CN104240876A - 电压非线性电阻体 - Google Patents

电压非线性电阻体 Download PDF

Info

Publication number
CN104240876A
CN104240876A CN201410245360.8A CN201410245360A CN104240876A CN 104240876 A CN104240876 A CN 104240876A CN 201410245360 A CN201410245360 A CN 201410245360A CN 104240876 A CN104240876 A CN 104240876A
Authority
CN
China
Prior art keywords
zinc oxide
nonlinear resistor
face
orientation
hkl
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.)
Granted
Application number
CN201410245360.8A
Other languages
English (en)
Other versions
CN104240876B (zh
Inventor
山崎哲
早濑徹
森本健司
川崎真司
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.)
NGK Insulators Ltd
Original Assignee
NGK Insulators 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 NGK Insulators Ltd filed Critical NGK Insulators Ltd
Publication of CN104240876A publication Critical patent/CN104240876A/zh
Application granted granted Critical
Publication of CN104240876B publication Critical patent/CN104240876B/zh
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01C—RESISTORS
    • H01C10/00—Adjustable resistors
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G9/00—Compounds of zinc
    • C01G9/02—Oxides; Hydroxides
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/74—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by peak-intensities or a ratio thereof only
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/20—Particle morphology extending in two dimensions, e.g. plate-like
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/30—Particle morphology extending in three dimensions
    • C01P2004/32—Spheres
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
    • 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
    • C04B2235/3217—Aluminum oxide or oxide forming salts thereof, e.g. bauxite, alpha-alumina
    • 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
    • C04B2235/3267—MnO2
    • 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
    • C04B2235/3284—Zinc oxides, zincates, cadmium oxides, cadmiates, mercury oxides, mercurates 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
    • C04B2235/3289—Noble metal oxides
    • C04B2235/3291—Silver oxides
    • 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
    • C04B2235/3294—Antimony oxides, antimonates, antimonites or oxide forming salts thereof, indium antimonate
    • 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
    • C04B2235/34—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
    • C04B2235/3418—Silicon oxide, silicic acids, or oxide forming salts thereof, e.g. silica sol, fused silica, silica fume, cristobalite, quartz or flint
    • 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
    • C04B2235/36—Glass starting materials for making ceramics, e.g. silica glass
    • 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
    • C04B2235/50—Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
    • C04B2235/52—Constituents or additives characterised by their shapes
    • C04B2235/5292—Flakes, platelets or plates
    • 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
    • C04B2235/50—Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
    • C04B2235/54—Particle size related information
    • C04B2235/5418—Particle size related information expressed by the size of the particles or aggregates thereof
    • C04B2235/5445—Particle size related information expressed by the size of the particles or aggregates thereof submicron sized, i.e. from 0,1 to 1 micron
    • 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
    • C04B2235/60—Aspects relating to the preparation, properties or mechanical treatment of green bodies or pre-forms
    • C04B2235/602—Making the green bodies or pre-forms by moulding
    • C04B2235/6025—Tape casting, e.g. with a doctor blade
    • 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
    • C04B2235/60—Aspects relating to the preparation, properties or mechanical treatment of green bodies or pre-forms
    • C04B2235/604—Pressing at temperatures other than sintering temperatures
    • 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
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/72—Products characterised by the absence or the low content of specific components, e.g. alkali metal free alumina ceramics
    • 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
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/74—Physical characteristics
    • C04B2235/78—Grain sizes and shapes, product microstructures, e.g. acicular grains, equiaxed grains, platelet-structures
    • C04B2235/787—Oriented grains
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01C—RESISTORS
    • H01C17/00—Apparatus or processes specially adapted for manufacturing resistors
    • H01C17/06—Apparatus or processes specially adapted for manufacturing resistors adapted for coating resistive material on a base
    • H01C17/065—Apparatus or processes specially adapted for manufacturing resistors adapted for coating resistive material on a base by thick film techniques, e.g. serigraphy
    • H01C17/06506—Precursor compositions therefor, e.g. pastes, inks, glass frits
    • H01C17/06513—Precursor compositions therefor, e.g. pastes, inks, glass frits characterised by the resistive component
    • H01C17/06533—Precursor compositions therefor, e.g. pastes, inks, glass frits characterised by the resistive component composed of oxides
    • H01C17/06546—Oxides of zinc or cadmium

