferably, the sintering process comprises two stages, a first sintering and a second sintering.
Preferably, the temperature of the first sintering is 400-550 ℃.
More preferably, the temperature of the first sintering is 500 ℃.
Preferably, the time of the first sintering is 2 to 4 hours.
More preferably, the time of the first sintering is 2h.
Preferably, the temperature rising rate of the first sintering temperature is 1-3 ℃/min.
Preferably, the temperature of the second sintering is 1000-1200 ℃.
Preferably, the second sintering time is 2-4 hours.
More preferably, the second sintering time is 2h.
Preferably, the temperature rising rate from the temperature of the first sintering to the temperature of the second sintering is 3-5 ℃/min.
Preferably, the preparation method of the ZnO pressure-sensitive ceramic further comprises the following steps: granulating and tabletting are sequentially carried out before sintering.
Preferably, the specific process of granulation is as follows: adding PVA with the mass fraction of 6-10% into ZnO pressure-sensitive ceramic material, mixing uniformly, granulating by hand, sieving, and taking powder between 60-100 meshes to obtain spherical powder with uniform size.
Preferably, the specific process of tabletting is as follows: adding the granulated powder into a die, pressing by adopting a manual tablet press, slowly pressurizing to 8-15 Mpa, maintaining the pressure for 10min, and demoulding to obtain the green sheet.
The ZnO varistor provided by the invention has the technical scheme that:
and the ZnO varistor is prepared from the ZnO voltage-sensitive ceramic.
The invention adds rare earth oxide Gd 2 O 3 The additive can inhibit the growth of crystal grains through the pinning effect, effectively improve the voltage-sensitive voltage gradient, optimize the microstructure and uniformity of ZnO voltage-sensitive ceramics through an additive sintering process, further improve the energy absorption capacity of the ZnO voltage-sensitive ceramics, and the voltage-sensitive voltage gradient of the ZnO voltage-sensitive resistor can reach 480-600V/mm, and the energy absorption capacity can reach 290J/cm 3 Lays a certain application foundation for miniaturization of the valve core of the lightning arrester and the protected electronic components.
The technical scheme of the preparation method of the ZnO varistor of the invention is as follows:
the preparation method of the ZnO varistor comprises the following steps: and carrying out silver coating and silver firing treatment on the ZnO voltage-sensitive ceramic.
The ZnO varistor prepared by the method has high voltage-sensitive voltage gradient and high energy absorption capacity, can effectively meet the requirements of low cost, high safety and reliability, small size and the like of a high-voltage arrester, and has great economic and social benefits.
Preferably, the temperature of the silver firing treatment is 600-820 ℃.
More preferably, the temperature of the silver firing treatment is 600 ℃.
Preferably, the silver burning treatment is carried out for 1-3 hours.
More preferably, the silver firing treatment is for 2 hours.
Preferably, the rate of temperature rise to the temperature of the silver firing treatment is 2 to 4 ℃/min.
More preferably, the rate of temperature rise to the temperature of the silver firing treatment is 2 ℃/min.
The piezoresistor element has the technical scheme that:
and a varistor element prepared from the ZnO voltage-sensitive ceramic or the ZnO varistor.
When the ZnO voltage-sensitive ceramic or ZnO piezoresistor is used for preparing a piezoresistor element, the requirements of low cost, high safety and reliability, small size and the like of the high-voltage arrester can be effectively met.
Drawings
FIG. 1 is an X-ray diffraction pattern of the ZnO varistor prepared in example 17;
FIG. 2 is an electron microscope photograph of the ZnO varistor prepared in example 18;
FIG. 3 is an electron microscope photograph of the ZnO varistor prepared in example 19;
FIG. 4 is an electron microscopic photograph of the ZnO varistor prepared in example 20.
Detailed Description
The technical scheme of the invention is further described below with reference to the specific embodiments. It should be noted that the purpose of this example is to further illustrate the present invention, and not to limit the scope of the present invention.
