CN116072365A - Sintering method of large-through-flow resistor disc - Google Patents
Sintering method of large-through-flow resistor disc Download PDFInfo
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- CN116072365A CN116072365A CN202211660233.5A CN202211660233A CN116072365A CN 116072365 A CN116072365 A CN 116072365A CN 202211660233 A CN202211660233 A CN 202211660233A CN 116072365 A CN116072365 A CN 116072365A
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- 238000005245 sintering Methods 0.000 title claims abstract description 59
- 238000000034 method Methods 0.000 title claims abstract description 45
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 86
- 239000011787 zinc oxide Substances 0.000 claims abstract description 43
- 239000000463 material Substances 0.000 claims abstract description 22
- 239000011265 semifinished product Substances 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims abstract description 8
- 239000006184 cosolvent Substances 0.000 claims abstract description 7
- 238000003825 pressing Methods 0.000 claims abstract description 7
- 239000000047 product Substances 0.000 claims abstract description 5
- 238000000227 grinding Methods 0.000 claims abstract description 4
- 238000002156 mixing Methods 0.000 claims abstract description 4
- 238000010438 heat treatment Methods 0.000 claims description 43
- 229910000416 bismuth oxide Inorganic materials 0.000 claims description 36
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 claims description 36
- 239000002245 particle Substances 0.000 claims description 18
- 238000001816 cooling Methods 0.000 claims description 15
- 230000008569 process Effects 0.000 claims description 13
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 9
- 238000004321 preservation Methods 0.000 claims description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 7
- 238000009826 distribution Methods 0.000 claims description 6
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims description 6
- 238000011049 filling Methods 0.000 claims description 5
- 229910000410 antimony oxide Inorganic materials 0.000 claims description 4
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 4
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 claims description 4
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 3
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 3
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 claims description 3
- 229910000423 chromium oxide Inorganic materials 0.000 claims description 3
- 229910000428 cobalt oxide Inorganic materials 0.000 claims description 3
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims description 3
- AJNVQOSZGJRYEI-UHFFFAOYSA-N digallium;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Ga+3].[Ga+3] AJNVQOSZGJRYEI-UHFFFAOYSA-N 0.000 claims description 3
- 238000005485 electric heating Methods 0.000 claims description 3
- 229910001195 gallium oxide Inorganic materials 0.000 claims description 3
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 claims description 3
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 3
- 230000000630 rising effect Effects 0.000 claims description 3
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 3
- 235000011150 stannous chloride Nutrition 0.000 claims description 3
- AXZWODMDQAVCJE-UHFFFAOYSA-L tin(II) chloride (anhydrous) Chemical compound [Cl-].[Cl-].[Sn+2] AXZWODMDQAVCJE-UHFFFAOYSA-L 0.000 claims description 3
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 3
- 239000008187 granular material Substances 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- PRBOKCFKSCWBCY-UHFFFAOYSA-N bismuth;oxoboron Chemical compound [Bi].O=[B] PRBOKCFKSCWBCY-UHFFFAOYSA-N 0.000 claims 1
- 239000000075 oxide glass Substances 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 239000013078 crystal Substances 0.000 description 23
- 239000012071 phase Substances 0.000 description 22
- 239000011521 glass Substances 0.000 description 14
- 239000011148 porous material Substances 0.000 description 8
- 239000002131 composite material Substances 0.000 description 6
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 5
- 229910052796 boron Inorganic materials 0.000 description 5
- YISOXLVRWFDIKD-UHFFFAOYSA-N bismuth;borate Chemical compound [Bi+3].[O-]B([O-])[O-] YISOXLVRWFDIKD-UHFFFAOYSA-N 0.000 description 4
- 239000005385 borate glass Substances 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000010304 firing Methods 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000012212 insulator Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000008707 rearrangement Effects 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000010532 solid phase synthesis reaction Methods 0.000 description 2
- 238000009827 uniform distribution Methods 0.000 description 2
- 230000002159 abnormal effect Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical group [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 239000000306 component Substances 0.000 description 1
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 1
- 239000008358 core component Substances 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000011267 electrode slurry Substances 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
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- 238000012986 modification Methods 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01C—RESISTORS
