CN112694324A - 一种氧化锌非线性电阻片及其制备方法 - Google Patents

一种氧化锌非线性电阻片及其制备方法 Download PDF

Info

Publication number
CN112694324A
CN112694324A CN202011468836.6A CN202011468836A CN112694324A CN 112694324 A CN112694324 A CN 112694324A CN 202011468836 A CN202011468836 A CN 202011468836A CN 112694324 A CN112694324 A CN 112694324A
Authority
CN
China
Prior art keywords
zinc oxide
oxide nonlinear
preparing
zno
resistor disc
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN202011468836.6A
Other languages
English (en)
Inventor
汪丽
穆忍超
刘凌云
柳建军
杨军
翟毅
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Xiangyang Tte Electric Co ltd
Original Assignee
Xiangyang Tte Electric Co ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Xiangyang Tte Electric Co ltd filed Critical Xiangyang Tte Electric Co ltd
Priority to CN202011468836.6A priority Critical patent/CN112694324A/zh
Publication of CN112694324A publication Critical patent/CN112694324A/zh
Pending legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • 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
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
    • C04B35/63—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B using additives specially adapted for forming the products, e.g.. binder binders
    • C04B35/6303—Inorganic additives
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/64—Burning or sintering processes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01C—RESISTORS
    • H01C17/00—Apparatus or processes specially adapted for manufacturing resistors
    • 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
    • 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
    • H01C7/12—Overvoltage protection resistors
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3231—Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
    • C04B2235/3232—Titanium oxides or titanates, e.g. rutile or anatase
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3231—Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
    • C04B2235/3241—Chromium oxides, chromates, or oxide-forming salts thereof
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3231—Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
    • C04B2235/3251—Niobium oxides, niobates, tantalum oxides, tantalates, or oxide-forming salts thereof
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3262—Manganese oxides, manganates, rhenium oxides or oxide-forming salts thereof, e.g. MnO
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/327—Iron group oxides, their mixed metal oxides, or oxide-forming salts thereof
    • C04B2235/3275—Cobalt oxides, cobaltates or cobaltites or oxide forming salts thereof, e.g. bismuth cobaltate, zinc cobaltite
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/327—Iron group oxides, their mixed metal oxides, or oxide-forming salts thereof
    • C04B2235/3279—Nickel oxides, nickalates, or oxide-forming salts thereof
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3298—Bismuth oxides, bismuthates or oxide forming salts thereof, e.g. zinc bismuthate
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/34—Non-metal oxides, non-metal mixed oxides, or salts thereof that form the non-metal oxides upon heating, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3409—Boron oxide, borates, boric acids, or oxide forming salts thereof, e.g. borax
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/44—Metal salt constituents or additives chosen for the nature of the anions, e.g. hydrides or acetylacetonate
    • C04B2235/442—Carbonates
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/44—Metal salt constituents or additives chosen for the nature of the anions, e.g. hydrides or acetylacetonate
    • C04B2235/443—Nitrates or nitrites

Landscapes

  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Ceramic Engineering (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Electromagnetism (AREA)
  • Compositions Of Oxide Ceramics (AREA)

Abstract

本发明提出了一种氧化锌非线性电阻片，各组分原料按按摩尔百分比如下：ZnO：93.4％～97.2％；Bi2O3：0.824％～0.905％；Co2O3：0.805％～0.871％；Cr2O3：0.07％～0.12％；MnCo3：0.48％～0.64％；Ni2O3：0.24％～0.32％；TiO2：0.65％～0.88％；Nb2O5：0.075％～0.11％；玻璃粉：0.045％～0.065％；Al(NO3)3·9H2O：0.0033％～0.0048％；H3BO3：0.52％～0.67％；BaCO3：0.28％～0.37％，采用本发明配方的氧化锌非线性电阻片方波性能高，电位梯度低。

