CN117185800A - Aluminum, dysprosium and boron co-doped zinc oxide varistor and preparation method thereof - Google Patents
Aluminum, dysprosium and boron co-doped zinc oxide varistor and preparation method thereof Download PDFInfo
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- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 title claims abstract description 120
- 239000011787 zinc oxide Substances 0.000 title claims abstract description 60
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 29
- 229910052796 boron Inorganic materials 0.000 title claims abstract description 17
- 229910052692 Dysprosium Inorganic materials 0.000 title claims abstract description 16
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 title claims abstract description 15
- KBQHZAAAGSGFKK-UHFFFAOYSA-N dysprosium atom Chemical compound [Dy] KBQHZAAAGSGFKK-UHFFFAOYSA-N 0.000 title claims abstract description 15
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 239000002994 raw material Substances 0.000 claims abstract description 18
- 239000002002 slurry Substances 0.000 claims description 64
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 42
- 238000000498 ball milling Methods 0.000 claims description 37
- 238000002156 mixing Methods 0.000 claims description 28
- 238000007599 discharging Methods 0.000 claims description 19
- 238000005245 sintering Methods 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 13
- 238000001694 spray drying Methods 0.000 claims description 12
- 239000011230 binding agent Substances 0.000 claims description 9
- 239000002270 dispersing agent Substances 0.000 claims description 9
- 239000000843 powder Substances 0.000 claims description 9
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical group [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 4
- 238000003825 pressing Methods 0.000 claims description 4
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 3
- 238000000465 moulding Methods 0.000 claims description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 2
- 239000000853 adhesive Substances 0.000 claims 2
- 230000001070 adhesive effect Effects 0.000 claims 2
- 230000032683 aging Effects 0.000 abstract description 9
- 239000008367 deionised water Substances 0.000 description 20
- 229910021641 deionized water Inorganic materials 0.000 description 20
- 239000003292 glue Substances 0.000 description 17
- 230000000630 rising effect Effects 0.000 description 13
- 238000010438 heat treatment Methods 0.000 description 11
- 239000000203 mixture Substances 0.000 description 9
- 239000000919 ceramic Substances 0.000 description 6
- 238000001816 cooling Methods 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 238000005303 weighing Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 238000011056 performance test Methods 0.000 description 4
- 229910015902 Bi 2 O 3 Inorganic materials 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 230000006978 adaptation Effects 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000000635 electron micrograph Methods 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
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Abstract
The application provides an aluminum, dysprosium and boron co-doped zinc oxide varistor which is prepared from the following raw materials: bi (Bi) 2 O 3 1.0～2.0％，Sb 2 O 3 1.0～2.0％，MnO 2 0.5～1.0％，NiO0.5～1.0％，Co 2 O 3 0.5～1.0％，B 2 O 3 0.1～0.5％，Dy 2 O 3 0.1 to 0.5 percent of ZnO91.5 to 96.5 percent and 0.1 to 0.5 percent of aluminum source. The application also provides a preparation method of the zinc oxide piezoresistor. The zinc oxide varistor provided by the application has high gradient voltage reaching 500V/m due to the co-doping of aluminum, dysprosium and boron, and has the advantages of low residual voltage, small leakage current, excellent aging performance, good temperature characteristic and the like.
Description
Technical Field
The application relates to the technical field of zinc oxide high-sensitivity resistors, in particular to an aluminum, dysprosium and boron co-doped zinc oxide varistor and a preparation method thereof.
Background
The zinc oxide varistor takes ZnO as a main body and adds a small amount of Bi 2 O 3 、Sb 2 O 3 、MnO 2 NiO and Co 2 O 3 And the raw materials are prepared by ball milling, drying, molding and sintering. The zinc oxide varistor has good nonlinear volt-ampere characteristics, is widely applied to the fields of power systems, electronic circuits, household appliances and the like, and is particularly outstanding in the aspects of high-performance surge absorption, overvoltage protection and gapless lightning arresters.