Landscapes

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

Abstract

本发明提供一种在高电流区中的电压较低且易于制造的电压非线性电阻体。本发明的电压非线性电阻体以氧化锌为主成分，其如下式所示的氧化锌的(100)面的取向度f(100)为0.40以上：f(100)＝I(100)/(I(100)+I(002)+I(101))其中，I(hkl)代表(hkl)面的X线衍射峰的积分强度值。

Description

电压非线性电阻体
技术领域
本发明涉及电压非线性电阻体。
背景技术
电压非线性电阻元件(压敏电阻元件)是具有电压非线性电阻体被夹在一对电极之间的结构的元件，作为从异常电压中保护电子电路等的元件，其被广泛用于各种传感器例如湿度传感器、温度传感器等、以及电源避雷器等中。电压非线性电阻体的电流电压特性如图2所示。具有优异的保护功能的电压非线性电阻体，其在图2的点线所封闭的高电流区中的电压VH较低。对于以氧化锌为主成分的电压非线性电阻体，已知其氧化锌晶粒内部的电阻率越小，电压VH越小，以及通过将Al、Ga、In等三价离子作为掺杂剂固溶于氧化锌中可减小氧化锌晶粒内部的电阻率等。此外，已知氧化锌因其六方晶系的晶体结构而具有各方异性的特性。
作为以氧化锌为主成分的电压非线性电阻体，专利文献1-2中有公开。专利文献1中公开了一种电压非线性电阻体，其通过沿c轴方向取向成形、烧结沿c轴方向结晶生长的针状氧化锌颗粒而制得，测定了该电压非线性电阻体的a轴方向和c轴方向的压敏电压。专利文献2中考虑到a轴方向的电导率较高，公开了(110)面取向的氧化锌烧结体。
[现有技术文献]
[专利文献]
[专利文献1]日本专利特公平4-48746号公报
[专利文献2]日本专利特开2002-121067号公报
发明内容
本发明所要解决的问题
然而，在专利文献1中，虽然通过挤压成形使针状氧化锌颗粒取向，但不清楚针状氧化锌颗粒的与挤压方向平行的面内(专利文献1的图1的上面)如(100)面或(110)面的取向程度。此外，虽然专利文献1公开了压敏电压(图2的虚线所封闭的平坦区中的电压)，但其没有公开或暗示高电流区中的电压VH。另一方面，在专利文献2中，虽然存在高电流区中的电压VH因氧化锌烧结体的(110)面取向而减小的可能性，但(110)面取向时需要在特定方向上施加高磁场，从而需要特殊设备用于制造该烧结体。
本发明的主要目的在于解决上述问题并提供在高电流区中的电压较低、容易制造的电压非线性电阻体。
用于解决技术问题的方案
本发明的电压非线性电阻体以氧化锌为主成分，其如下式所示的氧化锌(100)面的取向度f(100)为0.40以上。
f(100)＝I(100)/(I(100)+I(002)+I(101))
其中，I(hkl)表示(hkl)面的X线衍射峰的积分强度值。主成分是指占50重量％以上的重量比例的成分。
发明效果
根据本发明的电压非线性电阻体，因氧化锌的(100)面取向而沿着氧化锌的电导率较高的a轴方向取向。因此，氧化锌晶粒的内电阻变小，从而可能降低高电流区的电压。此外，本发明的电压非线性电阻体可通过如下工艺较容易地制造：通过对(100)面取向的板状氧化锌颗粒与助剂原料的混合物，采用使用了剪切力的方法获得使(100)面取向的成形体，然后对该成形体进行煅烧。
附图说明
图1所示为实施例1和对比例1的X射线衍射图。
图2所示为电压非线性电阻体的电流电压特性。
图3所示为压敏电阻元件10的截面图。
具体实施方式