Description

一种氧化锌非线性电阻片及其制备方法
技术领域
本发明涉及氧化锌非线性电阻片领域，尤其涉及一种电位梯度为35V/mm的氧化锌非线性电阻片及其制备方法。
背景技术
近年来，避雷器用放电计数器和在线监测仪已广泛的应用于各电压等级的供电系统中，它们可以精确的记录避雷器的放电次数及在线监测避雷器的泄露电流的变化，从而可使供电部门准确掌握避雷器的工作状态、使用寿命及避雷器安装点的过电压活动情况。
根据国标GB11032-2000对避雷器性能之要求，导致了与其串联的放电计数器及在线监测仪性能要求更加严格。具体为，对于使用在放电计数器及在线监测仪上的氧化锌非线性电阻片，其2ms方波性能需达到1500A以上，8/20ms雷电冲击下残压值U10KA小于1500。
现有的氧化锌非线性电阻片以ZnO为主成分，添加Bi，Sb，Mn，Co，Si等成分金属氧化物，然后经混合，成型，烧成工艺制成的避雷器用电阻片，作为放电计数器及在线监测仪用电阻片，由于电位梯度相对较高，为了能满足残压尽可能低的要求，制造厂家只能不断的降低成型厚度，这样在生产直径为D52、D60、D70等大规格阀片时，产品经烧结后会产生严重的翅曲、变形，客户根本无法使用，且产品合格率很低，即便是这样，用该料方生产的产品2ms方波性能也很难满足要求。
发明内容
有鉴于此，本发明提出了一种2ms方波性能高，电位梯度低的避雷器用氧化锌非线性电阻片及制备方法。
本发明的技术方案是这样实现的，本发明提供了一种氧化锌非线性电阻片，各组分原料按按摩尔百分比如下：ZnO：93.4％～97.2％；Bi2O3：0.824％～0.905％；Co2O3：0.805％～0.871％；Cr2O3：0.07％～0.12％；MnCo3：0.48％～0.64％；Ni2O3：0.24％～0.32％；TiO2：0.65％～0.88％；Nb2O5：0.075％～0.11％；玻璃粉：0.045％～0.065％；Al(NO3)3·9H2O：0.0033％～0.0048％；H3BO3：0.52％～0.67％；BaCO3：0.28％～0.37％。
在以上技术方案的基础上，优选的，所述各组分原料按按摩尔百分比如下：ZnO：95.4％；Bi2O3：0.895％；Co2O3：0.864％；Cr2O3：0.1％；MnCo3：0.597％；Ni2O3：0.299％；TiO2：0.795％；Nb2O5：0.1％；玻璃粉：0.053％；Al(NO3)3·9H2O：0.004％；H3BO3：0.573％；BaCO3：0.32％。
本发明还提供了一种氧化锌非线性电阻片的制备方法，优选的，包括如下步骤：
步骤1：按照所述的配方称取相关原料；
步骤2：将除ZnO及Al(NO3)3·9H2O外的其他原料加入高能砂磨机，球磨6～10小时后用去离子水配制成浆料；
步骤3：将去离子水、分散剂的混合溶液倒入搅拌器并启动搅拌器，慢慢加入ZnO，待ZnO添加完后，加入球磨好的浆料，并加入PVA水溶液、消泡剂及Al(NO3)3·9H2O溶液进行搅拌，原料经喷雾干燥后造粒形成造粒料，造粒料加压成型得到成型坯片；
步骤4；将成型坯片装入隧道炉中进行排胶，然后进行烧结，得到氧化锌非线性电阻片。
在以上技术方案的基础上，优选的，所述步骤3中慢慢加入ZnO的同时，加入消泡剂搅拌，防止混合溶液因气泡多导致液面高。
在以上技术方案的基础上，优选的，所述步骤4中排胶时采用不锈钢筛网盛放成型坯片，坯片之间保持距离，采用单层摆放排胶，以确保坯片内部的PVA完全挥发。
在以上技术方案的基础上，优选的，所述步骤4中烧结时将成型坯片放置于刚玉莫来石匣钵内进行烧结。
更进一步优选的，所述刚玉莫来石匣钵内外部均刷涂有所述步骤2中的浆料，且对浆料进行烘干，然后用刚玉莫来石匣钵盛放成型坯片。
更进一步优选的，所述刚玉莫来石匣钵底部放有垫料，所述垫料为氧化锌非线性电阻片成品粉碎后制成。
更进一步优选的，所述垫料内参杂有Bi2O3，用以弥补在高温烧结下铋的挥发。
在以上技术方案的基础上，优选的，所述分散剂是聚丙烯酸胺或者十四烷基醋酸胺，所述消泡剂是磷酸三丁酯或者正辛醇。
本发明的一种氧化锌非线性电阻片的制备方法相对于现有技术具有以下有益效果：
(1)本发明通过添加TiO2、BaCO3，对促进ZnO的烧结、晶粒的生长、改善晶界的稳定性，起着一定的良好作用，从而达到降低电位梯度目的；
(2)本发明通过添加Sb2O3、Cr2O3、Ni2O3、H3BO3、Nb2O5，用于提高ZnO陶瓷耐受2ms方波，大电流冲击及长期在电场作用下运行的稳定性。
具体实施方式