1. Specific examples of the additive for ZnO pressure sensitive ceramics of the present invention are as follows:
example 1
The additive for ZnO pressure-sensitive ceramics of the embodiment is composed of Gd 2 O 3 、Sb 2 O 3 And Bi 2 O 3 Is prepared by sintering; wherein, the mol ratio of each raw material in the additive is nGd 2 O 3 :nSb 2 O 3 :nBi 2 O 3 =0.75:1.10:0.70; the sintering temperature is 700 ℃, the sintering time is 2 hours, and the heating rate of heating to the sintering temperature is 3 ℃/min. The preparation method of the additive for ZnO pressure-sensitive ceramics of the embodiment comprises the following steps: gd is weighed according to the formula amount 2 O 3 ，Sb 2 O 3 And Bi (Bi) 2 O 3 Mixing; then placing the mixed raw materials into a planetary ball mill, adding absolute ethyl alcohol according to the proportion of adding 1.2mL absolute ethyl alcohol into each g of raw materials, performing wet grinding by taking absolute ethyl alcohol as a medium, wherein the rotating speed is 400r/min, the ball milling time is 5h, and then placing the slurry into a drying oven at 80 ℃ for dryingAnd (3) drying, placing the dried raw materials into a crucible, placing the crucible into a muffle furnace, heating to 700 ℃ at a speed of 3 ℃/min, preserving heat, sintering for 2 hours, and cooling to room temperature to obtain the additive for ZnO pressure-sensitive ceramics.
Example 2
The additive for ZnO pressure-sensitive ceramics of the embodiment is composed of Gd 2 O 3 、Sb 2 O 3 、Co 2 O 3 、MnO 2 、Bi 2 O 3 、NiO、SiO 2 And Cr (V) 2 O 3 Is prepared by sintering; wherein, the mol ratio of each raw material in the additive is nGd 2 O 3 :nSb 2 O 3 :nCo 2 O 3 :nMnO 2 :nBi 2 O 3 :nNiO:nSiO 2 :nCr 2 O 3 =0.75:1.10:0.80:0.70:0.70:0.50:1.50:0.30; the sintering temperature is 700 ℃, the sintering time is 2 hours, and the heating rate of heating to the sintering temperature is 3 ℃/min. The preparation method of the additive for ZnO pressure-sensitive ceramics of the embodiment comprises the following steps: gd is weighed according to the formula amount 2 O 3 ，Sb 2 O 3 ，Co 2 O 3 ，MnO 2 ，Bi 2 O 3 ，NiO，SiO 2 ，Cr 2 O 3 Mixing; and then placing the mixed raw materials into a planetary ball mill, adding absolute ethyl alcohol according to the proportion of adding 1.2mL of absolute ethyl alcohol into each g of raw materials, carrying out wet milling by taking the absolute ethyl alcohol as a medium, wherein the rotating speed is 400r/min, the ball milling time is 5h, then placing the slurry into a drying box at 80 ℃, drying, placing the dried raw materials into a crucible, placing into a muffle furnace, heating to 700 ℃ at the speed of 3 ℃/min, preserving heat, sintering for 2h, and cooling to the room temperature to obtain the additive for ZnO pressure-sensitive ceramics.