- H01C17/00—Apparatus or processes specially adapted for manufacturing resistors
- H01C17/30—Apparatus or processes specially adapted for manufacturing resistors adapted for baking
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01C—RESISTORS
- H01C7/00—Non-adjustable resistors formed as one or more layers or coatings; Non-adjustable resistors made from powdered conducting material or powdered semi-conducting material with or without insulating material
- H01C7/10—Non-adjustable resistors formed as one or more layers or coatings; Non-adjustable resistors made from powdered conducting material or powdered semi-conducting material with or without insulating material voltage responsive, i.e. varistors
- H01C7/105—Varistor cores
- H01C7/108—Metal oxide
- H01C7/112—ZnO type
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- Engineering & Computer Science (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Manufacturing & Machinery (AREA)
- Physics & Mathematics (AREA)
- Electromagnetism (AREA)
- Compositions Of Oxide Ceramics (AREA)
- Thermistors And Varistors (AREA)
Abstract
The invention relates to the field of zinc oxide resistor disc production processes, and discloses a large-through-flow resistor disc sintering method, which comprises the following steps: s1: mixing and grinding the main material and the cosolvent, and then drying and granulating; s2: pressing the pelleting material obtained in the step S1 into a resistor disc green body; s3: further drying and presintering the prepared prefabricated blank to obtain a zinc oxide resistor disc semi-finished product; s4: the inner ring of the semi-finished product of the zinc oxide resistor disc is filled with granulated materials with the same formula as the prefabricated blank, and the zinc oxide resistor disc finished product is obtained after sintering by adopting a multi-step curve sintering method.
Description
Technical Field
The invention relates to the field of zinc oxide resistor disc production processes, in particular to a large-through-flow resistor disc sintering method.
Background
The zinc oxide resistor disc is a core component of a metal oxide arrester of power grid operation protection equipment, when lightning overvoltage which is many times higher than normal voltage or operation overvoltage attack is encountered, the resistance value of the zinc oxide resistor disc can be instantaneously changed from high resistance to low resistance, so that strong instantaneous overcurrent flows into the ground through the zinc oxide resistor disc, the problem that the safety operation of the power grid is affected due to the overvoltage attack of electric equipment is avoided, and the installation of the metal oxide arrester connected with an insulator string in parallel on a power transmission line is always considered as one of the most effective means for preventing lightning trip. In recent years, a large number of line arresters with gaps are installed on the lines, so that the cumulative tripping rate of the lines is effectively reduced, and the damage of the surface of an insulator caused by lightning flashover is eliminated. However, when the zinc oxide resistor disc is prepared by the traditional solid phase method (such as patents CN105884345, CN101950648, CN101503292 and CN 110078494), metal oxides such as zinc oxide, bismuth oxide, antimony oxide and the like are directly ground, granulated, pressed and sintered to prepare a resistor disc finished product, and the resistor disc has the characteristic of simpler preparation process. However, because the center of the annular resistor disc is a round hole, when the traditional solid phase method is adopted for preparation, the microstructure of the traditional resistor disc is uneven, the porosity is high, the current passing capability is difficult to improve, the current passing capability of the resistor disc is reduced, the mechanical strength is reduced, the stress is uneven, and the resistor disc is easy to damage and even burst in the lightning protection process, so that the sintering method of the large current passing resistor disc is provided.
Disclosure of Invention
(one) solving the technical problems
Aiming at the defects of the prior art, the invention provides a sintering method of a large-through-flow resistor disc, which solves the problems.
(II) technical scheme
In order to achieve the above purpose, the present invention provides the following technical solutions: a sintering method of a large-through-flow resistor disc comprises the following steps:
s1: mixing and grinding the main material and the cosolvent, and then drying and granulating;
s2: pressing the pelleting material obtained in the step S1 into a resistor disc green body;
s3: further drying and presintering the prepared prefabricated blank, wherein the presintering temperature is 300-700 ℃, the heat preservation time is 1-4 h, and the heating speed is 2-5 ℃/min, so as to obtain a zinc oxide resistor disc semi-finished product;
s4: and filling the inner ring of the semi-finished product of the zinc oxide resistor disc with the granulated material with the same formula as the prefabricated blank, sintering by adopting a multi-step curve sintering method, applying direct current voltage with the voltage of 200V/mm-500V/mm to the two ends in the sintering temperature rising process of the resistor disc, and obtaining the finished product of the zinc oxide resistor disc after sintering.