下面将结合本发明实施方式，对本发明实施方式中的技术方案进行清楚、完整地描述，显然，所描述的实施方式仅仅是本发明一部分实施方式，而不是全部的实施方式。基于本发明中的实施方式，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方式，都属于本发明保护的范围。
制备实施例1-3的电阻片。
实施例1
ZnO：96.0077％；Bi2O3：0.824％；Co2O3：0.805％；Cr2O3：0.07％；MnCo3：0.48％；Ni2O3：0.24％；TiO2：0.65％；Nb2O5：0.075％；玻璃粉：0.045％；Al(NO3)3·9H2O：0.0033％；H3BO3：0.52％；BaCO3：0.28％。
实施例2
ZnO：95.4％；Bi2O3：0.895％；Co2O3：0.864％；Cr2O3：0.1％；MnCo3：0.597％；Ni2O3：0.299％；TiO2：0.795％；Nb2O5：0.1％；玻璃粉：0.053％；Al(NO3)3·9H2O：0.004％；H3BO3：0.573％；BaCO3：0.32％。
实施例3
ZnO：95.0442％；Bi2O3：0.905％；Co2O3：0.871％；Cr2O3：0.12％；MnCo3：0.64％；Ni2O3：0.32％；TiO2：0.88％；Nb2O5：0.11％；玻璃粉：0.065％；Al(NO3)3·9H2O：0.0048％；H3BO3：0.67％；BaCO3：0.37％。
ZnO是氧化锌电阻片的主要原料，微观结构呈六方型白色粉末球形或柱状，它是最终形成半导体结构的主体。
Bi2O3是构成ZnO非线性电阻片高阻晶界网络骨架结构必不可少的成分，对提高晶界势垒起着非常重要的作用。
TiO2、BaCO3对促进ZnO的烧结、晶粒的生长、改善晶界的稳定性，起着一定的良好作用，从而达到降低电位梯度目的。
Co2O3、MnCo3是提高氧化锌电阻片非线性功能的添加物，对改善氧化锌电阻片的非线性以及降低泄漏电流起着非常重要的作用。
Sb2O3、Cr2O3、Ni2O3、H3BO3、Nb2O5是提高氧化锌电阻片稳定性功能的添加物，均有助于提高氧化锌电阻片耐受2ms方波，大电流冲击及长期在电场作用下运行的稳定性。
玻璃粉的加入，可有效提高电阻片的耐工频老化性能。
Al(NO3)3·9H2O是降低ZnO晶粒电阻的功能添加物，硝酸铝的加入，不仅可明显降低电阻片的雷电冲击残压，使非线性区拓宽，而且可大大提高电阻片耐受大电流冲击的能力。
分别对实施例1-3进行制作，具体制作过程如下：
步骤1：按照所述的配方称取相关原料；
步骤2：将除ZnO及Al(NO3)3·9H2O外的其他原料加入高能砂磨机，实施例1球磨6小时后用去离子水配制成浆料，实施例2球磨8小时后用去离子水配制成浆料，实施例3球磨10小时后用去离子水配制成浆料；
步骤3：将去离子水、分散剂的混合溶液倒入搅拌器并启动搅拌器，慢慢加入ZnO，待ZnO添加完后，加入球磨好的浆料，并加入PVA水溶液、消泡剂及Al(NO3)3·9H2O溶液进行搅拌，原料经喷雾干燥后造粒形成造粒料，造粒料加压成型得到成型坯片；
步骤4；将成型坯片装入隧道炉中进行排胶，然后进行烧结，得到氧化锌非线性电阻片。
在具体实施方式中，作为优选的，所述步骤3中慢慢加入ZnO的同时，加入消泡剂搅拌，防止混合溶液因气泡多导致液面高。
所述步骤4中排胶时采用不锈钢筛网盛放成型坯片，坯片之间保持距离，采用单层摆放排胶，以确保坯片内部的PVA完全挥发。所述坯片之间距离优选为2～3mm。
所述步骤4中烧结为将成型坯片放置于刚玉莫来石匣钵内进行烧结。所述刚玉莫来石匣钵内外部均刷涂有所述步骤2中的浆料，且对浆料进行烘干，然后用刚玉莫来石匣钵盛放成型坯片。所述刚玉莫来石匣钵底部放有垫料，所述垫料为氧化锌非线性电阻片成品粉碎后制成。如此可防止混入其他杂质导致性能改变。垫料厚度优选为4～5mm。
所述垫料内参杂有Bi2O3，用以弥补在高温烧结下铋的挥发。
所述分散剂是聚丙烯酸胺或者十四烷基醋酸胺，所述消泡剂是磷酸三丁酯或者正辛醇。
对制作完成的氧化锌非线性电阻片进行性能测试，测试结果如下：
电测执行标准：中华人民共和国国家标准《交流无间隙金属氧化物避雷器GB11032-2000》，进行多次2ms方波电流冲击能量耐受试验，及多次8/20μs大电流冲击能量耐受试验。
市面正常电阻片为合肥科赛尔电气有限公司出售的高压交流氧化锌电阻片。
Figure BDA0002835441940000071
以上数据结果中，本发明的电阻片相比而言具有更高的2ms方波性能，电位梯度及8/20μs大电流冲击下残压值更低，效果更好。
以上所述仅为本发明的较佳实施方式而已，并不用以限制本发明，凡在本发明的精神和原则之内，所作的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。