Example 3
The additive for ZnO pressure-sensitive ceramics of the embodiment is composed of Gd 2 O 3 、Sb 2 O 3 、Co 2 O 3 、MnO 2 、Bi 2 O 3 、NiO、SiO 2 And Cr (V) 2 O 3 Is prepared by sintering; wherein, the mol ratio of each raw material in the additive is nGd 2 O 3 :nSb 2 O 3 :nCo 2 O 3 :nMnO 2 :nBi 2 O 3 :nNiO:nSiO 2 :nCr 2 O 3 =0.5:0.80:0.60:0.70:0.80:0.60:1.50:0.40; the sintering temperature is 800 ℃, the sintering time is 4 hours, and the heating rate for heating to the sintering temperature is 3 ℃/min. The preparation method of the additive for ZnO pressure-sensitive ceramics of the embodiment comprises the following steps: gd is weighed according to the formula amount 2 O 3 ，Sb 2 O 3 ，Co 2 O 3 ，MnO 2 ，Bi 2 O 3 ，NiO，SiO 2 ，Cr 2 O 3 Mixing; and then placing the mixed raw materials into a planetary ball mill, adding absolute ethyl alcohol according to the proportion of adding 1.2mL of absolute ethyl alcohol into each g of raw materials, carrying out wet milling by taking the absolute ethyl alcohol as a medium, wherein the rotating speed is 400r/min, the ball milling time is 5h, then placing the slurry into a drying box at 80 ℃, drying, placing the dried raw materials into a crucible, placing into a muffle furnace, heating to 800 ℃ at the speed of 3 ℃/min, preserving heat, sintering for 4h, and cooling to the room temperature to obtain the additive for ZnO pressure-sensitive ceramics.
Example 4
The additive for ZnO pressure-sensitive ceramics of the embodiment is composed of Gd 2 O 3 、Sb 2 O 3 、Co 2 O 3 、MnO 2 、Bi 2 O 3 、NiO、SiO 2 And Cr (V) 2 O 3 Mixing and sintering to prepare the composite material; wherein, the mol ratio of each raw material in the additive is nGd 2 O 3 :nSb 2 O 3 :nCo 2 O 3 :nMnO 2 :nBi 2 O 3 :nNiO:nSiO 2 :nCr 2 O 3 =0.25:0.90:0.70:0.90:0.60:0.80:1.30:0.50; the sintering temperature is 900 ℃, the sintering time is 2 hours, and the heating rate from the heating to the sintering temperature is 5 ℃/min; the preparation method of the additive for ZnO pressure-sensitive ceramics of the embodiment comprises the following steps: gd is weighed according to the formula amount 2 O 3 ，Sb 2 O 3 ，Co 2 O 3 ，MnO 2 ，Bi 2 O 3 ，NiO，SiO 2 ，Cr 2 O 3 Mixing; and then placing the mixed raw materials into a planetary ball mill, adding absolute ethyl alcohol according to the proportion of adding 1.2mL of absolute ethyl alcohol into each g of raw materials, carrying out wet milling by taking the absolute ethyl alcohol as a medium, wherein the rotating speed is 400r/min, the ball milling time is 5h, then placing the slurry into a drying box at 80 ℃, drying, placing the dried raw materials into a crucible, placing into a muffle furnace, heating to 900 ℃ at the speed of 5 ℃/min, preserving heat, sintering for 2h, and cooling to the room temperature to obtain the additive for ZnO pressure-sensitive ceramics.
Example 5
The additive for ZnO pressure-sensitive ceramics of the embodiment is composed of Gd 2 O 3 、Sb 2 O 3 、Co 2 O 3 、MnO 2 、Bi 2 O 3 、NiO、SiO 2 And Cr (V) 2 O 3 Mixing and sintering to prepare the composite material; wherein, the mol ratio of each raw material in the additive is nGd 2 O 3 :nSb 2 O 3 :nCo 2 O 3 :nMnO 2 :nBi 2 O 3 :nNiO:nSiO 2 :nCr 2 O 3 =1.0:1.20:0.90:0.50:0.50:0.60:1.60:0.10; the sintering temperature is 800 ℃, the sintering time is 3 hours, and the heating rate from the heating to the sintering temperature is 4 ℃/min; the preparation method of the additive for ZnO pressure-sensitive ceramics of the embodiment comprises the following steps: gd is weighed according to the formula amount 2 O 3 ，Sb 2 O 3 ，Co 2 O 3 ，MnO 2 ，Bi 2 O 3 ，NiO，SiO 2 ，Cr 2 O 3 Mixing; and then placing the mixed raw materials into a planetary ball mill, adding absolute ethyl alcohol according to the proportion of adding 1.2mL of absolute ethyl alcohol into each g of raw materials, carrying out wet milling by taking the absolute ethyl alcohol as a medium, wherein the rotating speed is 400r/min, the ball milling time is 5h, then placing the slurry into a drying box at 80 ℃, drying, placing the dried raw materials into a crucible, placing into a muffle furnace, heating to 800 ℃ at the speed of 4 ℃/min, preserving heat, sintering for 3h, and cooling to the room temperature to obtain the additive for ZnO pressure-sensitive ceramics.
