CN105016721B - Method for preparing ZnO varistor ceramic by co-doping aluminum ions, gallium ions and yttrium ions - Google Patents
Method for preparing ZnO varistor ceramic by co-doping aluminum ions, gallium ions and yttrium ions Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 24
- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 15
- 239000000919 ceramic Substances 0.000 title claims abstract description 15
- 229910052733 gallium Inorganic materials 0.000 title claims abstract description 15
- 229910052727 yttrium Inorganic materials 0.000 title claims abstract description 13
- -1 aluminum ions Chemical class 0.000 title claims abstract description 11
- 238000000498 ball milling Methods 0.000 claims abstract description 28
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 claims abstract description 23
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000002002 slurry Substances 0.000 claims abstract description 23
- UPWOEMHINGJHOB-UHFFFAOYSA-N oxo(oxocobaltiooxy)cobalt Chemical compound O=[Co]O[Co]=O UPWOEMHINGJHOB-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000005245 sintering Methods 0.000 claims abstract description 19
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000008367 deionised water Substances 0.000 claims abstract description 14
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 14
- 238000002156 mixing Methods 0.000 claims abstract description 14
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 11
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 11
- CHPZKNULDCNCBW-UHFFFAOYSA-N gallium nitrate Inorganic materials [Ga+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O CHPZKNULDCNCBW-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 11
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 11
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 11
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims abstract description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 5
- GHPGOEFPKIHBNM-UHFFFAOYSA-N antimony(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Sb+3].[Sb+3] GHPGOEFPKIHBNM-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000002994 raw material Substances 0.000 claims description 20
- 239000000843 powder Substances 0.000 claims description 16
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(III) oxide Inorganic materials O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 claims description 11
- 150000002500 ions Chemical class 0.000 claims description 10
- 238000002360 preparation method Methods 0.000 claims description 10
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Inorganic materials O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 claims description 8
- JLDSOYXADOWAKB-UHFFFAOYSA-N aluminium nitrate Inorganic materials [Al+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O JLDSOYXADOWAKB-UHFFFAOYSA-N 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- 239000008187 granular material Substances 0.000 claims description 5
- 238000007493 shaping process Methods 0.000 claims description 5
- 229910010293 ceramic material Inorganic materials 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 238000007780 powder milling Methods 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims 2
- 230000032683 aging Effects 0.000 abstract description 6
- 239000000463 material Substances 0.000 abstract description 5
- 230000005540 biological transmission Effects 0.000 abstract description 4
- 229910009253 Y(NO3)3 Inorganic materials 0.000 abstract description 3
- YEAUATLBSVJFOY-UHFFFAOYSA-N tetraantimony hexaoxide Chemical compound O1[Sb](O2)O[Sb]3O[Sb]1O[Sb]2O3 YEAUATLBSVJFOY-UHFFFAOYSA-N 0.000 description 7
- 238000000465 moulding Methods 0.000 description 4
- 239000000654 additive Substances 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 230000001419 dependent effect Effects 0.000 description 3
- 238000009413 insulation Methods 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 229910052761 rare earth metal Inorganic materials 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- 239000012071 phase Substances 0.000 description 2
- 150000002910 rare earth metals Chemical class 0.000 description 2
- 229910052596 spinel Inorganic materials 0.000 description 2
- 239000011029 spinel Substances 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000000887 hydrating effect Effects 0.000 description 1
- 238000011534 incubation Methods 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011268 mixed slurry Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
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- Thermistors And Varistors (AREA)
Abstract
The invention discloses a method for preparing ZnO varistor ceramic by adopting aluminum, gallium and yttrium ions to be doped together, which belongs to the field of materials2O3、Sb2O3、MnO2、Cr2O3、Co2O3、SiO2Mixing, adding deionized water and ball milling; adding ZnO and deionized water into the ball-milled slurry, and carrying out ball milling again; adding Al (NO) into the ball-milled ZnO slurry3)3、Ga(NO3)3、Y(NO3)3Or Y2O3Then ball milling is carried out again; and tabletting and sintering the ball-milled slurry. The resistance ceramic prepared by the method has the characteristics of small leakage current, high gradient, low residual voltage, large through-current capacity and stable aging performance, and can be more suitable for the application requirements of power transmission line arresters, GIS arresters and deeply-limited power system overvoltage.