本发明的电压非线性电阻体以氧化锌为主成分，该氧化锌的(100)面的取向度f(100)为0.40以上。在该情况下，由于使氧化锌的电导率较高的a轴方向取向，故氧化锌晶粒的内电阻减小，从而可能降低高电流区的电压。
本发明的电压非线性电阻体中，优选如下式所示的氧化锌的(002)面的取向度f(002)为0.10以下。在该情况中，由于未使氧化锌的电导率较低的c轴方向取向，故氧化锌晶粒的内电阻变小。
f(002)＝I(002)/(I(100)+I(002)+I(101))
考虑到产生非线性电阻特性，本发明的电压非线性电阻体优选包含铋(Bi)和镨(Pr)中的任意一种作为副成分。
本发明的电压非线性电阻体可包含Bi、Sb、Co、Mn、Cr、Ni、Si、Al、B、Ag(分别换算为如下量的Bi2O3、Sb2O3、Co2O3、MnO2、Cr2O3、NiO、SiO2、Al3+、B2O3、Ag2O)作为副成分：Bi2O3:0.1～5.0mol％、Sb2O3:0.02～5.0mol％、Co2O3:0.1～5.0mol％、MnO2:0.1～5.0mol％、Cr2O3:0～1.0mol％、NiO:0.1～5.0mol％、SiO2:0.001～10.0mol％、Al3+:0.001～0.05mol％、Bi2O3:0.0001～0.05mol％、Ag2O:0.001～0.05mol％。
本发明的电压非线性电阻体中，优选氧化锌晶体的平均粒径为3-15μm。
本发明的电压非线性电阻体中，优选结晶相由ZnO、Bi2O3和Zn7Sb2O12构成，或者由ZnO、Bi2O3、Zn7Sb2O12和Zn2SiO4构成。
本发明的电压非线性电阻体可用于片式压敏电阻中。
本发明的电压非线性电阻体可使用如下制造方法制造。即，可通过对以氧化锌为主成分的原料混合物使用剪切力，使氧化锌的(100)面取向成形以获得取向成形体，接着煅烧该取向成形体以获得本发明的电压非线性电阻体。
在上述制造方法中，作为原料混合物中的氧化锌，更优选使用50wt％以上的(100)面取向的板状氧化锌颗粒。此外，作为原料混合物，优选使用包含氧化锌作为主成份、Bi、Sb、Co、Mn、Cr、Ni、Si、Al、B、Ag作为副成分的混合物粉末，其中Bi、Sb、Co、Mn、Cr、Ni、Si、Al、B、Ag分别换算为如下量的Bi2O3、Sb2O3、Co2O3、MnO2、Cr2O3、NiO、SiO2、Al3+、B2O3、Ag2O：Bi2O3：0.1～5.0mol％、Sb2O3：0.02～5.0mol％、Co2O3：0.1～5.0mol％、MnO2：0.1～5.0mol％、Cr2O3：0～1.0mol％、NiO：0.1～5.0mol％、SiO2：0.001～10.0mol％、Al3+：0.001～0.05mol％、Bi2O3：0.0001～0.05mol％、Ag2O：0.001～0.05mol％。
上述制造方法中，在使用剪切力形成取向成形体时，例如，可采用流延成形、挤压成形、刮刀法等。此时，优选将原料混合物浆料化，然后使该浆料经由排料口形成片状取向成形体。此外，作为取向成形体，优选制造氧化锌的(100)面的取向度f(100)为0.50以上的取向成形体。这种取向成形体更优选氧化锌的(002)面的取向度f(002)在0.10以下。
上述制造方法中，优选在取向成形体脱脂后进行煅烧。煅烧优选在900-1200℃下进行，优选在大气中、常压下进行。进一步地，考虑到延长电压非线性电阻体的寿命，优选煅烧后，在400-600℃下进行热处理。此外，在使用片状取向成形体的情况下，在该煅烧之前，可将多个取向成形体层叠后进行加压成形。