2. The specific examples of the ZnO pressure-sensitive ceramic material of the invention are as follows:
example 6
The ZnO voltage-sensitive ceramic material of the embodiment consists of the additive for ZnO voltage-sensitive ceramic of the embodiment 1 and ZnO as a main material, wherein the ratio of the total mole number of the additive for ZnO voltage-sensitive ceramic to the mole number of ZnO as the main material is 2.55:97.45. The ZnO pressure-sensitive ceramic material of the embodiment is prepared by a preparation method comprising the following steps: weighing an additive for ZnO pressure-sensitive ceramic and ZnO powder according to the formula amount, mixing, then placing the mixed powder into a planetary ball mill, performing wet milling by taking absolute ethyl alcohol as a medium, wherein the rotating speed is 400r/min, the ball milling time is 5 hours, then placing the slurry into a drying oven at 80 ℃, drying, and sieving by a 100-mesh sieve to obtain the ZnO pressure-sensitive ceramic material.
Example 7
The ZnO voltage-sensitive ceramic material of the embodiment consists of the additive for ZnO voltage-sensitive ceramic of the embodiment 2 and ZnO as a main material, wherein the ratio of the total mole number of the additive for ZnO voltage-sensitive ceramic to the mole number of ZnO as the main material is 6.35:93.65. The ZnO pressure-sensitive ceramic material of the embodiment is prepared by a preparation method comprising the following steps: weighing an additive for ZnO pressure-sensitive ceramic and ZnO powder according to the formula amount, mixing, then placing the mixed powder into a planetary ball mill, performing wet milling by taking absolute ethyl alcohol as a medium, wherein the rotating speed is 400r/min, the ball milling time is 5 hours, then placing the slurry into a drying oven at 80 ℃, drying, and sieving by a 100-mesh sieve to obtain the ZnO pressure-sensitive ceramic material.
Example 8
The ZnO pressure-sensitive ceramic material of the embodiment consists of the additive for ZnO pressure-sensitive ceramic of the embodiment 3 and ZnO as a main material, wherein the ratio of the total mole number of the additive for ZnO pressure-sensitive ceramic to the mole number of ZnO as the main material is 5.9:94.1; the ZnO pressure-sensitive ceramic material of the embodiment is prepared by a preparation method comprising the following steps: weighing an additive for ZnO voltage-sensitive ceramic and ZnO powder according to the formula amount, mixing, then placing the mixed powder into a planetary ball mill, and performing wet milling by taking absolute ethyl alcohol as a medium, wherein the rotating speed is 400r/min, and the ball milling time is 5 hours; and then placing the slurry in a drying oven at 80 ℃ for drying, and sieving with a 100-mesh sieve to obtain the ZnO pressure-sensitive ceramic material.
Example 9
The ZnO pressure-sensitive ceramic material of the embodiment consists of the additive for ZnO pressure-sensitive ceramic of the embodiment 4 and ZnO as a main material, wherein the ratio of the total mole number of the additive for ZnO pressure-sensitive ceramic to the mole number of ZnO as the main material is 5.95:94.05; the ZnO pressure-sensitive ceramic material of the embodiment is prepared by a preparation method comprising the following steps: weighing an additive for ZnO voltage-sensitive ceramic and ZnO powder according to the formula amount, mixing, then placing the mixed powder into a planetary ball mill, and performing wet milling by taking absolute ethyl alcohol as a medium, wherein the rotating speed is 400r/min, and the ball milling time is 5 hours; and then placing the slurry in a drying oven at 80 ℃ for drying, and sieving with a 100-mesh sieve to obtain the ZnO pressure-sensitive ceramic material.