With the increasing performance requirements of the zinc oxide piezoresistor in the market, the conventional gradient piezoresistor cannot meet part of market demands at present, and a voltage gradient of 400V/mm or higher is required. Therefore, there is a need for further methods of providing high gradient zinc oxide varistors with higher performance.
Disclosure of Invention
The application solves the technical problem of providing the zinc oxide varistor co-doped with aluminum, dysprosium and boron, and the varistor provided by the application has the advantages of high voltage gradient, low residual voltage and small leakage current.
In view of the above, the application provides an aluminum, dysprosium and boron co-doped zinc oxide varistor prepared from the following raw materials:
preferably, said B 2 O 3 The content of (C) is 0.2-0.4 mol%.
Preferably, the Dy 2 O 3 The content of (C) is 0.2-0.4 mol%.
Preferably, the aluminum source is an easily-dissolved aluminum salt or aluminum oxide, the aluminum source is aluminum nitrate, and the content of the aluminum nitrate is 0.2-0.4 mol%.
The application also provides a preparation method of the zinc oxide piezoresistor, which comprises the following steps:
a) Bi is mixed according to the proportion relation 2 O 3 、Sb 2 O 3 、MnO 2 、NiO、Co 2 O 3 、B 2 O 3 、Dy 2 O 3 Mixing with water to obtain slurry 1;
b) Mixing the slurry 1, znO and water to obtain slurry 2;
c) Mixing the slurry 2, an aluminum source, a binder and a dispersing agent to obtain slurry 3;
d) Spray drying the slurry 3 and then forming to obtain a blank;
e) And (3) discharging the gel from the blank, and sintering to obtain the zinc oxide varistor.
Preferably, in step A), the mass ratio of powder to water is 1: (1.5-2), wherein the mixing mode is ball milling, and the ball milling time is 2-3 h; in the step B), the mass ratio of the slurry 1 to the water is 1: (0.5-1), wherein the mixing mode is ball milling, and the ball milling time is 1-2 h; in the step C), the mixing mode is ball milling, and the ball milling time is 1-2 h.
Preferably, the spray drying is carried out until the water content is 1.0-1.5%, the forming adopts a pressing mode, the pressing pressure is 100-150 MPa, and the pressure maintaining time is 5-15 s.
Preferably, the temperature rising rate of the glue discharging is 80-120 ℃/h, the temperature of the glue discharging is 300-500 ℃ and the time is 2-5 h.
Preferably, the sintering temperature is 1000-1500 ℃ and the sintering time is 2-5 h.
The application provides an aluminum, dysprosium and boron co-doped zinc oxide varistor, which is prepared from Bi 2 O 3 、Sb 2 O 3 、MnO 2 、NiO、Co 2 O 3 、B 2 O 3 、Dy 2 O 3 ZnO and an aluminum source; according to the zinc oxide varistor provided by the application, the boron, the dysprosium and the aluminum are introduced, and the content of components is controlled, so that the zinc oxide varistor has the advantages of high voltage gradient, low residual voltage, small leakage resistance, excellent ageing performance and the like.
Drawings
FIG. 1 is an electron micrograph of a commercial high gradient zinc oxide varistor (b) according to example 1 (a);
fig. 2 is a graph showing temperature characteristics of the zinc oxide varistor and the commercial high gradient zinc oxide varistor prepared in examples 1 to 3 of the present application.
Detailed Description
For a further understanding of the present application, preferred embodiments of the application are described below in conjunction with the examples, but it should be understood that these descriptions are merely intended to illustrate further features and advantages of the application, and are not limiting of the claims of the application.