Description
Technical Field
The invention belongs to the field of materials, and particularly relates to a method for preparing ZnO varistor ceramic with high gradient and low residual voltage characteristics by adopting aluminum, gallium and yttrium ions for common doping.
Background
The ZnO varistor is prepared by using ZnO as a main raw material and adding a small amount of Bi2O3、Sb2O3、MnO2、Cr2O3、Co2O3And silver glass powder and the like as auxiliary components and is prepared by adopting a ceramic sintering process. Due to the excellent nonlinear volt-ampere characteristics and energy absorption capacity, the lightning arrester taking the lightning arrester as a core device is key protection equipment of a power system and is key equipment matched with lightning overvoltage protection and power equipment insulation of the power system.
The voltage of the piezoresistor under the action of the 1mA direct current is generally called the piezovoltage U1mAThe voltage-dependent voltage per unit height is referred to as the voltage-dependent gradient. The higher the voltage-sensitive gradient, the smaller the height of the piezoresistor ceramic under the same voltage. Therefore, the ZnO piezoresistor with high gradient can reduce the height of a Gas Insulated Substation (GIS) arrester, realize the miniaturization of the GIS, shorten the height of a line arrester and be easily installed in parallel with a line insulator. And the excellent aging performance can ensure the safe and reliable operation of the lightning arrester. The residual voltage of the ZnO varistor is defined as the maximum voltage peak between the two terminals of the varistor through which the discharge current flows. The low residual voltage means that the residual voltage of the ZnO piezoresistor is low when large current passes through, the nonlinear characteristic is good, and the protection performance of the lightning arrester is good. The lightning arrester assembled by the ZnO piezoresistor with low residual voltage has better protection characteristic, can limit the overvoltage acting on equipment to a lower level, ensures the safety margin of the equipment, can ensure that the lightning arrester further reduces the insulation level of electrical equipment on the other hand, reduces the insulation structure of power transmission and transformation equipment, and further reduces the weight, the volume and the manufacturing cost of the power transmission and transformation equipment. The nonlinear characteristics of the ZnO varistor can be divided into three regions: small current regions, medium current regions, and large current regions. A large current region (>103A/cm2) The resistance of ZnO crystal grains in the area determines the residual voltage, and the position of the area appearing on an I-V characteristic plane determines the charge discharging capacity of the ZnO piezoresistor.
In the sintering process, the sintering temperature is reduced, the heat preservation time is shortened, and the voltage-sensitive voltage U of a small current region can be improved1mA. By controlling the content of Sb element or adding a certain amount of rare earth doping, partial spinel phase is generated in the sintering process, and the pinning effect of the spinel phase is utilizedThe growth rate of ZnO crystal grains is inhibited, and the purposes of improving the voltage-sensitive voltage and gradient can be achieved. For the I-V characteristic of the ZnO varistor in the large current area, which is mainly determined by the grain resistance, the grain resistance in the area needs to be reduced by a method for reducing the residual voltage of the ZnO varistor. The existing main method for reducing the grain resistance is to add a certain proportion of donor ions, and the addition of Al ions is mainly used industrially. Although the conventional disclosed formula and process can prepare a ZnO varistor valve plate with high gradient or low residual voltage, the combination of different formulas and processes can cause performance change which is difficult to expect, so that the ZnO varistor valve plate with high gradient, low residual voltage and excellent aging performance at the same time is not realized.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides a method for preparing ZnO varistor ceramic with high gradient and low residual voltage by adopting aluminum, gallium and yttrium ions for common doping. The ZnO varistor ceramic prepared by the invention has the characteristics of small leakage current, high gradient, low residual voltage, large through-current capacity and stable aging performance, and can be more suitable for the application requirements of power transmission line arresters, GIS arresters and deep limitation of overvoltage of power systems.