Example 10
The ZnO pressure-sensitive ceramic material of the embodiment consists of the additive for ZnO pressure-sensitive ceramic of the embodiment 5 and ZnO as a main material, wherein the ratio of the total mole number of the additive for ZnO pressure-sensitive ceramic to the mole number of ZnO as the main material is 6.4:93.6; the ZnO pressure-sensitive ceramic material of the embodiment is prepared by a preparation method comprising the following steps: weighing an additive for ZnO voltage-sensitive ceramic and ZnO powder according to the formula amount, mixing, then placing the mixed powder into a planetary ball mill, and performing wet milling by taking absolute ethyl alcohol as a medium, wherein the rotating speed is 400r/min, and the ball milling time is 5 hours; and then placing the slurry in a drying oven at 80 ℃ for drying, and sieving with a 100-mesh sieve to obtain the ZnO pressure-sensitive ceramic material.
3. Specific examples of the ZnO pressure sensitive ceramics of the present invention are as follows:
the ZnO pressure sensitive ceramics of the present example are obtained by sintering the pressure sensitive ceramic material of example 6, example 7, example 8, example 9 or example 10.
4. The specific examples of the preparation method of the ZnO pressure-sensitive ceramic of the invention are as follows:
example 11
The preparation method of the ZnO pressure-sensitive ceramic comprises the following steps:
according to an electronic ceramic preparation process, 13.361g of PVA with the mass fraction of 8% is added into 89.074g of ZnO pressure-sensitive ceramic material of example 6, after being uniformly mixed, manual granulation is carried out, then sieving is carried out, powder with the size of 60-100 meshes is taken, spherical powder with uniform size is obtained, then the spherical powder is added into a die, and is pressed by a manual tablet press, and the pressure is slowly increased to 9Mpa and maintained for 10min, thus obtaining a green sheet; placing the green sheets in a sagger, placing the sagger with the green sheets in a muffle furnace for high-temperature calcination, firstly heating to 500 ℃ at a speed of 1 ℃/min, preserving heat for 2 hours, heating to 1000 ℃ at a speed of 3 ℃/min, preserving heat for 2 hours, and then cooling to room temperature along with the furnace to obtain the ZnO pressure-sensitive ceramic.
Example 12
The preparation method of the ZnO pressure-sensitive ceramic comprises the following steps:
according to an electronic ceramic preparation process, 13.361g of PVA with the mass fraction of 8% is added into 89.074g of ZnO pressure-sensitive ceramic material of example 7, after being uniformly mixed, manual granulation is carried out, then sieving is carried out, powder with the size of 60-100 meshes is taken, spherical powder with uniform size is obtained, then the spherical powder is added into a die, and is pressed by a manual tablet press, and the pressure is slowly increased to 9Mpa and maintained for 10min, thus obtaining a green sheet; placing the green sheets in a sagger, placing the sagger with the green sheets in a muffle furnace for high-temperature calcination, firstly heating to 500 ℃ at a speed of 1 ℃/min, preserving heat for 2 hours, heating to 1000 ℃ at a speed of 3 ℃/min, preserving heat for 2 hours, and then cooling to room temperature along with the furnace to obtain the ZnO pressure-sensitive ceramic.