In view of the performance requirement of the zinc oxide piezoresistor on high voltage gradient in the prior art, the application provides the zinc oxide piezoresistor, which obtains the high gradient zinc oxide piezoresistor with the gradient of 500V/mm through co-doping of aluminum, dysprosium and boron, and has the advantages of low residual voltage, small leakage current, excellent aging performance and the like. Specifically, the embodiment of the application discloses an aluminum, dysprosium and boron co-doped zinc oxide varistor which is prepared from the following raw materials:
the preparation raw materials of the zinc oxide varistor provided by the application are Co-doped with aluminum, dysprosium and boron based on a conventional penta-component formula, wherein the penta-component formula is prepared by adding Bi, sb, mn, ni and Co oxides on the basis of ZnO, and the trace introduction of aluminum, dysprosium and boron improves the performance of the varistor.
In the present application, bi 2 O 3 The content of (C) is 1.0 to the whole range2.0mol%, specifically, the Bi 2 O 3 The content of (C) is 1.0mol%, 1.1mol%, 1.2mol%, 1.3mol%, 1.4mol%, 1.5mol%, 1.6mol%, 1.7mol%, 1.8mol%, 1.9mol% or 2.0mol%.
Sb 2 O 3 The content of (2) is 1.0-2.0 mol%, specifically, the Sb 2 O 3 The content of (C) is 1.0mol%, 1.1mol%, 1.2mol%, 1.3mol%, 1.4mol%, 1.5mol%, 1.6mol%, 1.7mol%, 1.8mol%, 1.9mol% or 2.0mol%.
MnO 2 The content of (C) is 0.5-1.0 mol%, specifically, the MnO 2 The content of (C) is 0.5mol%, 0.6mol%, 0.7mol%, 0.8mol%, 0.9mol% or 1.0mol%.
The content of NiO is 0.5 to 1.0mol%, specifically, the content of NiO is 0.5mol%, 0.6mol%, 0.7mol%, 0.8mol%, 0.9mol% or 1.0mol%.
Co 2 O 3 The content of (C) is 0.5-1.0 mol%, specifically, the Co is as follows 2 O 3 The content of (C) is 0.5mol%, 0.6mol%, 0.7mol%, 0.8mol%, 0.9mol% or 1.0mol%.
B 2 O 3 For improving the aging of the piezoresistor, the B 2 O 3 The content of (B) is 0.1-0.5 mol%, specifically 2 O 3 The content of (C) is 0.1mol%, 0.2mol%, 0.3mol%, 0.4mol% or 0.5mol%.
Dy 2 O 3 For increasing the gradient voltage of the piezoresistor, the Dy 2 O 3 The Dy content is 0.1 to 0.5mol%, specifically 2 O 3 The content of (C) is 0.1mol%, 0.2mol%, 0.3mol%, 0.4mol% or 0.5mol%.
ZnO is used as a basic component, the content of which is 91.5-96.5 mol%, and specifically, the content of ZnO is 92.0-95.0 mol%.
The introduction of aluminum in the aluminum source is used for improving the grain resistance, reducing the residual voltage and improving the temperature characteristic. The aluminum source of the application is selected from soluble aluminum salts or aluminum oxides, and is specifically selected from Al (NO 3 ) 3 The Al (NO) 3 ) 3 The content of (C) is 0.1-0.5 mol%, specifically, the content of Al (NO 3 ) 3 The content of (2) is 0.1mol%, 0.2mol%, 0.3mol%, 0.4mol% or 0.5mol%; the excessive aluminum content of the application is the larger leakage current of the piezoresistor.
The application also provides a preparation method of the zinc oxide piezoresistor, which comprises the following steps:
a) Bi is mixed according to the proportion relation 2 O 3 、Sb 2 O 3 、MnO 2 、NiO、Co 2 O 3 、B 2 O 3 、Dy 2 O 3 Mixing with water to obtain slurry 1;
b) Mixing the slurry 1, znO and water to obtain slurry 2;
c) Mixing the slurry 2, an aluminum source, a binder and a dispersing agent to obtain slurry 3;
d) Spray drying the slurry 3 and then forming to obtain a blank;
e) And (3) discharging the gel from the blank, and sintering to obtain the zinc oxide varistor.