Preferably, in the step S1, the main material composition is as follows: 85 to 95 parts of zinc oxide, 2 to 6 parts of bismuth oxide, 1 to 3 parts of cobalt oxide, 0.4 to 1.2 parts of nickel oxide, 0.2 to 1 part of manganese oxide, 1.5 to 5 parts of antimony oxide, 0.4 to 3 parts of silicon oxide, 0.1 to 0.5 part of zirconium oxide, 0.5 to 1.5 parts of chromium oxide, 0.1 to 0.5 part of gallium oxide, 0.1 to 0.5 part of yttrium oxide and 0.1 to 0.5 part of lead bismuth borate glass, and the melting point of the used lead bismuth borate glass is as low as below 500 ℃ and cannot volatilize at high temperature, so that the lead bismuth borate glass has good fluxing effect. And secondly, the lead bismuthate glass is an oxide or a composite oxide with low surface energy, which can be independently formed into glass, and in the firing process, the oxide or the composite oxide is easy to form a glass phase, further fills pores formed by volatilization of bismuth oxide, reduces pore formation and size, forms good engagement with crystal grains in the cooling process, further reduces the defect concentration of crystal boundaries, and improves the through-flow capability.
Preferably, the particle size distribution of the zinc oxide in the main material is 500+/-50 nanometers, 90+/-20 nanometers and 30+/-10 nanometers respectively, and the particle size of other oxides is 1000+/-200 nanometers.
Preferably, the cosolvent in the step S1 is composed of citric acid solution, anhydrous glycol and tin dichloride solution.
Preferably, in the step S2, the green body is subjected to electric heating treatment at the temperature of 100-250 ℃ and the heat preservation time of 1-3 hours during the pressing of the green body.
Preferably, the sintering process in the step S4 may be one of conventional heating sintering, spark plasma heating sintering, current assisted heating sintering, and microwave heating sintering.
Preferably, in the step S4, a sintering curve in the multi-step curve sintering method is as follows:
(1) raising the temperature from room temperature to 700 ℃ within 6 hours at a heating rate of 2-5 ℃/min;
(2) then the temperature is increased from 700 ℃ to 1000 ℃ within 3 hours at a heating rate of 2-5 ℃/min;
(3) then heating from 1000 ℃ to 1150 ℃ within 2 hours at a heating rate of 2-5 ℃/min, and preserving heat for 6 hours;
(4) then cooling from 1150 ℃ to 850 ℃ within 9h at a heating rate of 2-5 ℃/min;
(5) then cooling from 850 ℃ to 700 ℃ within 2 hours at a heating rate of 2-5 ℃/min;
(6) then cooling from 700 ℃ to 600 ℃ within 1h at a heating rate of 2-5 ℃/min; and finally naturally cooling to room temperature to prepare the finished zinc oxide resistor disc.
(III) beneficial effects
Compared with the prior art, the invention provides a sintering method of a large-through-flow resistor disc, which has the following beneficial effects:
1. according to the sintering method of the large-through-flow resistor, the crystal structure of bismuth oxide is regulated by adopting a multi-step sintering method and regulating the heating rate and the heat preservation time, so that the main crystal form of bismuth oxide in the resistor is alpha phase. The alpha-phase bismuth oxide has good wettability to the boundary of oxide crystal particles, improves the uniformity of the size of oxide crystal particles and the uniformity of the distribution of the crystal particles in the resistor disc, forms the alpha-phase bismuth oxide forming sintering method, has the advantages of closest surface energy, tight combination and large contact area with ZnO, reduces the generation of tiny pores, ensures that the porosity is less than 3 percent, and realizes the improvement of the current passing capability of the resistor disc.
2. The high-through-flow resistor disc sintering method has the advantages that the melting point of the lead bismuthate boron glass used in the main material is as low as below 500 ℃, and the lead bismuthate boron glass cannot volatilize at high temperature, so that the high-through-flow resistor disc sintering method has a good fluxing effect. And secondly, the lead bismuthate glass is an oxide or a composite oxide with low surface energy, which can be independently formed into glass, and in the firing process, the oxide or the composite oxide is easy to form a glass phase, further fills pores formed by volatilization of bismuth oxide, reduces pore formation and size, forms good engagement with crystal grains in the cooling process, further reduces the defect concentration of crystal boundaries, and improves the through-flow capability.
3. According to the sintering method of the large-through-flow resistor disc, the material is added into the inner ring for filling, so that the inner ring is not in direct contact with external air, the heating mode is similar to that of the cake-shaped disc, and the uniformity of the inside is improved; and secondly, by applying voltages to the two ends of the resistor, uniformly heating the resistor by internal current, wherein the temperature rise of the furnace body is lower than 800 ℃, and the internal bismuth oxide does not reach the volatilization temperature, so that the bismuth oxide in the green compact of the zinc oxide resistor is fully diffused, and a uniform distribution state is formed in the resistor, thereby further improving the current passing capability of the zinc oxide resistor.
Drawings
FIG. 1 is a schematic diagram of the structure of the present invention.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Referring to fig. 1, a sintering method of a large-current resistor disc includes the following steps:
s1: mixing and grinding the main material and the cosolvent, and then drying and granulating;
s2: pressing the pelleting material obtained in the step S1 into a resistor disc green body;
s3: further drying and presintering the prepared prefabricated blank, wherein the presintering temperature is 300-700 ℃, the heat preservation time is 1-4 h, and the heating speed is 2-5 ℃/min, so as to obtain a zinc oxide resistor disc semi-finished product;
s4: spraying aluminum or coating electrode slurry on the upper and lower surfaces of the obtained zinc oxide resistor disc semi-finished product, coating insulating glaze on the side surface, filling the inner ring of the zinc oxide resistor disc semi-finished product with granulated materials with the same formula as the prefabricated blank, sintering by adopting a multi-step curve sintering method, applying direct current voltage with the voltage of 200V/mm-500V/mm to the two ends in the sintering temperature-rising process of the resistor disc, obtaining the finished product of the zinc oxide resistor disc after sintering, and filling the inner ring with the materials by adding the materials so that the inner ring is not in direct contact with external air, wherein the heating form is similar to that of a cake-shaped sheet, and the internal uniformity is improved; and secondly, by applying voltages to the two ends of the resistor, uniformly heating the resistor by internal current, wherein the temperature rise of the furnace body is lower than 800 ℃, and the internal bismuth oxide does not reach the volatilization temperature, so that the bismuth oxide in the green compact of the zinc oxide resistor is fully diffused, and a uniform distribution state is formed in the resistor, thereby further improving the current passing capability of the zinc oxide resistor.
In the step S1, the main materials comprise the following components: 85 to 95 parts of zinc oxide, 2 to 6 parts of bismuth oxide, 1 to 3 parts of cobalt oxide, 0.4 to 1.2 parts of nickel oxide, 0.2 to 1 part of manganese oxide, 1.5 to 5 parts of antimony oxide, 0.4 to 3 parts of silicon oxide, 0.1 to 0.5 part of zirconium oxide, 0.5 to 1.5 parts of chromium oxide, 0.1 to 0.5 part of gallium oxide, 0.1 to 0.5 part of yttrium oxide and 0.1 to 0.5 part of lead bismuth borate glass are added into zinc oxide to improve the nonlinear characteristic of the resistor disc, increase the energy density and improve the barrier height, and nickel oxide is added to improve the reliability, the stability and the alternating-current aging characteristic of the zinc oxide resistor disc.
The melting point of the lead bismuthate boron glass used in the main material is as low as below 500 ℃, and the lead bismuthate boron glass cannot volatilize at high temperature, so that the lead bismuthate boron glass has a good fluxing effect. And secondly, the lead bismuthate glass is an oxide or a composite oxide with low surface energy, which can be independently formed into glass, and in the firing process, the oxide or the composite oxide is easy to form a glass phase, further fills pores formed by volatilization of bismuth oxide, reduces pore formation and size, forms good engagement with crystal grains in the cooling process, further reduces the defect concentration of crystal boundaries, and improves the through-flow capability.
The particle size distribution of zinc oxide in the main material is 500+ -50 nm, 90+ -20 nm, 30+ -10 nm, and the particle size of other oxides is 1000+ -200 nm.
The cosolvent in the step S1 comprises citric acid solution, anhydrous glycol and tin dichloride solution.
And S2, carrying out electric heating treatment on the green body during the green body pressing in the step, wherein the heating temperature is 100-250 ℃, and the heat preservation time is 1-3 h.
The sintering process in step S4 may be one of conventional heating sintering, spark plasma heating sintering, current assisted heating sintering, and microwave heating sintering.
In the step S4, the sintering curve in the multi-step curve sintering method is as follows: (1) raising the temperature from room temperature to 700 ℃ within 6 hours at a heating rate of 2-5 ℃/min;
(2) then the temperature is increased from 700 ℃ to 1000 ℃ within 3 hours at a heating rate of 2-5 ℃/min;
(3) then heating from 1000 ℃ to 1150 ℃ within 2 hours at a heating rate of 2-5 ℃/min, and preserving heat for 6 hours;
(4) then cooling from 1150 ℃ to 850 ℃ within 9h at a heating rate of 2-5 ℃/min;
(5) then cooling from 850 ℃ to 700 ℃ within 2 hours at a heating rate of 2-5 ℃/min;
(6) then cooling from 700 ℃ to 600 ℃ within 1h at a heating rate of 2-5 ℃/min; and finally naturally cooling to room temperature to prepare the finished zinc oxide resistor disc.
Bismuth oxide has four distinct crystalline phases, a-, b-, g-, and d-phase, respectively. The a-phase bismuth oxide is bismuth oxide in a monoclinic phase crystal form (space group is P21/c, lattice parameters are as follows: a=0.58496 nm, b=0.81648 nm, c= 0.75101 nm), the b-phase bismuth oxide is bismuth oxide in a tetragonal phase crystal form (space group is P421c, lattice parameters are as follows: a=b=0.5738 nm, c= 0.5731 nm), the g-phase bismuth oxide is bismuth oxide in a body-cubic phase crystal form (space group is I23, lattice parameters are as follows: a=b=c=1.025 nm), and the d-phase bismuth oxide is bismuth oxide in a face-cubic phase crystal form (space group is Fm3m, lattice parameters are as follows: a=b=c= 0.56595 nm). The different crystal forms represent the difference of the spatial arrangement modes of oxygen atoms and bismuth atoms in bismuth oxide. Bismuth oxide of different crystal forms have different physical properties.
It was found that, as an inherent property of the material, the interface energy between the a-phase bismuth oxide and the surface of the zinc oxide solid particles is minimum, and therefore the wettability of the boundary of the a-phase bismuth oxide to the zinc oxide particles is best. Wettability refers to the ability or tendency of a liquid to spread on a solid surface; interfacial energy refers to the free enthalpy at the interface per unit area and represents the energy that the liquid needs to overcome to spread across the solid surface. Because the wettability is better, firstly, the acting force of bismuth oxide, zinc oxide and the like is strong, the bismuth oxide, zinc oxide and the like are not easy to peel, and the thermal stability under the action of high current is better;
secondly, the sliding rearrangement resistance among particles such as zinc oxide is smaller, the rearrangement among the particles enables the distribution among the grains to be more uniform, and the microscopic uniformity of the resistor disc is improved; thirdly, the a-phase bismuth oxide can enable particles such as zinc oxide and the like immersed in the bismuth oxide to generate more uniform, reduce particles with abnormal growth and improve the current passing capability and microscopic uniformity of the resistor disc; finally, the resistor can be better wrapped around the oxide crystal, the number of tiny air holes is reduced, and the current passing capability of the resistor is further improved.
The sintering method of the large-through-flow resistor disc adopts a multi-step sintering method, and adjusts the crystal form structure of bismuth oxide by adjusting the temperature rising rate and the heat preservation time, so that the main crystal form of bismuth oxide in the resistor disc is alpha phase. The alpha-phase bismuth oxide has good wettability to the boundary of oxide crystal particles, improves the uniformity of the size of oxide crystal particles and the uniformity of the distribution of the crystal particles in the resistor disc, forms the alpha-phase bismuth oxide forming sintering method, has the advantages of closest surface energy, tight combination and large contact area with ZnO, reduces the generation of tiny pores, ensures that the porosity is less than 3 percent, and realizes the improvement of the current passing capability of the resistor disc.
Although embodiments of the present invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made therein without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (7)
1. The sintering method of the large-through-flow resistor disc is characterized by comprising the following steps of:
s1: mixing and grinding the main material and the cosolvent, and then drying and granulating;
s2: pressing the pelleting material obtained in the step S1 into a resistor disc green body;
s3: further drying and presintering the prepared prefabricated blank, wherein the presintering temperature is 300-700 ℃, the heat preservation time is 1-4 h, and the heating speed is 2-5 ℃/min, so as to obtain a zinc oxide resistor disc semi-finished product;
s4: and filling the inner ring of the semi-finished product of the zinc oxide resistor disc with the granulated material with the same formula as the prefabricated blank, sintering by adopting a multi-step curve sintering method, applying direct current voltage with the voltage of 200V/mm-500V/mm to the two ends in the sintering temperature rising process of the resistor disc, and obtaining the finished product of the zinc oxide resistor disc after sintering.
2. The method for sintering a large-current resistor disc according to claim 1, wherein the main material composition in the step S1 is as follows: 85 to 95 parts of zinc oxide, 2 to 6 parts of bismuth oxide, 1 to 3 parts of cobalt oxide, 0.4 to 1.2 parts of nickel oxide, 0.2 to 1 part of manganese oxide, 1.5 to 5 parts of antimony oxide, 0.4 to 3 parts of silicon oxide, 0.1 to 0.5 part of zirconium oxide, 0.5 to 1.5 parts of chromium oxide, 0.1 to 0.5 part of gallium oxide, 0.1 to 0.5 part of yttrium oxide and 0.1 to 0.5 part of lead bismuth boron oxide glass.
3. The method for sintering a large-current resistor disc according to claim 2, wherein the particle size distribution of zinc oxide in the main material is 500±50 nm, 90±20 nm, 30±10 nm, and the particle size of other oxides is 1000±200 nm.
4. The method for sintering a large-flow resistor sheet according to claim 1, wherein the cosolvent in the step S1 comprises citric acid solution, anhydrous ethylene glycol and tin dichloride solution.
5. The method for sintering a large-current resistor disc according to claim 1, wherein the green body is subjected to electric heating treatment in the step S2 during the pressing, the heating temperature is 100-250 ℃, and the heat preservation time is 1-3 h.
6. The method according to claim 1, wherein the sintering process in step S4 is one of conventional heating sintering, spark plasma heating sintering, current assisted heating sintering, and microwave heating sintering.
7. The method for sintering a large-current resistor sheet according to claim 1, wherein the sintering curve in the step S4 using the multi-step curve sintering method is:
(1) raising the temperature from room temperature to 700 ℃ within 6 hours at a heating rate of 2-5 ℃/min;
(2) then the temperature is increased from 700 ℃ to 1000 ℃ within 3 hours at a heating rate of 2-5 ℃/min;
(3) then heating from 1000 ℃ to 1150 ℃ within 2 hours at a heating rate of 2-5 ℃/min, and preserving heat for 6 hours;
(4) then cooling from 1150 ℃ to 850 ℃ within 9h at a heating rate of 2-5 ℃/min;
(5) then cooling from 850 ℃ to 700 ℃ within 2 hours at a heating rate of 2-5 ℃/min;
(6) then cooling from 700 ℃ to 600 ℃ within 1h at a heating rate of 2-5 ℃/min; and finally naturally cooling to room temperature to prepare the finished zinc oxide resistor disc.
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| CN111161932A (en) * | 2020-04-07 | 2020-05-15 | 湖南省湘电试研技术有限公司 | Lightning-protection annular zinc oxide resistance card for power distribution network and preparation method thereof |
| CN111462970A (en) * | 2020-04-08 | 2020-07-28 | 湖南省湘电试研技术有限公司 | Lightning-protection annular zinc oxide resistance card for distribution network and preparation method thereof |
| CN111508676A (en) * | 2020-04-24 | 2020-08-07 | 国网湖南省电力有限公司 | Small-size distribution network annular zinc oxide resistance card and preparation method thereof |
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| CN111161932A (en) * | 2020-04-07 | 2020-05-15 | 湖南省湘电试研技术有限公司 | Lightning-protection annular zinc oxide resistance card for power distribution network and preparation method thereof |
| CN111462970A (en) * | 2020-04-08 | 2020-07-28 | 湖南省湘电试研技术有限公司 | Lightning-protection annular zinc oxide resistance card for distribution network and preparation method thereof |
| CN111508676A (en) * | 2020-04-24 | 2020-08-07 | 国网湖南省电力有限公司 | Small-size distribution network annular zinc oxide resistance card and preparation method thereof |
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