本发明不限于上述实施方式，其可以各种方式实施，只要在本发明的技术范围内即可。
[实施例]
[实施例1]
氧化锌粉末的原料粉末通过如下方法制造。使用硝酸锌六水合物(关东化学株式会社制造)制备浓度为0.1M的Zn(NO3)2水溶液。此外，使用氢氧化钠(シグマアルドリッチ株式会社制造)制备浓度为0.1M的NaOH水溶液。将Zn(NO3)2水溶液与NaOH水溶液以1：1体积比混合，搅拌并在80℃下保持6小时，获得沉淀物。用离子交换水洗涤沉淀物3次后，通过干燥获得板状氧化锌一次粒子凝集而成的球状二次粒子。接着，使用直径为2mm的ZrO2制球体，以IPA(异丙醇)为分散介质，进行4小时的球磨粉碎处理，将氧化锌二次粒子粉碎为D50平均粒径(基于体积)为0.6μm的板状一次粒子。通过透射电子显微镜和选区电子衍射确定了该板状一次粒子沿(100)面取向。
按表1所示的组成，称量预定量的除了Al成分以外的助剂原料，使用直径为5mm的ZrO2制球体，以水为分散介质，对上述助剂原料进行16小时的球磨处理，将其粉碎成0.6μm的D50平均粒径。此处，B2O3、Ag2O的全部以及Bi2O3、SiO2的一部分来源于作为原料的由Bi2O3、SiO2、B2O3、Ag2O构成的玻璃料。向粉碎的混合物中混入预定量的Al3+(以硝酸铝水溶液形式引入)，对其进行干燥，获得助剂原料混合粉末。
[表1]
相对于100重量份的板状氧化锌一次粒子和助剂原料混合粉末(按表1所示的组成称量)的混合物，混入15重量份粘合剂(聚乙烯醇缩丁醛：商品号BM-2，积水化学工业株式会社制造)，6.2重量份塑化剂(DOP：二(2-乙基己基)邻苯二甲酸盐，黑金化成株式会社制造)和3重量份分散剂(商品名レオドールSP-030，花王株式会社制造)，以及分散介质(2-乙基己醇)。调节分散介质的量使得浆料粘度为20000-30000cP。通过刮刀法，将这样调整的浆料在PET薄膜上成形为干燥后厚度为24μm的片状。
通过XRD测定片状成形的带片(tape piece)(成形体)的(100)面和(002)面的取向度。该测定通过使用XRD装置(リガク株式会社制造，商品名RINT-TTRIII，平行光束光学系统)用X射线照射带成形体的表面时测定的XRD谱图来进行。表示(hkl)面的取向度的f(hkl)通过下式算出。本实施例中的取向度f(100)和f(002)的值各自为0.55和0.05。
f(hkl)＝I(hkl)/(I(100)+I(002)+I(101))
(I(hkl)为试样中的(hkl)面的X线衍射峰的积分强度值)
将获得的带切成直径为20mm的圆形，接着将100个切断的带片层叠，在将其放置在厚度为10mm的铝板上之后，进行真空包装。在85℃的温水中，以100kgf/cm2的压力对该真空包装物进行等静压成形，从而制得圆盘状成形体。将获得的成形体放置在脱脂炉中，在25℃/hr的升温速度、450℃的最高温度的条件下进行5小时脱脂。在30℃/hr的升温速度、1040℃的最高温度的条件下，在大气中将获得的脱脂体常压煅烧5小时。获得的烧成体的主成分为ZnO(重量比例为94.5重量％)
在烧成体的侧面上涂覆玻璃糊料(BL202，セントラル硝子株式会社制造)，在大气中、500℃下进行2小时热处理，通过焙烧该玻璃糊料形成侧面高电阻层，从而获得圆盘状氧化锌电压非线性电阻体。该热处理还有助于延长电压非线性电阻体的寿命。使用#800的SiC纸研磨获得的电压非线性电阻体的两端面，并洗涤。