In the preparation process of the zinc oxide piezoresistor, the application firstly prepares Bi according to the proportion relation 2 O 3 、Sb 2 O 3 、MnO 2 、NiO、Co 2 O 3 、B 2 O 3 、Dy 2 O 3 Mixing with water to obtain slurry 1; in the process, the mixing is carried out by adopting a ball milling mode, and the Bi is 2 O 3 、Sb 2 O 3 、MnO 2 、NiO、Co 2 O 3 、B 2 O 3 、Dy 2 O 3 As powder, the mass ratio of water to powder is (1.5-2): and 1, ball milling for 2-3 hours to uniformly disperse all raw materials to obtain slurry 1.
Mixing the slurry 1, znO and water to obtain slurry 2; in this process, the mass ratio of the water to the slurry 1 is (0.5 to 1): 1, the ball milling time is 1-2 hours, so that all raw materials are uniformly dispersed, and slurry 2 is obtained.
According to the application, aluminium is then added to the slurry 2The source is specifically Al (NO) 3 ) 3 And (3) continuously ball milling the mixture for 1 to 2 hours to obtain slurry 3. The binder and the dispersant are well known to those skilled in the art, and exemplified by polyvinyl alcohol, and polyacrylic acid.
The slurry 3 is then spray dried and molded to obtain a blank; the spray drying is a technical means well known to those skilled in the art, and the present application is not particularly limited to the specific embodiments thereof. And (3) spray drying until the water content of the green body is 1.0-1.5%. The molding adopts a compression molding mode, the compression pressure is 100-150 MPa, the pressure maintaining time is 5-15 s, specifically, the compression pressure is 120-140 MPa, and the pressure maintaining time is 8-10 s.
Finally, the blank is subjected to glue discharging under the open atmosphere condition; in the process, the temperature rising rate of the glue discharging is 80-120 ℃/h, the temperature of the glue discharging is 300-500 ℃ and the time is 2-5 h, more specifically, the temperature rising rate of the glue discharging is 90-110 ℃/h, the temperature is 350-450 ℃ and the time is 2-3 h. The glue is discharged and then sintered, the sintering is carried out under a closed atmosphere, the temperature is raised from room temperature to the sintering temperature, the sintering temperature is 1000-1500 ℃ for 2-5 h, and specifically, the sintering temperature is 1000-1100 ℃ for 2-3 h; the sintering is performed to densify the ceramic.
The zinc oxide varistor provided by the application has the advantages that the types and the proportions of auxiliary additives are regulated, al, dy and B elements are co-doped in the traditional zinc oxide varistor, the voltage gradient reaching 500V/mm is obtained, the residual voltage is about 1.6 (the diameter is 85 mm), and the leakage current is less than 5 mu A/cm 2 The alternating current charge rate is 100%, and the temperature characteristic is better than that of a zinc oxide varistor of a commercial high-gradient varistor.
In order to further understand the present application, the aluminum, dysprosium and boron co-doped zinc oxide varistor and the preparation method thereof provided by the present application are described in detail below with reference to examples, and the scope of protection of the present application is not limited by the following examples.
Example 1
Step 1, pressBi according to the following proportion 2 O 3 (2.0mol％)、Sb 2 O 3 (2.0mol％)、MnO 2 (1.0mol％)、NiO(1.0mol％)、Co 2 O 3 (1.0mol％)、B 2 O 3 (0.5mol％)、Dy 2 O 3 Weighing and mixing (0.5 mol%) and placing the mixture into a ball milling tank of a planetary ball mill, adding deionized water, wherein the weight ratio of the deionized water to the powder is 1.5:1, and mixing and ball milling the mixture for 2 hours to uniformly disperse all the raw materials to obtain slurry 1;
step 2, adding ZnO (91.5 mol%) and deionized water into the slurry 1, wherein the weight ratio of the deionized water to the slurry is 0.5:1, and continuing ball milling for 1h to uniformly disperse all raw materials to obtain slurry 2;
step 3, adding Al (NO) to the slurry 2 3 ) 3 (0.5 mol%) and adding a binder and a dispersing agent, and continuing ball milling for 1h to obtain slurry 3;
step 4, spray drying the slurry 3 until the water content is 1.2%, ageing, and then using a hydraulic press and a cylindrical die with the diameter of 85mm to press and shape the particles, wherein the forming pressure is 150MPa, and the pressure maintaining time is 10s;
and 5, heating the green body obtained in the step 4 for 3 hours at a temperature rising rate of 100 ℃ per hour to a glue discharging temperature of 500 ℃ under an open atmosphere condition, preserving heat and discharging glue, cooling to room temperature, and heating up for 11 hours at a temperature rising rate of 100 ℃ per hour to a sintering temperature of 1020 ℃ under a closed atmosphere condition, and preserving heat for 3 hours to enable the ceramic to be sintered compactly.