Example 13
The preparation method of the ZnO pressure-sensitive ceramic comprises the following steps:
according to an electronic ceramic preparation process, 13.256g of PVA with the mass fraction of 8% is added into 88.372g of ZnO pressure-sensitive ceramic material of example 8, after being uniformly mixed, manual granulation is carried out, then sieving is carried out, powder with the size of 60-100 meshes is taken, spherical powder with uniform size is obtained, then the spherical powder is added into a die, and is pressed by a manual tablet press, and the pressure is slowly increased to 9Mpa and maintained for 10min, thus obtaining a green sheet; placing the green sheets in a sagger, placing the sagger with the green sheets in a muffle furnace for high-temperature calcination, firstly heating to 500 ℃ at the speed of 3 ℃/min, preserving heat for 3 hours, heating to 1100 ℃ at the speed of 3 ℃/min, preserving heat for 2 hours, and then cooling to room temperature along with the furnace to obtain the ZnO pressure-sensitive ceramic.
Example 14
The preparation method of the ZnO pressure-sensitive ceramic comprises the following steps:
according to an electronic ceramic preparation process, 13.150g of PVA with the mass fraction of 8% is added into 87.670g of ZnO pressure-sensitive ceramic material of example 9, after being uniformly mixed, manual granulation is carried out, then sieving is carried out, powder with the size of 60-100 meshes is taken to obtain spherical powder with uniform size, then the spherical powder is added into a die, and is pressed by a manual tablet press, and the pressure is slowly increased to 9Mpa and maintained for 10min, thus obtaining a green sheet; placing the green sheets in a sagger, placing the sagger with the green sheets in a muffle furnace for high-temperature calcination, firstly heating to 400 ℃ at the speed of 2 ℃/min, preserving heat for 4 hours, heating to 1200 ℃ at the speed of 5 ℃/min, preserving heat for 2 hours, and then cooling to room temperature along with the furnace to obtain the ZnO pressure-sensitive ceramic.
Example 15
The preparation method of the ZnO pressure-sensitive ceramic comprises the following steps:
according to an electronic ceramic preparation process, 13.467g of PVA with the mass fraction of 8% is added into 89.778g of ZnO pressure-sensitive ceramic powder of example 10, after being uniformly mixed, manual granulation is carried out, then sieving is carried out, powder with the size of 60-100 meshes is taken to obtain spherical powder with uniform size, then the spherical powder is added into a die, and is pressed by a manual tablet press, and the pressure is slowly increased to 9Mpa and maintained for 10min, thus obtaining a green sheet; placing the green sheets in a sagger, placing the sagger with the green sheets in a muffle furnace for high-temperature calcination, firstly heating to 550 ℃ at the speed of 2 ℃/min, preserving heat for 2 hours, heating to 1100 ℃ at the speed of 4 ℃/min, preserving heat for 2 hours, and then cooling to room temperature along with the furnace to obtain the ZnO pressure-sensitive ceramic.
5. The specific embodiment of the ZnO varistor of the invention is as follows:
the ZnO varistor of the present example was prepared from the ZnO voltage-sensitive ceramics prepared in example 11, example 12, example 13, example 14 or example 15.
6. The specific embodiment of the preparation method of the ZnO varistor is as follows:
example 16
The preparation method of the ZnO varistor of the embodiment comprises the following steps:
and (3) placing the ZnO voltage-sensitive ceramic prepared in the example 11 into a sagger, placing into a muffle furnace, heating to 600 ℃ at a speed of 2 ℃/min, preserving heat for 2 hours, and cooling to room temperature to obtain the ZnO varistor.
Example 17
The preparation method of the ZnO varistor of the embodiment comprises the following steps:
and (3) placing the ZnO voltage-sensitive ceramic prepared in the example 12 into a sagger, placing into a muffle furnace, heating to 600 ℃ at a speed of 2 ℃/min, preserving heat for 2 hours, and cooling to room temperature to obtain the ZnO varistor.
As shown in FIG. 1, the principal crystal phase of the prepared varistor is ZnO and contains a small amount of spinel Zn 7 Sb 2 O 12 、Bi 6 Gd 2 O 12 And Gd 3 Sb 5 O 12 And waiting for the second phase.