获得的烧成体(圆盘状氧化锌电压非线性电阻体)的圆盘上表面中的(100)面和(002)面的取向度f(100)和f(002)的值各自为0.43和0.01。此外，以相同方式制造的烧成体中，与圆盘面垂直且与PET薄膜的拉伸方向平行的面中的(002)面的取向度f//(002)的值以及与圆盘面垂直且与PET薄膜的拉伸方向垂直的面中的(002)面的取向度f⊥(002)的值均为0.30，未观察到面内方向中的c轴取向的各向异性。f//(hkl)和f⊥(hkl)的计算式与f(hkl)的相同。
通过在前述获得的直径17mm×高1.6mm的电压非线性电阻体的研磨两端面(圆盘的上下表面)上涂覆In-Ga电极，获得压敏电阻原件，接着对其电流-电压特性进行测定。2mA/cm2的电流值(图2中的平坦区)时的发生电压为363V/mm，2kA/cm2的电流值(图2中的高电流区)时的发生电压为590V/mm。
图3所示为实施例1中的压敏电阻元件的截面图。该压敏电阻元件10具有在电压非线性电阻体12的侧面上的高电阻层14，以及在电压非线性电阻体12的上下表面上的一对电极16和18，在电压非线性电阻体12的上下表面中的(100)面的取向度f(100)的数值较高。
[比较例1]
按表1所示的组成，称量预定量的除了氧化锌和Al成分以外的助剂原料，以与实施例相同的方式球磨粉碎助剂原料混合物，接着以与实施例相同的方式制造板状氧化锌一次粒子，然后添加预定量的硝酸铝水溶液，将水含量调整成50wt％，将其与微量的粘合剂、分散剂以及消泡剂一起超音波搅拌60分钟，在进行30分钟羽毛搅拌混合后，通过喷涂干燥器粒化获得粒化物。在粒化物通过网孔为200μm的筛子后，在800kgf/cm2的成形压力下，将其单轴加压成形为直径26mm×高10mm。
获得的成形体的(100)面和(002)面的取向度f(100)和f(002)的值各自为0.35和0.13。
在与实施例相同的条件下对成形体进行脱脂、煅烧后，通过以与实施例相同的方式形成侧面高电阻层，获得氧化锌电压非线性电阻体。使用#800的SiC纸研磨获得的电压非线性电阻体的两端面，并洗涤。
获得的烧成体的(100)面和(002)的曲线度f(100)和f(002)的值各自为0.29和0.15。此外，在以相同的方式制造的烧成体中，与加压方向垂直的彼此正交的两个面中的(002)面的取向度f//(002)和f⊥(002)的值均为0.25，没有观察到面内方向中的c轴取向的各向异性。
将In-Ga电极涂覆在按前述获得的直径20mm×高8mm的电压非线性电阻体中经研磨的两端面上，并进行电流-电压特性的测定。2mA/cm2的电流值(图2中的平坦区)时的发生电压为365V/mm，2kA/cm2的电流值(图2中的高电流区)时的发生电压为608V/mm。
将实施例1和比较例1中获得的结果汇总在表2中。此外，图1所示为实施例1和比较中获得的成形体和烧成体的XRD图。与实施例1中的成形体和烧结体相比，比较例1中的成形体和烧结体具有较低值的f(100)，这可能是因为实施例1中在成形时施加了易于使其沿a轴方向取向的剪切力，而比较例1中没有施加这样的剪切力。
[表2]
*12mA/cm2的电流值时的发生电压(单位：V/mm)
*22kA/cm2的电流值时的发生电压(单位：V/mm)
[产业上的应用可能性]
本发明的电压非线性电阻体可用于各种传感器例如湿度传感器、温度传感器等以及电源避雷器等。
[符号说明]
10  压敏电阻元件
12  电压非线性电阻体
14  高电阻层
16  和18电极