Claims (10)

1.一种氧化锌非线性电阻片，其特征在于：各组分原料按按摩尔百分比如下：ZnO：93.4％～97.2％；Bi2O3：0.824％～0.905％；Co2O3：0.805％～0.871％；Cr2O3：0.07％～0.12％；MnCo3：0.48％～0.64％；Ni2O3：0.24％～0.32％；TiO2：0.65％～0.88％；Nb2O5：0.075％～0.11％；玻璃粉：0.045％～0.065％；Al(NO3)3·9H2O：0.0033％～0.0048％；H3BO3：0.52％～0.67％；BaCO3：0.28％～0.37％。
2.如权利要求1所述的一种氧化锌非线性电阻片，其特征在于：所述各组分原料按按摩尔百分比如下：ZnO：95.4％；Bi2O3：0.895％；Co2O3：0.864％；Cr2O3：0.1％；MnCo3：0.597％；Ni2O3：0.299％；TiO2：0.795％；Nb2O5：0.1％；玻璃粉：0.053％；Al(NO3)3·9H2O：0.004％；H3BO3：0.573％；BaCO3：0.32％。
3.一种按权利要求1所述的氧化锌非线性电阻片的制备方法，其特征在于：包括如下步骤：
步骤1：按照所述的配方称取相关原料；
步骤2：将除ZnO及Al(NO3)3·9H2O外的其他原料加入高能砂磨机，球磨6～10小时后用去离子水配制成浆料；
步骤3：将去离子水、分散剂的混合溶液倒入搅拌器并启动搅拌器，慢慢加入ZnO，待ZnO添加完后，加入球磨好的浆料，并加入PVA水溶液、消泡剂及Al(NO3)3·9H2O溶液进行搅拌，原料经喷雾干燥后造粒形成造粒料，造粒料加压成型得到成型坯片；
步骤4；将成型坯片装入隧道炉中进行排胶，然后进行烧结，得到氧化锌非线性电阻片。
4.如权利要求3所述的一种氧化锌非线性电阻片的制备方法，其特征在于：所述步骤3中慢慢加入ZnO的同时，加入消泡剂搅拌，防止混合溶液因气泡多导致液面高。
5.如权利要求3所述的一种氧化锌非线性电阻片的制备方法，其特征在于：所述步骤4中排胶时采用不锈钢筛网盛放成型坯片，坯片之间保持距离，采用单层摆放排胶，以确保坯片内部的PVA完全挥发。
6.如权利要求3所述的一种氧化锌非线性电阻片的制备方法，其特征在于：所述步骤4中烧结时将成型坯片放置于刚玉莫来石匣钵内进行烧结。
7.如权利要求6所述的一种氧化锌非线性电阻片的制备方法，其特征在于：所述刚玉莫来石匣钵内外部均刷涂有所述步骤2中的浆料，且对浆料进行烘干，然后用刚玉莫来石匣钵盛放成型坯片。
8.如权利要求7所述的一种氧化锌非线性电阻片的制备方法，其特征在于：所述刚玉莫来石匣钵底部放有垫料，所述垫料为氧化锌非线性电阻片成品粉碎后制成。
9.如权利要求8所述的一种氧化锌非线性电阻片的制备方法，其特征在于：所述垫料内参杂有Bi2O3，用以弥补在高温烧结下铋的挥发。
10.如权利要求3所述的一种氧化锌非线性电阻片的制备方法，其特征在于：所述分散剂是聚丙烯酸胺或者十四烷基醋酸胺，所述消泡剂是磷酸三丁酯或者正辛醇。
CN202011468836.6A 2020-12-14 2020-12-14 一种氧化锌非线性电阻片及其制备方法 Pending CN112694324A (zh)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202011468836.6A CN112694324A (zh) 2020-12-14 2020-12-14 一种氧化锌非线性电阻片及其制备方法