The invention provides a method for preparing ZnO varistor ceramic by adopting aluminum, gallium and yttrium ions to be doped together, which is characterized by comprising the following steps:
1) preparation of raw materials
ZnO (87.5-95.8 mol%) and Bi in the following proportion2O3(0.5～2.0mol％)、Sb2O3(0.5～1.5mol％)、MnO2(0.5～1.0mol％)、Cr2O3(0.5～1.0mol％)、Co2O3(0.5～1.5mol％)、SiO2(1.0 to 2.0 mol%) and Al (NO)3)3(0.1～1.0mol％)、Ga(NO3)3(0.1～1.0mol％)、Y(NO3)3Or Y2O3(0.5-1.5 mol%) to prepare an initial raw material.
2) Preparation of additional slurry
Preparing the raw materials in the step 1)Prepared Bi2O3、Sb2O3、MnO2、Cr2O3、Co2O3、SiO2Mixing the materials as auxiliary additives, putting the materials into a ball milling tank of a planetary ball mill, adding deionized water, mixing and ball milling the materials for 8 to 10 hours until all mixed raw materials are uniformly dispersed, wherein the weight ratio of the deionized water to the powder is 1: 1.5.
3) Mixing the auxiliary addition slurry with ZnO
Adding the ZnO prepared in the step 1) into the auxiliary addition slurry obtained in the step 2), adding deionized water, wherein the weight ratio of the deionized water to the slurry is 1-2: 1, mixing and ball-milling for 8-10 hours, and uniformly dispersing all mixed raw materials.
4) Adding Al, Ga and Y ions
Adding the Al (NO) prepared in the step 1) into the uniformly mixed ZnO slurry obtained in the step 3)3)3、Ga(NO3)3、Y(NO3)3Or Y2O3And continuing ball milling for 1-2 hours to prepare powder.
5) Shaping of
Spraying and hydrating the powder obtained in the step 4), and tabletting the granules by using a hydraulic tablet press and a cylindrical die with the diameter of 50mm, wherein the molding pressure is 150MPa, and the pressure maintaining time is 3 minutes.
6) Sintering
And (3) under the condition of closed atmosphere, keeping the temperature for 5 hours at about 400 ℃ by adopting the heating rate of 100-250 ℃/per hour (the heating rate is slower when the temperature is higher), heating to the sintering temperature of 1240-1260 ℃ from the room temperature, and keeping the temperature for 3-4 hours at the sintering temperature, so that the ceramic is sintered compactly.
The invention has the characteristics and beneficial effects that: the traditional raw material mixing grinding process and sintering process are adopted, and Al, Ga and rare earth Y elements are simultaneously added into ZnO and mixed slurry by adjusting the components and the proportion of auxiliary additives. Under the combined action of Al and Ga ions, Al and Ga are dissolved into zinc lattices in a solid solution manner in the sintering process, so that crystal grains are reducedThe resistor reduces the residual voltage of a large current area, the quantity of interstitial zinc ions is reduced due to the existence of Ga ions, the aging stability of the ZnO varistor ceramic is improved, and compared with the method of simply adding Al ions, the leakage current is effectively inhibited. The added rare earth element Y effectively inhibits the growth of ZnO grains in the process of liquid phase sintering, and promotes the inflection point voltage U1mAThe method is remarkably improved; on a V-I characteristic curve, the inversion region is shifted to the right, so that the current discharge capacity of the ZnO varistor prepared by the formula is improved. In conclusion, the residual voltage ratio of the ZnO varistor ceramic can be controlled to be less than 1.5, the voltage gradient is not less than 450V/mm, and the leakage current is less than 1 muA/cm2The nonlinear coefficient is more than 80, and the prepared ZnO varistor ceramic has the characteristics of high gradient, low residual voltage, large through-current capacity, small leakage current and stable aging performance.
DETAILED DESCRIPTION OF EMBODIMENT (S) OF INVENTION
The present invention will be described in further detail with reference to specific examples.
The first embodiment is as follows:
1) preparation of raw materials
The low residual voltage ZnO varistor ceramic material comprises ZnO (90 mol%) and Bi in the following proportion2O3(1.5mol％)、Sb2O3(1mol％)、MnO2(1mol％)、Cr2O3(1mol％)、Co2O3(1mol％)、SiO2(1.5mol％)、Al(NO3)3(1mol％)、Ga(NO3)3(1 mol%) and Y (NO)3)3(1 mol%) starting materials were prepared.