Claims (2)

1.一种电压非线性电阻体，其以氧化锌为主成分，且如下式所示的所述氧化锌的(100)面的取向度f(100)为0.40以上：
f(100)＝I(100)/(I(100)+I(002)+I(101))
其中，I(hkl)代表(hkl)面的X线衍射峰的积分强度值。
2.如权利要求1所述的电压非线性电阻体，其特征在于，如下式所示的所述氧化锌的(002)面的取向度f(002)为0.10以下：
f(002)＝I(002)/(I(100)+I(002)+I(101))
其中，I(hkl)代表(hkl)面的X线衍射峰的积分强度值。
CN201410245360.8A 2013-06-07 2014-06-04 电压非线性电阻体 Active CN104240876B (zh)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2013120403 2013-06-07
JP2013-120403 2013-06-07

Publications (2)

Publication Number Publication Date
CN104240876A true CN104240876A (zh) 2014-12-24
CN104240876B CN104240876B (zh) 2018-03-13

Family

ID=50819671

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201410245360.8A Active CN104240876B (zh) 2013-06-07 2014-06-04 电压非线性电阻体

Country Status (6)

Country Link
US (1) US9034217B2 (zh)
EP (1) EP2818451B1 (zh)
JP (1) JP6280441B2 (zh)
KR (1) KR102142027B1 (zh)
CN (1) CN104240876B (zh)
TW (1) TWI595515B (zh)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10020415B2 (en) * 2016-01-12 2018-07-10 National University Of Singapore Device incorporating an oxide film and method of fabricating the same
JP6827164B2 (ja) * 2016-12-05 2021-02-10 パナソニックＩｐマネジメント株式会社 バリスタおよびその製造方法
CN106747406A (zh) * 2017-02-14 2017-05-31 爱普科斯电子元器件(珠海保税区)有限公司 无铅高绝缘陶瓷涂层氧化锌避雷器阀片及其制备方法
JP7169776B2 (ja) * 2018-06-06 2022-11-11 Koa株式会社 酸化亜鉛バリスタおよびその製造方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0276204A (ja) * 1988-09-13 1990-03-15 Tdk Corp ＺｎＯ薄膜バリスタ
JP2002121067A (ja) * 2000-10-10 2002-04-23 Kyocera Corp 酸化亜鉛質焼結体およびその製造方法
US20110101333A1 (en) * 2009-10-30 2011-05-05 Semiconductor Energy Laboratory Co., Ltd. Semiconductor device

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS63295463A (ja) 1987-05-26 1988-12-01 Inax Corp 酸化亜鉛バリスタ
JP2651039B2 (ja) 1990-06-15 1997-09-10 松下電子工業株式会社 半導体装置
JP2001010867A (ja) * 1999-06-21 2001-01-16 Murata Mfg Co Ltd セラミック原料造粒粉末の製造方法
JP4592209B2 (ja) * 2000-04-28 2010-12-01 株式会社豊田中央研究所 結晶配向バルクＺｎＯ系焼結体材料の製造方法およびそれにより製造された熱電変換デバイス
JP2004149367A (ja) * 2002-10-31 2004-05-27 Japan Science & Technology Agency 酸化亜鉛粒子又は膜製造用水溶液及び酸化亜鉛粒子又は膜の製造方法
WO2013031782A1 (ja) * 2011-08-31 2013-03-07 株式会社ニコン 酸化亜鉛薄膜の製造方法及びデバイス