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202011468836.6A CN112694324A (zh) 2020-12-14 2020-12-14 一种氧化锌非线性电阻片及其制备方法

Publications (1)

Publication Number Publication Date
CN112694324A true CN112694324A (zh) 2021-04-23

Family

ID=75509099

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202011468836.6A Pending CN112694324A (zh) 2020-12-14 2020-12-14 一种氧化锌非线性电阻片及其制备方法

Country Status (1)

Country Link
CN (1) CN112694324A (zh)

Citations (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001052907A (ja) * 1999-08-10 2001-02-23 Toshiba Corp セラミック素子とその製造方法
CN1614720A (zh) * 2004-12-03 2005-05-11 江苏苏净集团有限公司 纳米掺杂复合低压氧化锌压敏电阻及其制作工艺
CN1963961A (zh) * 2006-11-21 2007-05-16 江苏苏净集团有限公司 微波烧结氧化锌压敏电阻的方法
CN101503291A (zh) * 2009-03-07 2009-08-12 抚顺电瓷制造有限公司 高压交流氧化锌电阻片配方
CN101503292A (zh) * 2009-03-07 2009-08-12 抚顺电瓷制造有限公司 直流氧化锌电阻片配方
CN101531507A (zh) * 2009-04-10 2009-09-16 孙丹峰 高能型氧化锌压敏电阻复合粉体及该压敏电阻的制造方法
CN101700976A (zh) * 2009-11-20 2010-05-05 中国西电电气股份有限公司 一种高压避雷器用非线性电阻片的配方及其制造方法
CN101759431A (zh) * 2009-12-10 2010-06-30 华中科技大学 一种低电位梯度氧化锌压敏电阻材料及其制备方法
CN102424577A (zh) * 2011-09-20 2012-04-25 桂林电子科技大学 一种低压压敏电阻陶瓷材料及其制备方法
CN102584206A (zh) * 2012-01-19 2012-07-18 深圳顺络电子股份有限公司 一种氧化锌压敏电阻生料
CN103030390A (zh) * 2012-12-28 2013-04-10 深圳顺络电子股份有限公司 一种氧化锌压敏电阻材料及制备方法
CN103400676A (zh) * 2013-07-30 2013-11-20 扬州发运电气有限公司 低压高能氧化锌电阻片制造方法
CN103693953A (zh) * 2013-11-27 2014-04-02 广西新未来信息产业股份有限公司 一种中低压氧化锌压敏电阻及其制备方法
CN108751980A (zh) * 2018-07-10 2018-11-06 芜湖市元奎新材料科技有限公司 氧化锌压敏电阻陶瓷及其制备方法
CN111816398A (zh) * 2020-06-23 2020-10-23 上海大学 可改善大电流冲击稳定性的电阻片制备方法