The ZnO varistor prepared in the embodiment is tested for voltage-sensitive voltage gradient, leakage current and energy absorption capacity according to a test method specified in GB/T16528-1996, and nonlinear coefficients according to a test method specified in GB/T10193-1997, and the characteristic parameters of the ZnO varistor prepared in the embodiment are as follows: the voltage-sensitive voltage gradient is 486V/mm, the nonlinear coefficient alpha is 52, and the leakage current I L 1.47 μA, energy absorption capacity of 290J/cm 3 。
Example 18
The preparation method of the ZnO varistor of the embodiment comprises the following steps:
the ZnO voltage-sensitive ceramic prepared in example 13 is silver coated on both sides, placed in a sagger, placed in a muffle furnace, heated to 600 ℃ at a speed of 2 ℃/min, and cooled to room temperature after heat preservation for 2 hours, so as to obtain the ZnO varistor.
The ZnO varistor prepared in this example was analyzed by using an electron microscope, and the result is shown in FIG. 2. As can be seen from FIG. 2, znO was preparedThe micro-uniformity of the piezoresistor is good, and the microstructure of the piezoresistor is composed of a main crystal phase ZnO and Bi at a grain boundary 2 O 3 And a second phase composition at the grain boundary/three grain boundary.
The ZnO varistor prepared in the embodiment is tested for voltage-sensitive voltage gradient, leakage current and energy absorption capacity according to a test method specified in GB/T16528-1996, and nonlinear coefficients according to a test method specified in GB/T10193-1997, and the characteristic parameters of the ZnO varistor prepared in the embodiment are as follows: the voltage-sensitive voltage gradient is 543V/mm, the nonlinear coefficient alpha is 58, and the leakage current I L 1.23 mu A, energy absorption capacity of 257J/cm 3 。
Example 19
The preparation method of the ZnO varistor of the embodiment comprises the following steps:
and (3) placing the ZnO voltage-sensitive ceramic prepared in the example 14 with silver on both sides in a sagger, placing in a muffle furnace, heating to 600 ℃ at a speed of 2 ℃/min, preserving heat for 2 hours, and cooling to room temperature to obtain the ZnO varistor.
As shown in FIG. 3, it can be seen from FIG. 3 that the ZnO varistor prepared in this example has good microscopic uniformity and microstructure composed of main crystal phase ZnO and Bi at grain boundary 2 O 3 And a second phase composition at the grain boundary/three grain boundary.
The ZnO varistor prepared in the embodiment is tested for voltage-sensitive voltage gradient, leakage current and energy absorption capacity according to a test method specified in GB/T16528-1996, and nonlinear coefficients according to a test method specified in GB/T10193-1997, and the characteristic parameters of the ZnO varistor prepared in the embodiment are as follows: the voltage-sensitive voltage gradient is 578V/mm, the nonlinear coefficient alpha is 56, and the leakage current I L 1.32 mu A, energy absorption capacity of 243J/cm 3 。
Example 20
The preparation method of the ZnO varistor of the embodiment comprises the following steps:
the ZnO voltage-sensitive ceramic prepared in example 15 is silver coated on both sides, placed in a sagger, placed in a muffle furnace, heated to 600 ℃ at a speed of 2 ℃/min, and cooled to room temperature after heat preservation for 2 hours, so as to obtain the ZnO varistor.
As shown in FIG. 4, it can be seen from FIG. 4 that the ZnO varistor prepared in this example has good microscopic uniformity and microstructure composed of main crystal phase ZnO and Bi at grain boundary 2 O 3 And a second phase composition at the grain boundary/three grain boundary.