Various performance tests are carried out on the zinc oxide piezoresistor prepared according to the process, and the electrical performance is shown in table 1;
TABLE 1 Performance data sheet for Zinc oxide varistors prepared in example 1
Note that: "v" indicates passing the test.
As can be seen from fig. 1, the microstructure of example 1 (fig. 1 a) and the commercial high gradient zinc oxide varistor (fig. 1 b) is smaller in grain size and more uniformly distributed in example 1 than the commercial high gradient zinc oxide varistor.
Example 2
Step 1, bi in the following ratio 2 O 3 (1.0mol％)、Sb 2 O 3 (1.0mol％)、MnO 2 (0.5mol％)、NiO(0.5mol％)、Co 2 O 3 (0.5mol％)、B 2 O 3 (0.1mol％)、Dy 2 O 3 Weighing and mixing (0.1 mol%) and placing the mixture into a ball milling tank of a planetary ball mill, adding deionized water, wherein the weight ratio of the deionized water to the powder is 1.5:1, and mixing and ball milling the mixture for 2 hours to uniformly disperse all the raw materials to obtain slurry 1;
step 2, znO (96.2 mol%) and deionized water are added into the slurry 1, the weight ratio of the deionized water to the slurry is 0.5:1, and ball milling is continued for 1h, so that all raw materials are uniformly dispersed, and slurry 2 is obtained;
step 3, adding Al (NO) to the slurry 2 3 ) 3 (0.1 mol%) and adding a binder and a dispersing agent, and continuing ball milling for 1h to obtain slurry 3;
step 4, spray drying the slurry 3 until the water content is 1.2%, ageing, and then using a hydraulic press and a cylindrical die with the diameter of 85mm to press and shape the particles, wherein the forming pressure is 150MPa, and the pressure maintaining time is 10s;
and 5, heating the green body obtained in the step 4 for 3 hours at a temperature rising rate of 100 ℃ per hour to a glue discharging temperature of 500 ℃ under an open atmosphere condition, preserving heat and discharging glue, cooling to room temperature, and heating up for 11 hours at a temperature rising rate of 100 ℃ per hour to a sintering temperature of 1100 ℃ under a closed atmosphere condition, and preserving heat for 3 hours to enable the ceramic to be sintered compactly.
Various performance tests are carried out on the zinc oxide piezoresistor prepared according to the process, and the electrical performance is shown in table 2;
TABLE 2 Performance data sheet of Zinc oxide piezoresistors prepared in this example
Example 3
Step 1, bi in the following ratio 2 O 3 (1.5mol％)、Sb 2 O 3 (1.5mol％)、MnO 2 (0.8mol％)、NiO(0.8mol％)、Co 2 O 3 (0.8mol％)、B 2 O 3 (0.3mol％)、Dy 2 O 3 Weighing and mixing (0.3 mol%) and placing the mixture into a ball milling tank of a planetary ball mill, adding deionized water, wherein the weight ratio of the deionized water to the powder is 1.5:1, and mixing and ball milling the mixture for 2 hours to uniformly disperse all the raw materials to obtain slurry 1;
step 2, znO (93.7 mol%) and deionized water are added into the slurry 1, the weight ratio of the deionized water to the slurry is 0.5:1, and ball milling is continued for 1h, so that all raw materials are uniformly dispersed, and slurry 2 is obtained;
step 3, adding Al (NO) to the slurry 2 3 ) 3 (0.3 mol%) and adding a binder and a dispersing agent, and continuing ball milling for 1h to obtain slurry 3.
Step 4, spray drying the slurry 3 until the water content is 1.2%, ageing, and then using a hydraulic press and a cylindrical die with the diameter of 85mm to press and shape the particles, wherein the forming pressure is 150MPa, and the pressure maintaining time is 10s;
and 5, heating the green body obtained in the step 4 for 3 hours at a temperature rising rate of 100 ℃ per hour to a glue discharging temperature of 500 ℃ under an open atmosphere condition, preserving heat and discharging glue, cooling to room temperature, and heating up for 11 hours at a temperature rising rate of 100 ℃ per hour to a sintering temperature of 1100 ℃ under a closed atmosphere condition, and preserving heat for 3 hours to enable the ceramic to be sintered compactly.
Various performance tests are carried out on the zinc oxide piezoresistor prepared according to the process. The electrical properties are shown in table 3;
TABLE 3 Performance data sheet for Zinc oxide varistors prepared in example 3
Comparative example 1
Step 1, bi in the following ratio 2 O 3 (1.5mol％)、Sb 2 O 3 (1.5mol％)、MnO 2 (0.8mol％)、NiO(0.8mol％)、Co 2 O 3 Weighing and mixing (0.8 mol%) and placing the mixture into a ball milling tank of a planetary ball mill, adding deionized water, wherein the weight ratio of the deionized water to the powder is 1.5:1, and mixing and ball milling the mixture for 2 hours to uniformly disperse all the raw materials to obtain slurry 1;
step 2, znO (94.6 mol%) and deionized water are added into the slurry 1, the weight ratio of the deionized water to the slurry is 0.5:1, and ball milling is continued for 1h, so that all raw materials are uniformly dispersed, and slurry 2 is obtained;
and step 3, adding a binder and a dispersing agent into the slurry 2, and continuing ball milling for 1h to obtain slurry 3.
Step 4, spray drying the slurry 3 until the water content is 1.2%, ageing, and then using a hydraulic press and a cylindrical die with the diameter of 85mm to press and shape the particles, wherein the forming pressure is 150MPa, and the pressure maintaining time is 10s;
and 5, heating the green body obtained in the step 4 for 3 hours at a temperature rising rate of 100 ℃ per hour to a glue discharging temperature of 500 ℃ under an open atmosphere condition, preserving heat and discharging glue, cooling to room temperature, and heating up for 11 hours at a temperature rising rate of 100 ℃ per hour to a sintering temperature of 1100 ℃ under a closed atmosphere condition, and preserving heat for 3 hours to enable the ceramic to be sintered compactly.
Various performance tests are carried out on the zinc oxide piezoresistor prepared according to the process. The electrical properties are shown in table 4;
TABLE 4 Performance data sheet for Zinc oxide piezoresistors prepared in comparative example 1
Note that: "/" indicates that the test was not passed.
Comparative example 2
Step 1, bi in the following ratio 2 O 3 (1.5mol％)、Sb 2 O 3 (1.5mol％)、MnO 2 (0.8mol％)、NiO(0.8mol％)、Co 2 O 3 (0.8mol％)、B 2 O 3 (1.0mol％)、Dy 2 O 3 (1.0 mol%) weighing and mixing, putting into a ball milling tank of a planetary ball mill, adding deionized water, mixing and ball milling for 2 hours, wherein the weight ratio of the deionized water to the powder is 1.5:1, and dispersing all the raw materials uniformly to obtain slurry 1;
step 2, adding ZnO (91.6 mol%) and deionized water into the slurry 1, wherein the weight ratio of the deionized water to the slurry is 0.5:1, and continuing ball milling for 1h to uniformly disperse all raw materials to obtain slurry 2;
step 3, adding Al (NO) to the slurry 2 3 ) 3 (1.0 mol%) and adding a binder and a dispersing agent, and continuing ball milling for 1h to obtain slurry 3;
step 4, spray drying the slurry 3 until the water content is 1.2%, ageing, and then using a hydraulic press and a cylindrical die with the diameter of 85mm to press and shape the particles, wherein the forming pressure is 150MPa, and the pressure maintaining time is 10s;
and 5, heating the green body obtained in the step 4 for 3 hours at a temperature rising rate of 100 ℃ per hour to a glue discharging temperature of 500 ℃ under an open atmosphere condition, preserving heat and discharging glue, cooling to room temperature, and heating up for 11 hours at a temperature rising rate of 100 ℃ per hour to a sintering temperature of 1100 ℃ under a closed atmosphere condition, and preserving heat for 3 hours to enable the ceramic to be sintered compactly.
TABLE 5 Performance data sheet for Zinc oxide piezoresistors prepared in comparative example 2
The temperature characteristics of examples 1, 2 and 3 and the commercial high-gradient D85 zinc oxide varistor for the line arrester are relatively changed, as shown in fig. 2, the voltage gradient of the zinc oxide varistor in the heating process is tested, and the voltage gradient of examples 1, 2 and 3 is smaller in change and higher in thermal stability when the temperature is raised compared with the commercial high-gradient D85 zinc oxide varistor for the line arrester.
The above description of the embodiments is only for aiding in the understanding of the method of the present application and its core ideas. It should be noted that it will be apparent to those skilled in the art that various modifications and adaptations of the application can be made without departing from the principles of the application and these modifications and adaptations are intended to be within the scope of the application as defined in the following claims.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present application. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the application. Thus, the present application is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (9)
1. The zinc oxide varistor co-doped with aluminum, dysprosium and boron is prepared from the following raw materials:
2. the zinc oxide varistor of claim 1, wherein B 2 O 3 The content of (C) is 0.2-0.4 mol%.
3. The zinc oxide varistor of claim 1, wherein Dy 2 O 3 The content of (C) is 0.2-0.4 mol%.
4. The zinc oxide varistor of claim 1, wherein the aluminum source is a readily soluble aluminum salt or alumina, the aluminum source is aluminum nitrate, and the aluminum nitrate is present in an amount of 0.2 to 0.4mol%.
5. The method for preparing the zinc oxide varistor of claim 1, comprising the steps of:
a) Bi is mixed according to the proportion relation 2 O 3 、Sb 2 O 3 、MnO 2 、NiO、Co 2 O 3 、B 2 O 3 、Dy 2 O 3 Mixing with water to obtain slurry 1;
b) Mixing the slurry 1, znO and water to obtain slurry 2;
c) Mixing the slurry 2, an aluminum source, a binder and a dispersing agent to obtain slurry 3;
d) Spray drying the slurry 3 and then forming to obtain a blank;
e) And (3) discharging the gel from the blank, and sintering to obtain the zinc oxide varistor.
6. The method according to claim 5, wherein in the step A), the mass ratio of the powder to the water is 1: (1.5-2), wherein the mixing mode is ball milling, and the ball milling time is 2-3 h; in the step B), the mass ratio of the slurry 1 to the water is 1: (0.5-1), wherein the mixing mode is ball milling, and the ball milling time is 1-2 h; in the step C), the mixing mode is ball milling, and the ball milling time is 1-2 h.
7. The method according to claim 5, wherein the spray drying is performed until the water content is 1.0-1.5%, the molding is performed by pressing, the pressing pressure is 100-150 MPa, and the dwell time is 5-15 s.
8. The preparation method according to claim 5, wherein the temperature rise rate of the adhesive discharge is 80-120 ℃/h, the temperature of the adhesive discharge is 300-500 ℃ and the time is 2-5 h.
9. The method according to claim 5, wherein the sintering temperature is 1000 to 1500 ℃ for 2 to 5 hours.
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