CN113105229B - Zinc oxide resistance card and preparation method thereof - Google Patents

Zinc oxide resistance card and preparation method thereof Download PDF

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CN113105229B
CN113105229B CN202110335629.1A CN202110335629A CN113105229B CN 113105229 B CN113105229 B CN 113105229B CN 202110335629 A CN202110335629 A CN 202110335629A CN 113105229 B CN113105229 B CN 113105229B
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zinc oxide
mol
temperature
resistance card
sintering
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CN113105229A (en
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王博闻
高朋召
陈宝辉
陈会会
张佩
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State Grid Corp of China SGCC
State Grid Hunan Electric Power Co Ltd
Disaster Prevention and Mitigation Center of State Grid Hunan Electric Power Co Ltd
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State Grid Corp of China SGCC
State Grid Hunan Electric Power Co Ltd
Disaster Prevention and Mitigation Center of State Grid Hunan Electric Power Co Ltd
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Abstract

The invention relates to the technical field of inorganic non-metallic materials, and particularly discloses a zinc oxide resistance card with excellent comprehensive performance and a preparation method thereof. On the basis of the existing solid phase method, the invention improves the density of the green body through the grain size grading of the raw materials, overcomes the influences of factors such as high porosity and low sintering density which are easy to appear in the single raw material grain size, poorer grain size uniformity after sintering, uncontrollable grain boundary thickness and the like on the performance of the zinc oxide resistance card, and further improves the sintering compactness of the resistance card. The invention further improves the uniformity of the particle size after sintering and regulates the thickness of a crystal boundary layer by controlling crystallization of the resistor disc after sintering, thereby improving the electrical property of the zinc oxide resistor disc. The zinc oxide resistance card prepared by the method has the advantages of potential gradient, nonlinear coefficient, high energy density, low leakage current and residual voltage ratio and the like, and the preparation process is simple, has low requirements on equipment and is easy for batch production.

Description

Zinc oxide resistance card and preparation method thereof
Technical Field
The invention relates to the technical field of inorganic non-metallic materials, in particular to a zinc oxide resistance card.
Background
With the development of ultra-high voltage (500-750kV) and ultra-high voltage (higher than 750kV) power transmission and transformation technologies, higher and higher requirements are put forward on the safety, reliability and miniaturization of ZnO varistor discs serving as lightning arrester core elements, and the research on ZnO varistor discs with high potential gradient and large overcurrent capacity becomes one of the keys for developing new generation ZnO lightning arresters at home and abroad. The development of ultrahigh voltage high-power transmission and transformation projects such as western-to-east power transmission, south-to-north mutual power supply and the like in China enables the transmission voltage of a power grid to be continuously improved, the transmission capacity to be continuously increased, and the development of a ZnO arrester with high potential gradient and large through current capacity is also an urgent need for the construction of ultrahigh voltage and extra-high voltage power grids in China.
Since the development of ZnO varistor in japan and usa in the 20 th century and 70 th era and its wide use in lightning arresters for electric power systems, various countries compete with each other and invested in research and exploration of ZnO varistor. The material system of the ZnO varistor sheet is subjected to ZnO-Bi 2 O 3 The ZnO varistor is improved from a ZnO-rare earth system to a multi-element system, and the potential gradient and the energy tolerance density of the ZnO varistor are greatly improved by designing and optimizing the material composition. In Japan, the potential gradient of ZnO resistance card in commercial lightning arrester reaches 400 V.mm -1 The square wave through-flow capacity reaches 300J cm -3 And is about 1 time higher than that of the traditional piezoresistor sheet. The development of the material is lagged in China, and advanced countries such as America, Japan and the like have developed deep research on the material, but technical blockages are formed in China.
Therefore, the independent development of a preparation technology capable of producing a novel ZnO material with large through-flow density and high potential gradient has important significance.
Disclosure of Invention
In order to solve the problems in the prior art, the invention aims to provide a zinc oxide resistance card and a preparation method thereof.
In order to realize the purpose of the invention, the technical scheme of the invention is as follows:
in a first aspect, the invention provides a preparation method of a zinc oxide resistance card, wherein zinc oxide with various particle size distributions and other oxides with the same particle size distribution are used as raw materials; the particle size distribution of the zinc oxide is respectively 500 +/-50 nanometers, 90 +/-20 nanometers and 30 +/-10 nanometers, and the particle size of other oxides is 1000 +/-200 nanometers.
Preferably, the raw materials comprise: the contents of zinc oxide are respectively as follows: 5-50 mol% of 500 +/-50 nm, 5-80 mol% of 90 +/-20 nm and 5-60 mol% of 30 +/-10 nm; the amount of other oxides added is 0.1-8.0 mol%.
More preferably, the raw materials comprise: the contents of zinc oxide are respectively as follows: 10-45 mol% of 500 +/-50 nm, 10-60 mol% of 90 +/-20 nm and 15-55 mol% of 30 +/-10 nm; the amount of other oxides added is 0.2 to 6.0 mol%.
Further, other oxides include, but are not limited to, bismuth trioxide (Bi) 2 O 3 ) Antimony trioxide (Sb) 2 O 3 ) Chromium oxide (Cr) 2 O 3 ) Cobalt oxide (Co) 2 O 3 ) Cobaltosic oxide (Co) 3 O 4 ) Nickel oxide (Ni) 2 O 3 ) Manganese dioxide (MnO) 2 ) Yttrium oxide (Y) 2 O 3 ) Aluminum oxide (Al) 2 O 3 ) Silicon dioxide (SiO) 2 ) Gallium sesquioxide (Ga) 2 O 3 ) And the like; the purity of the oxide is more than or equal to 99 percent.
Further, the preparation method specifically comprises the following steps:
(1) drying the powder material composed of zinc oxide and other oxides to constant weight, adding into a planetary ball mill, taking ethanol as a medium, and ZrO adding 2 Ball as abrasive, 400 r.min -1 Ball milling;
(2) drying the ball-milled slurry to constant weight to remove ethanol;
(3) adding 4wt% of polyvinyl alcohol (PVA) binder aqueous solution into the dried mixed oxide, sealing and ageing for 24 hours;
(4) molding the aged material into a disc-shaped green body with the thickness of 3.0mm under 100 MPa;
(5) drying the pressed green body to constant weight, and then drying at 1-6 deg.C/min -1 The temperature rise rate is increased to 900- -1 Cooling to 400 ℃ at the cooling rate, and then cooling along with the furnace;
(6) the sintered zinc oxide resistance card is heated at 10 ℃ per minute –1 Raising the temperature rise rate to 100-800 ℃, preserving the heat for 10-60min, and then quickly putting the mixture into deionized water at 15-80 ℃ for 10-20min to obtain the resistance card after primary crystallization;
the crystallization operation can be repeated for a plurality of times to obtain resistance cards with different crystallization times;
(7) polishing the upper and lower surfaces of the crystallized zinc oxide resistance card, covering with silver paste, and performing heat treatment in air at 400-800 ℃ for 5-30min to obtain the zinc oxide resistance card.
Wherein, in the step (1), the drying temperature is 40-100 ℃, preferably 60-90 ℃, and the drying time is 12-36h, preferably 18-30 h; the ball milling time is 2-10h, preferably 4-8 h.
According to the invention, ethanol is selected as a ball milling medium, so that slight hydrolysis of partial oxides in the ball milling process can be avoided when water is used as the medium, thereby affecting the compactness of the final resistance card, and the problem of toxicity caused by using methanol as the ball milling medium can be avoided, so that the next drying step is difficult to be carried out under conventional conditions. Selective ZrO 2 The ball is the abrasive material, can avoid the abrasive dust to the resistance card constitution and the influence of electrical property.
Wherein, in the step (2), the drying temperature is 50-90 ℃, preferably 60-80 ℃, and the drying time is 12-72 hours, preferably 24-48 hours.
Wherein, in the step (3), the addition amount of the polyvinyl alcohol (PVA) binder aqueous solution is 5-30 wt% of the total mass of the mixed oxide, and preferably 5-20 wt%.
Wherein in the step (5), the temperature is controlled at 2-5 ℃ per minute -1 The temperature rise rate is increased to 1000-1200 ℃, the temperature is kept for 2-6h, and after the sintering is finished, the temperature is increased to 2-5 ℃ for min -1 Cooling to 400 ℃ at the cooling rate, and then cooling along with the furnace.
Wherein, in the step (6), the temperature is 10 ℃ min –1 The temperature rise rate is increased to 200-500 ℃, the temperature is preserved for 20-40min, and then the mixture is quickly put into deionized water at 20-70 ℃.
Wherein, in the step (7), the heat treatment temperature is 500-700 ℃, and the treatment time is 10-20 min.
In a second aspect, the invention also provides the zinc oxide resistance card prepared by the preparation method.
The raw materials or reagents involved in the invention are all common commercial products, and the operations involved are all routine operations in the field unless otherwise specified.
The above-described preferred conditions may be combined with each other to obtain a specific embodiment, in accordance with common knowledge in the art.
The invention has the beneficial effects that:
the invention provides a preparation method of a zinc oxide resistance card with excellent comprehensive performance, which is based on the existing solid phase method, improves the density of a green body through the grain size grading of raw materials, further improves the sintering compactness of the resistance card, further improves the uniformity of the grain size after sintering and regulates and controls the thickness of a grain boundary layer through the controlled crystallization of the resistance card after sintering, thereby improving the electrical performance of the zinc oxide resistance card.
The invention overcomes the influence of factors such as high porosity, low sintering density, poor particle size uniformity after sintering, uncontrollable grain boundary thickness and the like on the performance of the zinc oxide resistance card, wherein the factors are easy to appear in the single raw material grain diameter.
The zinc oxide resistance card prepared by the method has the advantages of potential gradient, nonlinear coefficient, high energy density, low leakage current and residual voltage ratio and the like, and the preparation process is simple, has low requirements on equipment and is easy for batch production. The high-performance zinc oxide resistance card prepared by the method is expected to be widely applied to the construction of ultrahigh voltage and extra-high voltage power grids in China.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate embodiments consistent with the invention and together with the description, serve to explain the principles of the invention.
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious for those skilled in the art that other drawings can be obtained according to the drawings without inventive exercise.
FIG. 1 is an SEM photograph of zinc oxide resistance sheets obtained in example 1 before and after crystallization;
FIG. 2 is an I-V curve of the zinc oxide resistor sheet obtained in example 1 before and after crystallization.
Detailed Description
In order that the above objects, features and advantages of the present invention may be more clearly understood, a solution of the present invention will be further described below. It should be noted that the embodiments of the present invention and features of the embodiments may be combined with each other without conflict.
In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention, but the present invention may be practiced in other ways than those described herein; it is to be understood that the embodiments described in this specification are only some embodiments of the invention, and not all embodiments.
Preferred embodiments of the present invention will be described in detail with reference to the following examples. It is to be understood that the following examples are given for illustrative purposes only and are not intended to limit the scope of the present invention. Various modifications and alterations of this invention will become apparent to those skilled in the art without departing from the spirit and scope of this invention.
The experimental procedures used in the following examples are all conventional procedures unless otherwise specified.
Materials, reagents and the like used in the following examples are commercially available unless otherwise specified.
Example 1
The formula of the raw materials is as follows: 96.30 mol% ZnO, 1.00 mol% Bi 2 O 3 ，1.00mol％Sb 2 O 3 ，0.50mol％Cr 2 O 3 ，0.50mol％Co 2 O 3 ，0.50mol％MnO 2 ，0.10mol％Y 2 O 3 And 0.10 mol% of Al 2 O 3 。
Wherein, 96.30 mol% ZnO comprises: 20 mol% of 500 nano particles; 55 mol% of 90 nano particles; and 21.30 mol% of 30 nano particles.
Second, preparation method
1. Drying the above oxides at 80 deg.C for 24 hr, weighing at a certain proportion, adding into planetary ball mill, adding ethanol as medium, and ZrO 2 Ball as abrasive, 400 r.min -1 Ball milling for 6 h;
2. drying the ball-milled slurry at 80 ℃ for 36h to remove ethanol;
3. adding a PVA binder aqueous solution accounting for 4wt% of the total weight of the powder into the dried mixed oxide, sealing and ageing for 24 hours;
4. molding the aged mixed oxide into a disc-shaped green body with the diameter of 30mm and the thickness of 3.0mm under 100 MPa;
5. the blanks are dried at 60 ℃ for 24h with constant weight and then dried at 3 ℃ min –1 The temperature rise rate is increased to 1100 ℃ and the temperature is preserved for 3h, and after the sintering is finished, the temperature is increased to 2 ℃ and min between 1100 ℃ and 400 DEG C –1 Cooling at a cooling rate of 400 ℃ followed by furnace cooling.
6. The sintered ZnO resistance card is heated at 10 ℃ min –1 The temperature rise rate is increased to 300 ℃, the temperature is preserved for 30min, then the resistance card is quickly put into deionized water at 30 ℃ for 10min, the operation is repeated for 3 times, and the resistance card crystallized for 3 times at 300 ℃ is obtained;
7. and (3) polishing the upper surface and the lower surface of the ZnO resistor before and after crystallization respectively, covering silver paste, and then preserving heat in the air for 15min at 600 ℃ to form electrodes, and testing the performance.
The potential gradient, nonlinear coefficient, energy density, leakage current and residual voltage ratio of the obtained resistance chip before crystallization are 1045.6V mm –1 、40.25、396.28J·cm -3 、2.32μA·cm –2 And 1.32. The potential gradient, the nonlinear coefficient, the energy density, the leakage current and the residual voltage ratio of the crystallized resistor disc are 1180.7V-mm respectively –1 、44.32、407.36J·cm -3 、2.15μA·cm –2 And 1.20.
Example 2
The formula of the raw materials is as follows: 94.6 mol% ZnO, 1.0 mol% Bi 2 O 3 ,1.0mol％Sb 2 O 3 ,1.0mol％Co 2 O 3 ,1.0mol％SiO 2 ,0.5mol％MnO 2 ,0.5mol％Cr 2 O 3 ，0.40mol％Ga 2 O 3 。
Wherein, 94.6 mol% of ZnO comprises: 30 mol% of 500-micron particles; 40 mol% of 90 nano particles; and 24.60 mol% of 30 nano particles.
Second, the preparation method
1. Drying the above oxides at 80 deg.C for 24 hr, weighing at a certain proportion, adding into planetary ball mill, adding ethanol as medium, ZrO, adding into the planetary ball mill, and mixing 2 Ball as abrasive, 400 r.min -1 Ball milling for 6 h;
2. drying the slurry subjected to ball milling at 80 ℃ for 36 hours to constant weight to remove ethanol;
3. adding a PVA binder aqueous solution accounting for 4wt% of the total mass of the powder into the dried mixed oxide, sealing and ageing for 24 hours;
4. molding the aged mixed oxide into a disc-shaped green body with the diameter of 40mm and the thickness of 3.0mm under 100 MPa;
5. drying the blank at 70 ℃ for 20h with constant weight, and then drying at 4 ℃ for min –1 The temperature rise rate is increased to 1150 ℃ and the temperature is preserved for 2h, and after the sintering is finished, the temperature is increased to 4 ℃ and min between 1150 ℃ and 400 DEG C –1 Cooling at a cooling rate of 400 ℃ followed by furnace cooling.
6. The sintered ZnO resistance card is at 10 ℃ per minute –1 Raising the temperature rise rate to 400 ℃, preserving the heat for 20min, and then quickly putting the mixture into deionized water at 40 ℃ for 10min to obtain a crystallized resistor disc;
7. and respectively polishing the upper and lower surfaces of the ZnO resistor sheet before and after crystallization, covering with silver paste, and then heating in air at 580 ℃ for 10 minutes to form electrodes, and testing the performance.
The potential gradient, nonlinear coefficient, energy density, leakage current and residual voltage ratio of the obtained resistance chip before crystallization are 1326.2 V.mm respectively -1 、47.5、367.48J·cm -3 1.28 and 1.45. The potential gradient, the nonlinear coefficient, the energy density, the leakage current and the residual voltage ratio of the crystallized resistor disc are 1365.4V-mm respectively -1 、50.5、352.43J·cm -3 1.26 and 1.41.
Example 3
The formula of the raw materials is as follows: 95.41 mol% of ZnO; bi 2 O 3 1.30mol％；Sb 2 O 3 1.50mol％；MnO 2 0.75mol％；Co 3 O 4 0.60mol％；Ni 2 O 3 0.40mol％；Al 2 O 3 0.04mol％。
Wherein, 95.41 mol% ZnO comprises: 40 mol% of 500 micron particles, 35 mol% of 90 nanometer particles and 20.41 mol% of 30 nanometer particles.
Second, preparation method
1. Drying the above materials at 80 deg.C for 24 hr, weighing at a certain proportion, adding into planetary ball mill, adding ethanol as medium, and ZrO 2 Ball as abrasive, 400 r.min -1 Ball milling for 6 h;
2. drying the slurry after ball milling at 70 ℃ for 48h to constant weight to remove ethanol;
3. adding a PVA binder aqueous solution accounting for 4wt% of the total mass of the powder into the dried mixed oxide, sealing and ageing for 24 hours;
4. molding the aged mixed oxide into a disc-shaped green body with the diameter of 60mm and the thickness of 3.0mm under 100 MPa;
5. drying the blank at 60 ℃ for 30h, and then drying at 2 ℃ for min –1 The temperature rise rate is increased to 1050 ℃ and the temperature is preserved for 6h, and after the sintering is finished, the temperature is increased to 2 ℃ and min between 1050 ℃ and 400 DEG C –1 Cooling at a cooling rate of 400 ℃ followed by furnace cooling.
6. The sintered ZnO resistance card is at 10 ℃ per minute –1 Raising the temperature rise rate to 200 ℃, preserving the heat for 30min, then quickly putting the zinc oxide resistance card into deionized water at 40 ℃ for 10min, and repeating the operation for four times to obtain the crystallized zinc oxide resistance card;
7. and respectively polishing the upper surface and the lower surface of the ZnO resistor before and after crystallization, covering silver paste, and heating in air at 650 ℃ for 10min to form electrodes for testing performance.
The potential gradient, nonlinear coefficient, energy density, leakage current and residual voltage ratio of the obtained resistance chip before crystallization are 827.3 V.mm respectively -1 、62.4、356.65J·cm -3 1.45 and 1.69. The potential gradient, nonlinear coefficient, energy density, leakage current and residual voltage ratio of the crystallized resistor disc are 935.6 V.mm respectively -1 、74.3、387.2J·cm -3 1.40 and 1.52.
Example 4
The formula of the raw materials is as follows: 96.30 mol% ZnO，1.00mol％Bi 2 O 3 ，1.00mol％Sb 2 O 3 ，0.50mol％Cr 2 O 3 ，0.50mol％Co 2 O 3 ，0.50mol％MnO 2 ，0.10mol％Y 2 O 3 And 0.10 mol% Al 2 O 3 。
Wherein 96.30 mol% ZnO comprises: 20 mol% of 500 nano particles; 55 mol% of 90 nano particles; and 21.30 mol% of 30 nano particles.
Second, preparation method
1. Drying the above oxides at 80 deg.C for 24 hr, weighing at a certain proportion, adding into planetary ball mill, adding ethanol as medium, and ZrO 2 Ball as abrasive, 400 r.min -1 Ball milling for 6 h;
2. drying the ball-milled slurry at 80 ℃ for 36h to remove ethanol;
3. adding a PVA binder aqueous solution accounting for 4wt% of the total mass of the powder into the dried mixed oxide, sealing and ageing for 24 hours;
4. molding the aged mixed oxide into a disc-shaped green body with the diameter of 30mm and the thickness of 3.0mm under 100 MPa;
5. the blanks are dried at 60 ℃ for 24h with constant weight and then dried at 3 ℃ for min –1 The temperature rise rate is increased to 1100 ℃ and the temperature is preserved for 3h, and after the sintering is finished, the temperature is increased to 2 ℃ and min between 1100 ℃ and 400 DEG –1 Cooling at a cooling rate of 400 ℃ followed by furnace cooling.
6. The sintered ZnO resistance card is at 10 ℃ per minute –1 Raising the temperature rise rate to 200 ℃, preserving the heat for 30min, then quickly putting the mixture into deionized water at the temperature of 30 ℃ for 10min, and repeating the operation for 3 times to obtain the resistance card crystallized for 3 times at the temperature of 300 ℃;
7. and (3) polishing the upper surface and the lower surface of the ZnO resistor before and after crystallization respectively, covering silver paste, and then preserving heat in the air for 15min at 600 ℃ to form electrodes, and testing the performance.
The potential gradient, nonlinear coefficient, energy density, leakage current and residual voltage ratio of the obtained resistance chip before crystallization are 1045.6V mm –1 、40.25、396.28J·cm -3 、2.32μA·cm –2 And 1.32. Post crystallizationThe potential gradient, nonlinear coefficient, energy density, leakage current and residual voltage ratio of the resistor plate are 1095.4V mm –1 、41.66、400.87J·cm -3 、2.28μA·cm –2 And 1.29.
Comparative example 1
The formula of the raw materials is as follows: 96.30 mol% ZnO, 1.00 mol% Bi 2 O 3 ，1.00mol％Sb 2 O 3 ，0.50mol％Cr 2 O 3 ，0.50mol％Co 2 O 3 ，0.50mol％MnO 2 ，0.10mol％Y 2 O 3 And 0.10 mol% of Al 2 O 3 . Wherein, ZnO is 500 nano-particles.
Second, the preparation method
1. Drying the above oxides at 80 deg.C for 24 hr, weighing at a certain proportion, adding into planetary ball mill, adding ethanol as medium, and ZrO 2 Ball as abrasive, 400 r.min -1 Ball milling for 6 h;
2. drying the ball-milled slurry at 80 ℃ for 36h to remove ethanol;
3. adding a PVA binder aqueous solution accounting for 4wt% of the total weight of the powder into the dried mixed oxide, sealing and ageing for 24 hours;
4. molding the aged mixed oxide into a disc-shaped green body with the diameter of 30mm and the thickness of 3.0mm under 100 MPa;
5. the blanks are dried at 60 ℃ for 24h with constant weight and then dried at 3 ℃ min –1 The temperature rise rate is increased to 1100 ℃ and the temperature is preserved for 3h, and after the sintering is finished, the temperature is increased to 2 ℃ and min between 1100 ℃ and 400 DEG –1 Cooling at a cooling rate of 400 ℃ followed by furnace cooling.
6. The sintered ZnO resistance card is heated at 10 ℃ min –1 The temperature rise rate is increased to 300 ℃, the temperature is preserved for 30min, then the resistance card is quickly put into deionized water at 30 ℃ for 10min, the operation is repeated for 3 times, and the resistance card crystallized for 3 times at 300 ℃ is obtained;
7. and (3) polishing the upper surface and the lower surface of the ZnO resistor before and after crystallization respectively, covering silver paste, and then preserving heat in the air for 15min at 600 ℃ to form electrodes, and testing the performance.
Electric resistance of the resistive sheet obtained before crystallizationThe bit gradient, the nonlinear coefficient, the energy density, the leakage current and the residual voltage ratio are respectively 964.2V mm –1 、32.45、357.69J·cm -3 、2.78μA·cm –2 And 1.38. The potential gradient, the nonlinear coefficient, the energy density, the leakage current and the residual voltage ratio of the crystallized resistor disc are 996.2V mm respectively –1 、40.63、382.33J·cm -3 、2.66μA·cm –2 And 1.30.
Comparative example 2
The formula of the raw materials is as follows: 96.30 mol% ZnO, 1.00 mol% Bi 2 O 3 ，1.00mol％Sb 2 O 3 ，0.50mol％Cr 2 O 3 ，0.50mol％Co 2 O 3 ，0.50mol％MnO 2 ，0.10mol％Y 2 O 3 And 0.10 mol% Al 2 O 3 。
Wherein 96.30 mol% ZnO comprises: 20 mol% of 500 nano particles; 55 mol% of 90 nano particles; 30 nano particles 21.30 mol%.
Second, preparation method
1. Drying the above oxides at 80 deg.C for 24 hr, weighing at a certain proportion, adding into planetary ball mill, adding ethanol as medium, and ZrO 2 Ball as abrasive, 400 turns min -1 Ball milling for 6 h;
2. drying the slurry subjected to ball milling at 80 ℃ for 36 hours to remove ethanol;
3. adding a PVA binder aqueous solution accounting for 4wt% of the total mass of the powder into the dried mixed oxide, sealing and ageing for 24 hours;
4. molding the aged mixed oxide into a disc-shaped green body with the diameter of 30mm and the thickness of 3.0mm under 100 MPa;
5. the blanks are dried at 60 ℃ for 24h with constant weight and then dried at 3 ℃ for min –1 The temperature rise rate is increased to 1100 ℃ and the temperature is preserved for 3h, and after the sintering is finished, the temperature is increased to 2 ℃ and min between 1100 ℃ and 400 DEG –1 Cooling at a cooling rate of 400 ℃ followed by furnace cooling.
6. The sintered ZnO resistance card is at 10 ℃ per minute –1 The temperature rise rate is increased to 600 ℃, the temperature is kept for 30min, then the mixture is quickly put into deionized water at 30 ℃ for 10min, and the resistance cardThe direct cracking failed to test the performance.
Comparative example 3
The formula of the raw materials is as follows: 96.30 mol% ZnO, 1.00 mol% Bi 2 O 3 ，1.00mol％Sb 2 O 3 ，0.50mol％Cr 2 O 3 ，0.50mol％Co 2 O 3 ，0.50mol％MnO 2 ，0.10mol％Y 2 O 3 And 0.10 mol% Al 2 O 3 。
Wherein, 96.30 mol% ZnO comprises: 20 mol% of 500 nano particles; 55 mol% of 90 nano particles; 30 nano particles 21.30 mol%.
Second, preparation method
1. Drying the above oxides at 80 deg.C for 24 hr, weighing at a certain proportion, adding into planetary ball mill, adding ethanol as medium, and ZrO 2 Ball as abrasive, 400 turns min -1 Ball milling for 6 h;
2. drying the slurry subjected to ball milling at 80 ℃ for 36 hours to remove ethanol;
3. adding a PVA binder aqueous solution accounting for 4wt% of the total weight of the powder into the dried mixed oxide, sealing and ageing for 24 hours;
4. molding the aged mixed oxide into a disc-shaped green body with the diameter of 30mm and the thickness of 3.0mm under 100 MPa;
5. the blanks are dried at 60 ℃ for 24h with constant weight and then dried at 3 ℃ min –1 The temperature rise rate is increased to 1100 ℃ and the temperature is preserved for 3h, and after the sintering is finished, the temperature is increased to 2 ℃ and min between 1100 ℃ and 400 DEG –1 Cooling at a cooling rate of 400 ℃ followed by furnace cooling.
6. The sintered ZnO resistance card is at 10 ℃ per minute –1 The temperature rise rate is increased to 100 ℃, the temperature is kept for 30min, then the resistance card is quickly put into deionized water at 30 ℃ for 10min, the operation is repeated for 3 times, and the resistance card crystallized for 3 times at 100 ℃ is obtained;
7. and (3) polishing the upper surface and the lower surface of the ZnO resistor before and after crystallization respectively, covering silver paste, and then preserving heat in the air for 15min at 600 ℃ to form electrodes, and testing the performance.
The potential gradient and the nonlinear coefficient of the resistance chip obtained before crystallization,The energy density, the leakage current and the residual voltage ratio are 1045.6V mm respectively –1 、40.25、396.28J·cm -3 、2.32μA·cm –2 And 1.32. The potential gradient, the nonlinear coefficient, the energy density, the leakage current and the residual voltage ratio of the crystallized resistor disc are 1052.2V mm respectively –1 、41.45、398.22J·cm -3 、2.33μA·cm –2 And 1.31.
The foregoing are merely exemplary embodiments of the present invention, which enable those skilled in the art to understand or practice the present invention. 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 invention. Thus, the present invention 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. A preparation method of zinc oxide resistance card is characterized in that zinc oxide with various particle size distributions and other oxides with the same particle size distribution are adopted as raw materials; the particle size distribution of the zinc oxide is respectively 500 +/-50 nanometers, 90 +/-20 nanometers and 30 +/-10 nanometers, and the particle size distribution of other oxides is 1000 +/-200 nanometers;
other oxides include, but are not limited to, bismuth trioxide, antimony trioxide, chromium trioxide, cobalt trioxide, cobaltosic oxide, nickel trioxide, manganese dioxide, yttrium oxide, aluminum oxide, silicon dioxide, gallium trioxide; purity of said oxide
Figure DEST_PATH_IMAGE002
99%；
The preparation method comprises the following steps:
(1) drying the powder material composed of zinc oxide and other oxides to constant weight, adding into a planetary ball mill, taking ethanol as a medium, and ZrO 2 The ball is used as an abrasive material for 300- -1 Ball milling;
(2) drying the ball-milled slurry to constant weight to remove ethanol;
(3) adding 4wt% of polyvinyl alcohol binder aqueous solution into the dried mixed oxide, sealing and ageing for 24 h;
(4) molding the aged material into a disc-shaped green body with the thickness of 3.0mm under 100 MPa;
(5) drying the pressed green body to constant weight, and adding 1-6% of the dried green body o C·min -1 The temperature rise rate is increased to 900-1200 ℃, the temperature is preserved for 1 to 8 hours, and after the sintering is finished, the temperature is preserved for 1 to 6 hours o C·min -1 Cooling to 400 o C, cooling the furnace;
(6) the sintered zinc oxide resistance card is heated at 10 ℃ min –1 The temperature rise rate is increased to 100-800 ℃, the temperature is preserved for 10-60min, and then the mixture is quickly placed in the temperature-keeping chamber for 15-80 min o C, in deionized water for 10-20min to obtain crystallized resistor discs;
crystallization is carried out once or more times;
(7) and polishing the upper surface and the lower surface of the crystallized zinc oxide resistance card, covering with silver paste, and performing heat treatment in air at 400-800 ℃ for 5-30min to obtain the zinc oxide resistance card.
2. The method of claim 1, wherein the starting material comprises: the contents of zinc oxide are respectively: 5-50 mol% of 500 +/-50 nm, 5-80 mol% of 90 +/-20 nm and 5-60 mol% of 30 +/-10 nm; the amount of other oxides added is 0.1 to 8.0 mol%.
3. The method of claim 2, wherein the starting material comprises: the contents of zinc oxide are respectively as follows: 10-45 mol% of 500 +/-50 nm, 10-60 mol% of 90 +/-20 nm and 15-55 mol% of 30 +/-10 nm; the amount of other oxides added is 0.2 to 6.0 mol%.
4. The method according to claim 1, 2 or 3, wherein in the step (5), the amount of the surfactant is 2 to 5 o C·min -1 The temperature rise rate is increased to 1000-1200 ℃, the temperature is kept for 2-6h, and after the sintering is finished, the temperature is increased by 2-5 o C·min -1 Cooling to 400 deg.C o And C, cooling the furnace.
5. The process according to claim 1, 2 or 3, wherein in the step (6), the temperature is 10 ℃ min –1 The temperature rise rate is increased to 200-500 ℃, the temperature is preserved for 20-40min, and then the mixture is quickly placed into a container with the temperature of 20-70 DEG C o C in deionized water.
6. The production method according to claim 1, 2 or 3, wherein in the step (3), the polyvinyl alcohol binder aqueous solution is added in an amount of 5 to 30 wt% based on the total mass of the mixed oxides.
7. The method according to claim 6, wherein the aqueous polyvinyl alcohol binder solution is added in an amount of 5 to 20 wt% based on the total mass of the mixed oxides.
8. The preparation method according to claim 1, 2 or 3, wherein the heat treatment temperature in step (7) is 500-700 ℃ and the treatment time is 10-20 min.
9. A zinc oxide resistor sheet prepared by the method of any one of claims 1 to 8.
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