The ZnO varistor prepared in the embodiment is tested for voltage-sensitive voltage gradient, leakage current and energy absorption capacity according to a test method specified in GB/T16528-1996, and nonlinear coefficients according to a test method specified in GB/T10193-1997, and the characteristic parameters of the ZnO varistor prepared in the embodiment are as follows: the voltage-sensitive voltage gradient is 592V/mm, the nonlinear coefficient alpha is 61, and the leakage current I L 1.08 mu A, energy absorption capacity of 243J/cm 3 。
In other examples, the ZnO voltage-sensitive ceramics prepared in examples 9-12 were silver coated on both sides, placed in a sagger, and placed in a muffle furnace, and heated to 600 ℃, 820 ℃ at the rates of 2 ℃/min, 3 ℃/min and 4 ℃/min, and then cooled to room temperature after heat preservation for 1h, 2h and 3h, and the characteristic parameters of the ZnO piezoresistor obtained were equivalent to the results obtained in examples 13-16.
7. Specific examples of the varistor element of the present invention are as follows:
the varistor element of this example was prepared from the ZnO pressure sensitive ceramics of example 11, example 12, example 13, example 14 or example 15 or from the ZnO varistor of example 16, example 17, example 18, example 19 or example 20.

Claims (11)

1. A preparation method of ZnO pressure-sensitive ceramic is characterized in that the ZnO pressure-sensitive ceramic is obtained by sintering ZnO pressure-sensitive ceramic material; the sintering treatment comprises a first sintering stage and a second sintering stage; the temperature of the first sintering is 400-550 ℃; the time of the first sintering is 2-4 hours; the temperature of the second sintering is 1000-1200 ℃; the second sintering time is 2-4 h;
the ZnO voltageThe sensitive ceramic material comprises ZnO and an additive for ZnO pressure sensitive ceramic, wherein the additive for ZnO pressure sensitive ceramic is prepared by sintering the following raw materials: gd (Gd) 2 O 3 、Bi 2 O 3 、Sb 2 O 3 、Co 2 O 3 、MnO 2 、NiO、SiO 2 And Cr (V) 2 O 3 The method comprises the steps of carrying out a first treatment on the surface of the The additive for ZnO pressure-sensitive ceramics is prepared by sintering the following raw materials in parts by mole based on 100 parts by mole of the total mole of ZnO and the additive for ZnO pressure-sensitive ceramics:
Gd 2 O 3 0.25～1.00，Sb 2 O 3 0.80～1.20，Co 2 O 3 0.60～0.90，MnO 2 0.50～0.90，Bi 2 O 3 0.50～0.80，NiO 0.60～0.80，SiO 2 1.30～1.60，Cr 2 O 3 0.10～0.50；
the sintering temperature is 700-900 ℃ and the sintering time is 2-4 h when the additive is manufactured.
2. The method for producing a ZnO pressure sensitive ceramic according to claim 1, wherein the particle diameter of the ZnO pressure sensitive ceramic material is not more than 0.15mm.
3. The method of producing a ZnO pressure sensitive ceramic according to claim 1, wherein a rate of temperature rise to the first sintering temperature is 1 to 3 ℃/min.
4. The method of producing a ZnO pressure sensitive ceramic according to claim 1, wherein a rate of temperature rise from the temperature of the first sintering to the temperature of the second sintering is 3 to 5 ℃/min.
5. The method for preparing a ZnO pressure sensitive ceramic according to claim 1, wherein the rate of heating to the sintering temperature is 3 ℃/min to 5 ℃/min when preparing the additive.
6. A ZnO pressure-sensitive ceramic produced by the process for producing a ZnO pressure-sensitive ceramic of claim 1.
7. A ZnO varistor prepared from the ZnO pressure sensitive ceramic of claim 6.
8. The preparation method of the ZnO varistor is characterized by comprising the following steps of: silver coating and silver firing are performed on the ZnO voltage-sensitive ceramic of claim 6.
9. The method for preparing the ZnO varistor according to claim 8, wherein the silver firing treatment temperature is 600-820 ℃; the silver burning treatment time is 1-3 h.
10. The method of manufacturing a ZnO varistor according to claim 8, wherein the rate of heating up to the temperature of the silver firing treatment is 2-4 ℃/min.
11. A varistor element made from the ZnO pressure sensitive ceramic of claim 6 or from the ZnO varistor of claim 7.
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