2) Preparation of additional slurry
Adding Bi2O3(1.5mol％)、Sb2O3(1mol％)、MnO2(1mol％)、Cr2O3(1mol％)、Co2O3(1 mol%) and SiO2(1.5 mol%) into a ball milling tank of a planetary ball mill, adding deionized water with the weight 1.5 times of the powder, and ball milling for 8 hours.
3) Mixing the auxiliary addition slurry with ZnO
Adding 90% mol of ZnO into the auxiliary addition slurry after ball milling, adding deionized water with the weight 1.5 times that of the powder, mixing all the mixed raw materials, and ball milling for 8 hours until the mixed raw materials are uniformly dispersed.
4) Adding Al, Ga and Y ions
Adding Al (NO) into the uniformly mixed ZnO slurry3)3(1mol％)、Ga(NO3)3(1 mol%) and Y (NO)3)3(1 mol%) and ball milling was continued for 2 hours.
5) Shaping of
And (3) after the powder obtained in the last step is sprayed and contains water, tabletting the granules by using a hydraulic tablet press and a cylindrical die with the diameter of 50mm, wherein the molding pressure is 150MPa, and the pressure maintaining time is 3 minutes.
6) Sintering
Sintering the green body in a closed atmosphere by using a high-temperature electric furnace, wherein the specific temperature and the control time are as follows:
raising the temperature for 2 hours from room temperature to 400 ℃;
keeping the temperature at 400 ℃ for 5 hours;
heating for 3 hours from 400 ℃ to 900 ℃;
raising the temperature for 3 hours from 900 ℃ to 1250 ℃;
preserving the heat for 3 hours at 1250 ℃;
and (5) naturally cooling.
Various performance tests are carried out on the ZnO varistor sample prepared by the process. The leakage current is suppressed, and the average value is 0.97 mu A/cm2The mean value of the nonlinear coefficient is 85, the mean value of the voltage-dependent voltage gradient is 470V/mm, and the mean value of the residual voltage ratio is 1.49.
Example two:
1) preparation of raw materials
The low residual voltage ZnO varistor ceramic material comprises ZnO (95.8 mol%) and Bi in the following proportion2O3(0.5mol％)、Sb2O3(0.5mol％)、MnO2(0.5mol％)、Cr2O3(0.5mol％)、Co2O3(0.5mol％)、SiO2(1mol％)、Al(NO3)3(0.1mol％)、Ga(NO3)3(0.1 mol%) and Y2O3(0.5 mol%) starting materials were prepared.
2) Preparation of additional slurry
Adding Bi2O3(0.5mol％)、Sb2O3(0.5mol％)、MnO2(0.5mol％)、Cr2O3(0.5mol％)、Co2O3(0.5mol％)、SiO2(1 mol%) is put into a ball milling tank of a planetary ball mill, deionized water with the weight 1.5 times of the powder is added, and ball milling is carried out for 10 hours.
3) Mixing the auxiliary addition slurry with ZnO
Adding 95.8% mol of ZnO into the auxiliary addition slurry after ball milling, adding deionized water with the weight 1.5 times that of the powder, mixing all the mixed raw materials, and ball milling for 10 hours until the mixed raw materials are uniformly dispersed.
4) Adding Al, Ga and Y ions
Adding Al (NO) into the uniformly mixed ZnO slurry3)3(0.1mol％)、Ga(NO3)3(0.1 mol%) and Y2O3(0.5 mol%) and ball milling was continued for 2 hours.
5) Shaping of
And (3) after the powder obtained in the last step is sprayed and contains water, tabletting the granules by using a hydraulic tablet press and a cylindrical die with the diameter of 50mm, wherein the molding pressure is 150MPa, and the pressure maintaining time is 3 minutes.
6) Sintering
Sintering the green body in a closed atmosphere by using a high-temperature electric furnace, wherein the specific temperature and the control time are as follows:
raising the temperature for 2 hours from room temperature to 400 ℃;
keeping the temperature at 400 ℃ for 5 hours;
heating for 3 hours from 400 ℃ to 900 ℃;
raising the temperature for 3 hours from 900 ℃ to 1250 ℃;
incubation at 1240 ℃ for 4 hours;
and (5) naturally cooling.
Various performance tests are carried out on the ZnO varistor sample prepared by the process. Leakage of itThe current is inhibited, the mean value is 0.85 muA/cm2The mean value of the nonlinear coefficient is 80, the mean value of the voltage-sensitive voltage gradient is 450V/mm, and the mean value of the residual voltage ratio is 1.50.
Example three:
1) preparation of raw materials
The low residual voltage ZnO varistor ceramic material comprises ZnO (87.5 mol%) and Bi in the following proportion2O3(2mol％)、Sb2O3(1.5mol％)、MnO2(1mol％)、Cr2O3(1mol％)、Co2O3(1.5mol％)、SiO2(2mol％)、Al(NO3)3(1mol％)、Ga(NO3)3(1 mol%) and Y (NO)3)3(1.5 mol%) starting materials were prepared.
2) Preparation of auxiliary additive for ball milling
Adding Bi2O3(2mol％)、Sb2O3(1.5mol％)、MnO2(1mol％)、Cr2O3(1mol％)、Co2O3(1.5 mol%) and SiO2(2 mol%) is put into a ball milling tank of a planetary ball mill, deionized water with the weight 1.5 times of the powder is added, and ball milling is carried out for 10 hours.
3) Mixing the auxiliary addition slurry with ZnO
Adding 87.5% mol of ZnO into the auxiliary addition slurry after ball milling, adding deionized water with the weight 1.5 times that of the powder, mixing all the mixed raw materials, and ball milling for 10 hours until the mixed raw materials are uniformly dispersed.
4) Adding Al, Ga and Y ions
Adding Al (NO) into the uniformly mixed ZnO slurry3)3(1mol％)、Ga(NO3)3(1 mol%) and Y (NO)3)3(1.5 mol%) and ball milling was continued for 1 hour.
5) Shaping of
And (3) after the powder obtained in the last step is sprayed and contains water, tabletting the granules by using a hydraulic tablet press and a cylindrical die with the diameter of 50mm, wherein the molding pressure is 150MPa, and the pressure maintaining time is 3 minutes.
6) Sintering
Sintering the green body in a closed atmosphere by using a high-temperature electric furnace, wherein the specific temperature and the control time are as follows:
raising the temperature for 2 hours from room temperature to 400 ℃;
keeping the temperature at 400 ℃ for 5 hours;
heating for 3 hours from 400 ℃ to 900 ℃;
raising the temperature for 3 hours from 900 ℃ to 1250 ℃;
keeping the temperature at 1260 ℃ for 3 hours;
and (5) naturally cooling.
Various performance tests are carried out on the ZnO varistor sample prepared by the process. The leakage current is suppressed, and the average value is 0.93 mu A/cm2The mean value of nonlinear coefficient 83, the mean value of voltage-sensitive voltage gradient 480V/mm and the mean value of residual voltage ratio 1.49.
Claims (1)
1. A method for preparing ZnO varistor ceramic by co-doping aluminum, gallium and yttrium ions is characterized by comprising the following steps:
1) preparation of raw materials
The ZnO varistor ceramic material comprises the following components in percentage by mol of ZnO 90% and Bi2O31.5％、Sb2O31％、MnO21％、Cr2O31％、Co2O31％、SiO21.5％、Al(NO3)31％、Ga(NO3)31% and Y (NO)3)31% of initial raw materials are prepared;
2) preparation of additional slurry
Bi is mixed according to the proportion2O3、Sb2O3、MnO2、Cr2O3、Co2O3And SiO2Putting the mixture into a ball milling tank of a planetary ball mill, adding deionized water with the weight 1.5 times that of the powder, and ball milling the mixture for 8 hours;
3) mixing the auxiliary addition slurry with ZnO
Adding 90% of ZnO into the auxiliary addition slurry after ball milling, adding deionized water with the weight 1.5 times that of the powder, mixing and ball milling all the mixed raw materials for 8 hours until the mixed raw materials are uniformly dispersed;
4) adding Al, Ga and Y ions
Adding Al (NO) into the uniformly mixed ZnO slurry3)3、Ga(NO3)3And Y (NO)3)3Continuing ball milling for 2 hours;
5) shaping of
After the powder obtained in the previous step is sprayed and contains water, a hydraulic tablet press and a cylindrical die with the diameter of 50mm are used for tabletting and forming the granules, the forming pressure is 150MPa, and the pressure maintaining time is 3 minutes;
6) sintering
Sintering the green body in a closed atmosphere by using a high-temperature electric furnace, wherein the specific temperature and the control time are as follows:
raising the temperature for 2 hours from room temperature to 400 ℃;
keeping the temperature at 400 ℃ for 5 hours;
heating for 3 hours from 400 ℃ to 900 ℃;
raising the temperature for 3 hours from 900 ℃ to 1250 ℃;
preserving the heat for 3 hours at 1250 ℃;
and (5) naturally cooling.
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| CN105837201A (en) * | 2016-04-06 | 2016-08-10 | 清华大学 | Making method of low-residual voltage piezoresistor of low-resistivity ZnO crystal grains |
| CN105859279A (en) * | 2016-04-06 | 2016-08-17 | 清华大学 | Novel process method for preparing zinc oxide piezoresistor ceramic with excellent properties |
| CN106966716A (en) * | 2017-03-14 | 2017-07-21 | 清华大学 | The preparation method of high-voltage gradient ZnO voltage-sensitive ceramic microballoons |
| CN106904959B (en) * | 2017-04-13 | 2020-11-10 | 贵州大学 | Y3+、Ga3+Composite donor doped ZnO pressure-sensitive ceramic and preparation method thereof |
| CN106892658B (en) * | 2017-04-13 | 2020-11-10 | 贵州大学 | In3+、Ga3+Composite donor doped ZnO pressure-sensitive ceramic and preparation method thereof |
| WO2020019274A1 (en) * | 2018-07-27 | 2020-01-30 | 清华大学 | Method for optimizing zinc oxide varistor |
| CN109678490A (en) * | 2018-11-26 | 2019-04-26 | 新疆大学 | A kind of doping boron and the direct current ZnO varistor of ruthenium ion and preparation method thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1610019A (en) * | 2004-11-22 | 2005-04-27 | 山东大学 | Multielement doped modified zinc oxide pressure sensitive material for lightning protection |
| CN101786874A (en) * | 2010-01-15 | 2010-07-28 | 清华大学 | Process method for preparing low residual voltage ZnO varistor ceramic |
| CN102030522A (en) * | 2010-11-17 | 2011-04-27 | 西安交通大学 | Low-equilibrium temperature ZnO-Bi2O3 series voltage-sensitive ceramic dielectric |
| CN102126852A (en) * | 2011-03-22 | 2011-07-20 | 襄樊市三三电气有限公司 | Method for preparing zinc oxide piezoresistor ceramic |
| CN102557610A (en) * | 2011-12-30 | 2012-07-11 | 贵州大学 | High-potential-gradient zinc oxide varistor, and making method and application thereof |
| CN103396116A (en) * | 2013-08-13 | 2013-11-20 | 广东风华高新科技股份有限公司 | Zinc-oxide piezoresistor raw material, preparation method thereof and piezoresistor |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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-
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- 2015-07-01 CN CN201510378829.XA patent/CN105016721B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1610019A (en) * | 2004-11-22 | 2005-04-27 | 山东大学 | Multielement doped modified zinc oxide pressure sensitive material for lightning protection |
| CN101786874A (en) * | 2010-01-15 | 2010-07-28 | 清华大学 | Process method for preparing low residual voltage ZnO varistor ceramic |
| CN102030522A (en) * | 2010-11-17 | 2011-04-27 | 西安交通大学 | Low-equilibrium temperature ZnO-Bi2O3 series voltage-sensitive ceramic dielectric |
| CN102126852A (en) * | 2011-03-22 | 2011-07-20 | 襄樊市三三电气有限公司 | Method for preparing zinc oxide piezoresistor ceramic |
| CN102557610A (en) * | 2011-12-30 | 2012-07-11 | 贵州大学 | High-potential-gradient zinc oxide varistor, and making method and application thereof |
| CN103396116A (en) * | 2013-08-13 | 2013-11-20 | 广东风华高新科技股份有限公司 | Zinc-oxide piezoresistor raw material, preparation method thereof and piezoresistor |
Non-Patent Citations (1)
| Title |
|---|
| 稀土掺杂的高电压梯度 ZnO 压敏电阻;何金良;《中国科学 E辑》;20091231;第39卷(第1期);109-113 * |
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