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0276204A (ja) * 1988-09-13 1990-03-15 Tdk Corp ＺｎＯ薄膜バリスタ
JP2002121067A (ja) * 2000-10-10 2002-04-23 Kyocera Corp 酸化亜鉛質焼結体およびその製造方法
US20110101333A1 (en) * 2009-10-30 2011-05-05 Semiconductor Energy Laboratory Co., Ltd. Semiconductor device
CN102640279A (zh) * 2009-10-30 2012-08-15 株式会社半导体能源研究所 半导体器件

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
ENDER SUVACI等: "Processing of textured zinc oxide varistors via template grain growth", 《JOURNAL OF EUROPEAN CERAMIC SOCIETY》 *
JIANG LINING等: "Influence of texture on electrical properties of ZnO ceramics prepared by extrusion and spark plasma sintering", 《CERAMICS INTERNATIONAL》 *

Also Published As

Publication number Publication date
EP2818451A1 (en) 2014-12-31
US9034217B2 (en) 2015-05-19
EP2818451B1 (en) 2020-05-27
KR102142027B1 (ko) 2020-08-06
CN104240876B (zh) 2018-03-13
TW201511044A (zh) 2015-03-16
KR20140143695A (ko) 2014-12-17
JP2015015455A (ja) 2015-01-22
TWI595515B (zh) 2017-08-11
US20140361229A1 (en) 2014-12-11
JP6280441B2 (ja) 2018-02-14

Similar Documents

Publication Publication Date Title
CN102428586B (zh) 钨青铜型压电材料及其制备方法
Aydın et al. Determination of optical band gap of ZnO: ZnAl 2 O 4 composite semiconductor nanopowder materials by optical reflectance method
CN104240876A (zh) 电压非线性电阻体
CN103030390B (zh) 一种氧化锌压敏电阻材料及制备方法
US10643768B2 (en) Thermistor sintered body and thermistor element
JP7169776B2 (ja) 酸化亜鉛バリスタおよびその製造方法
KR100958665B1 (ko) 산화아연계 타깃
Fah et al. Effect of high-energy mechanical activation on the microstructure and electrical properties of ZnO-based varistors
CN108395217A (zh) 一种铌掺杂锰镍基负温度系数热敏电阻及其制备方法
JP5149262B2 (ja) 酸化インジウム−酸化亜鉛系焼結体ターゲット及びその製造法
CN105693235B (zh) 高介微波介质陶瓷材料及其制备方法
JP2002121067A (ja) 酸化亜鉛質焼結体およびその製造方法
Mahesh et al. Effect of two-step sintering on rare earth (RE= Y 2 O 3, Pr 6 O 11) doped ZnO–Bi 2 O 3 varistors processed from ‘nano-precursor’powders
CN104926301A (zh) 压电器件
Singh et al. Effect of Fe2O3 doping on structural properties of ZnO-V2O5 based varistor system
KR102628407B1 (ko) 배향 무연 압전 세라믹 조성물 및 이의 제조방법
JP2013197460A (ja) 熱電変換材料の製造方法及び熱電変換材料
JP4337436B2 (ja) サーミスタ素子の製造方法
Liu et al. Molten salt synthesis of doped nanocrystalline ZnO powders and applications in varistor ceramics
Chandramouli et al. Dielectric and pyroelectric properties of monovalent-lithium modified trivalent-samarium doped barium strontium sodium niobate tungsten bronze structured ceramics
Cai et al. Synthesis and dielectric properties of new compounds with pyrochlore type structure
JP6052279B2 (ja) ベータアルミナ質焼結体とその製造方法
CN110642603A (zh) 一种基于氧化镍的高精度新型ntc热敏电阻材料
EP2955166A1 (en) Piezoelectric oriented ceramic and method for manufacturing same
Kharchouche et al. Elaboration and electrical characterization of ZnO-based varistor ceramics in different sintering temperatures

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant