CN116143511A - 一种低压比高通流能力氧化锌电阻片的制备方法 - Google Patents
一种低压比高通流能力氧化锌电阻片的制备方法 Download PDFInfo
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- CN116143511A CN116143511A CN202211723212.3A CN202211723212A CN116143511A CN 116143511 A CN116143511 A CN 116143511A CN 202211723212 A CN202211723212 A CN 202211723212A CN 116143511 A CN116143511 A CN 116143511A
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- resistor disc
- zinc oxide
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- low voltage
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- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 title claims abstract description 76
- 239000011787 zinc oxide Substances 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 238000005245 sintering Methods 0.000 claims abstract description 9
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000011521 glass Substances 0.000 claims abstract description 8
- 239000000843 powder Substances 0.000 claims abstract description 8
- 229910052709 silver Inorganic materials 0.000 claims abstract description 8
- 239000004332 silver Substances 0.000 claims abstract description 8
- 229910021193 La 2 O 3 Inorganic materials 0.000 claims abstract description 6
- 239000002994 raw material Substances 0.000 claims abstract description 3
- 238000004321 preservation Methods 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 7
- 238000005469 granulation Methods 0.000 claims description 5
- 230000003179 granulation Effects 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 5
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 4
- 239000000654 additive Substances 0.000 claims description 4
- 230000000996 additive effect Effects 0.000 claims description 4
- 238000000227 grinding Methods 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 238000000465 moulding Methods 0.000 claims description 3
- 239000007921 spray Substances 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 238000000498 ball milling Methods 0.000 claims description 2
- 239000011248 coating agent Substances 0.000 claims description 2
- 238000000576 coating method Methods 0.000 claims description 2
- 238000007599 discharging Methods 0.000 claims description 2
- 239000003292 glue Substances 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 239000000463 material Substances 0.000 claims description 2
- 230000000630 rising effect Effects 0.000 claims description 2
- 239000002002 slurry Substances 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 238000005507 spraying Methods 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- JLDSOYXADOWAKB-UHFFFAOYSA-N aluminium nitrate Chemical compound [Al+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O JLDSOYXADOWAKB-UHFFFAOYSA-N 0.000 claims 2
- 239000011230 binding agent Substances 0.000 claims 1
- -1 granulating Substances 0.000 claims 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 abstract description 20
- 239000000395 magnesium oxide Substances 0.000 abstract description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 9
- 239000013078 crystal Substances 0.000 abstract description 9
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 abstract description 8
- 229910052681 coesite Inorganic materials 0.000 abstract description 4
- 229910052906 cristobalite Inorganic materials 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 4
- 239000000377 silicon dioxide Substances 0.000 abstract description 4
- 235000012239 silicon dioxide Nutrition 0.000 abstract description 4
- 229910052682 stishovite Inorganic materials 0.000 abstract description 4
- 229910052905 tridymite Inorganic materials 0.000 abstract description 4
- 229910052761 rare earth metal Inorganic materials 0.000 abstract description 3
- 229910001404 rare earth metal oxide Inorganic materials 0.000 abstract description 3
- 150000002910 rare earth metals Chemical class 0.000 abstract description 3
- 239000006104 solid solution Substances 0.000 abstract description 3
- 229910052596 spinel Inorganic materials 0.000 abstract description 3
- 239000011029 spinel Substances 0.000 abstract description 3
- 239000011701 zinc Substances 0.000 abstract description 3
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(iii) oxide Chemical compound O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 description 6
- UPWOEMHINGJHOB-UHFFFAOYSA-N oxo(oxocobaltiooxy)cobalt Chemical compound O=[Co]O[Co]=O UPWOEMHINGJHOB-UHFFFAOYSA-N 0.000 description 6
- 239000000306 component Substances 0.000 description 5
- 229910044991 metal oxide Inorganic materials 0.000 description 5
- 150000004706 metal oxides Chemical class 0.000 description 4
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Inorganic materials O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000012360 testing method Methods 0.000 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 3
- XNDZQQSKSQTQQD-UHFFFAOYSA-N 3-methylcyclohex-2-en-1-ol Chemical compound CC1=CC(O)CCC1 XNDZQQSKSQTQQD-UHFFFAOYSA-N 0.000 description 2
- 230000002159 abnormal effect Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000012010 growth Effects 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- PPNAOCWZXJOHFK-UHFFFAOYSA-N manganese(2+);oxygen(2-) Chemical compound [O-2].[Mn+2] PPNAOCWZXJOHFK-UHFFFAOYSA-N 0.000 description 2
- VASIZKWUTCETSD-UHFFFAOYSA-N manganese(II) oxide Inorganic materials [Mn]=O VASIZKWUTCETSD-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000034655 secondary growth Effects 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000007767 bonding agent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000008358 core component Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
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- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/453—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on zinc, tin, or bismuth oxides or solid solutions thereof with other oxides, e.g. zincates, stannates or bismuthates
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- H01—ELECTRIC ELEMENTS
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- 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
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Abstract
本发明涉及避雷器用电阻片技术领域，且公开了一种低压比高通流能力氧化锌电阻片的制备方法，所述氧化锌电阻片由以下重量比的原料烧结而成：Bi2O3：2％‑4％；Sb2O3：2％‑4％；Co2O3：1.5％‑2.5％；Mn3O4：0.50％‑0.80％；Cr2O3：0.3％‑0.7％；NiO：0.30％‑0.70％；SiO2：0.5％‑0.8％；MgO：0.06％‑0.15％；La2O3：0.05％‑0.1％；Al(NO3)3·9H2O：0.02％‑0.06％；银玻璃粉：0.10％‑0.20％；ZnO：86.0％‑90.0％。配方中引进MgO以及稀土La2O3成分，使ZnO电阻片晶粒尺寸更加均匀，大幅度提高了通流能力。氧化镁可在ZnO晶粒边界可形成稳定的尖晶石固溶体，La2O3作为一种稀土金属氧化物，其离子半径大于Zn2+，La3+主要停留在ZnO晶界处，起“钉扎效应”的作用。通过调节添加配比，改善电阻片结构均匀性，提高通流能力的作用。
Description
技术领域
本发明涉及避雷器用电阻片技术领域，具体为一种低压比高通流能力氧化锌电阻片的制备方法。
背景技术
近年来，随着特高压交直流输电在我国的快速应用，国家电网对配电用避雷器保护水平及通流能力提出了更高的要求。ZnO电阻片作为避雷器的核心部件，它的性能参数直接决定了避雷器的电气性能。但目前氧化锌电阻片的保护水平和通流能力都较低。用低残压比和高通流能力氧化锌电阻片组装输配电系统中的金属氧化物避雷器，不仅可以减小其重量和体积，而且进一步提高避雷器及整个电力系统运行的安全可靠性。
发明内容
(一)解决的技术问题
针对现有技术的不足，本发明提供了一种低压比高通流能力氧化锌电阻片的制备方法，采用该配方制备出的电阻片，能够满足配电系统对电阻片残压、大电流和重复转移电荷等各方面性能的要求。
(二)技术方案
为实现上述目的，本发明提供如下技术方案：所述氧化锌电阻片由以下重量比的原料烧结而成：Bi2O3：2％-4％；Sb2O3：2％-4％；Co2O3：1.5％-2.5％；Mn3O4：0.50％-0.80％；Cr2O3：0.3％-0.7％；NiO：0.30％-0.70％；SiO2：0.5％-0.8％；MgO：0.06％-0.15％；La2O3：0.05％-0.1％；Al(NO3)3·9H2O：0.02％-0.06％；银玻璃粉：0.10％-0.20％；ZnO：86.0％-90.0％；
采用本发明配方制备电阻片的工艺为：将按重量百分比称取添加剂Bi2O3、Sb2O3、Co2O3、Mn3O4、Cr2O3、NiO、SiO2、MgO及银玻璃粉进行砂磨至一定粒度，然后加入硝酸铝、结合剂及主料ZnO混料，再经喷雾造粒、含水、成型、排胶、预烧、高阻层涂布、烧结、研磨、热处理、喷涂铝电极、涂釉等工序即得。
优选的，所述添加剂的球磨粒度为：平均粒径0.5-0.6μm。
优选的，所述喷雾造粒浆料含固量：65-68％，造粒平均粒径：80-110μm。
优选的，所述成型密度：3.0-3.05g/cm3。
优选的，所述烧结工艺中电阻片烧结过程温度曲线主要包括：升温速率45-50℃/h，保温温度1000-1050℃，保温时间6-8h，降温速率70-80℃/h。
(三)有益效果
与现有技术相比，本发明提供了一种低压比高通流能力氧化锌电阻片的制备方法，具备以下有益效果：
1、配方中增加了四氧化三锰和九水合硝酸铝的用量，显著降低了氧化锌晶粒的电阻率，有效的提高了电阻片的非线性系数，降低了残压比。
2、配方中引进MgO以及稀土La2O3成分，使ZnO电阻片晶粒尺寸更加均匀，大幅度提高了通流能力。氧化镁可在ZnO晶粒边界可形成稳定的尖晶石固溶体。La2O3作为一种稀土金属氧化物，其离子半径大于Zn2+，La3+主要停留在ZnO晶界处，起“钉扎效应”的作用。通过调节添加配比，这两种金属氧化物都具有抑制ZnO晶粒的异常生长，改善电阻片结构均匀性，提高通流能力的作用；采用延长保温时间的方式降低电阻片的保温阶段温度，避免了氧化锌晶粒的二次生长，提高电阻片微观结构的均匀性。
具体实施方式
下面将结合本发明的实施例，对本发明实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例仅仅是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。
实施例一：
包括下述组分及重量百分比：
Bi2O3：3.12％；Sb2O3：3.33％；Co2O3：1.95％；Mn3O4：0.55％；Cr2O3：0.42％；NiO：0.38％；SiO2：0.71％；MgO：0.06％；La2O3：0.05％；Al(NO3)3·9H2O：0.03％；银玻璃粉：0.15％；ZnO：89.25％。
实施例二：
包括下述组分及重量百分比：
Bi2O3：3.52％；Sb2O3：3.53％；Co2O3：2.35％；Mn3O4：0.65％；Cr2O3：0.42％；NiO：0.38％；SiO2：0.71％；MgO：0.06％；La2O3：0.08％；Al(NO3)3·9H2O：0.05％；银玻璃粉：0.15％；ZnO：88.1％。
实施例三：
包括下述组分及重量百分比：
Bi2O3：3.52％；Sb2O3：3.65％；Co2O3：2.35％；Mn3O4：0.75％；Cr2O3：0.42％；NiO：0.38％；SiO2：0.71％；MgO：0.08％；La2O3：0.075％；Al(NO3)3·9H2O：0.055％；银玻璃粉：0.15％；ZnO：87.86％。
采用上述实施例1、2、3所述配方制备的电阻片，规格48*20mm，各试验参数如下：
电测试验：电测执行标准：中华人民共和国能源行业标准NB/T 42152-2018《非线性金属氧化物电阻片通用技术要求》。
8/20μs雷电冲击重复转移电荷试验：
4/10μs大电流冲击耐受试验：
本实施例的氧化锌电阻片经试验后被证明效果良好，与常规方法制备的氧化锌电阻片相比，残压比降低0.05，通流能力提高了20％，电阻片在冲击后的稳定性显著改善，整体性能大大提高，相对于传统电阻片具有保护性能好、通流能力高等特点，完全达到预期要求。
本发明的有益效果是：本发明配方中增加了四氧化三锰和九水合硝酸铝的用量，显著降低了氧化锌晶粒的电阻率，有效的提高了电阻片的非线性系数，降低了残压比；配方中引进MgO以及稀土La2O3成分，使ZnO电阻片晶粒尺寸更加均匀，大幅度提高了通流能力。氧化镁可在ZnO晶粒边界可形成稳定的尖晶石固溶体。La2O3作为一种稀土金属氧化物，其离子半径大于Zn2+，La3+主要停留在ZnO晶界处，起“钉扎效应”的作用。通过调节添加配比，这两种金属氧化物都具有抑制ZnO晶粒的异常生长，改善电阻片结构均匀性，提高通流能力的作用；采用延长保温时间的方式降低电阻片的保温阶段温度，避免了氧化锌晶粒的二次生长，提高电阻片微观结构的均匀性。
尽管已经示出和描述了本发明的实施例，对于本领域的普通技术人员而言，可以理解在不脱离本发明的原理和精神的情况下可以对这些实施例进行多种变化、修改、替换和变型，本发明的范围由所附权利要求及其等同物限定。
Claims (5)
1.一种低压比高通流能力氧化锌电阻片的制备方法，其特征在于，所述氧化锌电阻片由以下重量比的原料烧结而成：Bi2O3：2％-4％；Sb2O3：2％-4％；Co2O3：1.5％-2.5％；Mn3O4：0.50％-0.80％；Cr2O3：0.3％-0.7％；NiO：0.30％-0.70％；SiO2：0.5％-0.8％；MgO：0.06％-0.15％；La2O3：0.05％-0.1％；Al(NO3)3·9H2O：0.02％-0.06％；银玻璃粉：0.10％-0.20％；ZnO：86.0％-90.0％；
采用本发明配方制备电阻片的工艺为：将按重量百分比称取添加剂Bi2O3、Sb2O3、Co2O3、Mn3O4、Cr2O3、NiO、SiO2、MgO及银玻璃粉进行砂磨至一定粒度，然后加入硝酸铝、结合剂及主料ZnO混料，再经喷雾造粒、含水、成型、排胶、预烧、高阻层涂布、烧结、研磨、热处理、喷涂铝电极、涂釉等工序即得。
2.根据权利要求1所述的一种低压比高通流能力氧化锌电阻片的制备方法，其特征在于，所述添加剂的球磨粒度为：平均粒径0.5-0.6μm。
3.根据权利要求1所述的一种低压比高通流能力氧化锌电阻片的制备方法，其特征在于，所述喷雾造粒浆料含固量：65-68％，造粒平均粒径：80-110μm。
4.根据权利要求1所述的一种低压比高通流能力氧化锌电阻片的制备方法，其特征在于，所述成型密度：3.0-3.05g/cm3。
5.根据权利要求1所述的一种低压比高通流能力氧化锌电阻片的制备方法，其特征在于，所述烧结工艺中电阻片烧结过程温度曲线主要包括：升温速率45-50℃/h，保温温度1000-1050℃，保温时间6-8h，降温速率70-80℃/h。
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