Patent Citations (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001052907A (ja) * 1999-08-10 2001-02-23 Toshiba Corp セラミック素子とその製造方法
CN1614720A (zh) * 2004-12-03 2005-05-11 江苏苏净集团有限公司 纳米掺杂复合低压氧化锌压敏电阻及其制作工艺
CN1963961A (zh) * 2006-11-21 2007-05-16 江苏苏净集团有限公司 微波烧结氧化锌压敏电阻的方法
CN101503291A (zh) * 2009-03-07 2009-08-12 抚顺电瓷制造有限公司 高压交流氧化锌电阻片配方
CN101503292A (zh) * 2009-03-07 2009-08-12 抚顺电瓷制造有限公司 直流氧化锌电阻片配方
CN101531507A (zh) * 2009-04-10 2009-09-16 孙丹峰 高能型氧化锌压敏电阻复合粉体及该压敏电阻的制造方法
CN101700976A (zh) * 2009-11-20 2010-05-05 中国西电电气股份有限公司 一种高压避雷器用非线性电阻片的配方及其制造方法
CN101759431A (zh) * 2009-12-10 2010-06-30 华中科技大学 一种低电位梯度氧化锌压敏电阻材料及其制备方法
CN102424577A (zh) * 2011-09-20 2012-04-25 桂林电子科技大学 一种低压压敏电阻陶瓷材料及其制备方法
CN102584206A (zh) * 2012-01-19 2012-07-18 深圳顺络电子股份有限公司 一种氧化锌压敏电阻生料
CN103030390A (zh) * 2012-12-28 2013-04-10 深圳顺络电子股份有限公司 一种氧化锌压敏电阻材料及制备方法
CN103400676A (zh) * 2013-07-30 2013-11-20 扬州发运电气有限公司 低压高能氧化锌电阻片制造方法
CN103693953A (zh) * 2013-11-27 2014-04-02 广西新未来信息产业股份有限公司 一种中低压氧化锌压敏电阻及其制备方法
CN108751980A (zh) * 2018-07-10 2018-11-06 芜湖市元奎新材料科技有限公司 氧化锌压敏电阻陶瓷及其制备方法
CN111816398A (zh) * 2020-06-23 2020-10-23 上海大学 可改善大电流冲击稳定性的电阻片制备方法

Similar Documents

Publication Publication Date Title
CN101503292B (zh) 直流氧化锌电阻片
EP2599759A1 (en) Process for producing zinc oxide varistor having high potential gradient and high non-linearity coefficient
CN105272208B (zh) 一种氧化锌压敏电阻器介质材料及其制备方法
CN107473731B (zh) 一种高能量型压敏电阻及其制造方法
CN102167579B (zh) 一种低温烧结的ZnO-Bi2O3-B2O3系压敏电阻材料及其制备方法
CN110922056B (zh) 一种用于电阻片的高绝缘无机高阻釉及制备方法
CN101503291B (zh) 高压交流氧化锌电阻片
EP1798741B1 (en) Current/voltage nonlinear resistor
CN105884345A (zh) 一种高电压梯度、低残压、低泄露电流的陶瓷及其制备方法
CN101447265A (zh) 氧化锌多层片式压敏电阻的制造方法
CN112694324A (zh) 一种氧化锌非线性电阻片及其制备方法
CN110423110A (zh) 一种超高非线性ZnO-Bi2O3基压敏陶瓷及其制备方法
CN110922182A (zh) 高梯度、低泄漏电流陶瓷的制备方法
CN115020051A (zh) 一种氧化锌压敏电阻器介质材料及其制备方法
CN102300832A (zh) 可变电阻陶瓷和含该可变电阻陶瓷的多层构件以及该可变电阻陶瓷的制备方法
EP2367178B1 (en) Voltage nonlinear resistor, lightning arrester loaded with voltage nonlinear resistor, and process for producing voltage nonlinear resistor
CN110060829A (zh) 一种氧化物电阻片加工工艺
CN110615677A (zh) 低温烧结氧化锌压敏电阻陶瓷材料、其制备方法及其电阻器的制备方法
KR101817831B1 (ko) 산화아연계 배리스터의 제조 방법
JP7359329B1 (ja) 酸化アンチモン代替酸化亜鉛素子
JP2692210B2 (ja) 酸化亜鉛形バリスタ
JP5334636B2 (ja) 電圧非直線抵抗体、電圧非直線抵抗体を搭載した避雷器及び電圧非直線抵抗体の製造方法
JPH05234716A (ja) 酸化亜鉛バリスタ
CN115662718A (zh) 一种高梯度非线性电阻片及其制备方法
CN114355028A (zh) 一种避雷器在线监测器用阀片配方

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
RJ01 Rejection of invention patent application after publication
RJ01 Rejection of invention patent application after publication

Application publication date: 20210423