WO2023273901A1 - Résistance en forme de tige en oxyde métallique non linéaire et procédé de préparation associé - Google Patents

Résistance en forme de tige en oxyde métallique non linéaire et procédé de préparation associé Download PDF

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Publication number
WO2023273901A1
WO2023273901A1 PCT/CN2022/099125 CN2022099125W WO2023273901A1 WO 2023273901 A1 WO2023273901 A1 WO 2023273901A1 CN 2022099125 W CN2022099125 W CN 2022099125W WO 2023273901 A1 WO2023273901 A1 WO 2023273901A1
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WO
WIPO (PCT)
Prior art keywords
rod
shaped resistor
resistor
shaped
metal oxide
Prior art date
Application number
PCT/CN2022/099125
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English (en)
Chinese (zh)
Inventor
谢清云
蒙晓记
胡小定
甘雨
迟秀才
Original Assignee
西安西电避雷器有限责任公司
中国西电电气股份有限公司
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Publication of WO2023273901A1 publication Critical patent/WO2023273901A1/fr

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    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01C—RESISTORS
    • H01C17/00—Apparatus or processes specially adapted for manufacturing resistors
    • 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
    • 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
    • H01C17/075—Apparatus or processes specially adapted for manufacturing resistors adapted for coating resistive material on a base by thin film techniques
    • H01C17/10—Apparatus or processes specially adapted for manufacturing resistors adapted for coating resistive material on a base by thin film techniques by flame spraying
    • 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
    • H01C7/12—Overvoltage protection resistors

Definitions

  • the invention relates to the technical field of manufacturing nonlinear metal oxide resistors (varistors) for high-voltage arresters, and relates to a method for preparing nonlinear metal oxide rod-shaped resistors.
  • the invention also relates to a non-linear metal oxide rod-shaped resistor for a high-voltage arrester prepared by the preparation method.
  • Nonlinear metal oxide resistors are the core components of metal oxide arresters, and thus are the key components that determine the performance of the arrester. In the current production and manufacture of arresters, it is necessary to combine multiple pie-shaped or ring-shaped resistors, each of which needs to be formed, ground and sprayed with aluminum.
  • nonlinear metal oxide resistors adopts axial dry pressing and "vertical firing” methods.
  • pressure is applied in the axial direction. Due to the friction between the green body and the mold, it is difficult to form a high-height-diameter resistor with uniform density; It increases the amount of deformation, and it is difficult to meet the technical requirements; therefore, the ratio of the height to diameter of the produced resistors is generally relatively low, most of which are between 0.2 and 0.8, and the maximum does not exceed 2, all of which are in the shape of discs or rings. Therefore, it is called “resistor sheet”.
  • the object of the present invention is to provide a method for preparing a nonlinear metal oxide rod resistor.
  • a method for preparing a nonlinear metal oxide rod resistor On the basis of adopting the isostatic pressing forming technology, changing the dry pressing forming method and the sintering method, a nonlinear metal oxide rod-shaped resistor with a large aspect ratio is obtained.
  • Another object of the present invention is to provide a nonlinear metal oxide rod-shaped resistor with a large aspect ratio obtained by the preparation method.
  • the present invention provides the following technical solutions:
  • a method for preparing a nonlinear metal oxide rod-shaped resistor comprising the steps of:
  • the rod-shaped resistor green body is made by isostatic pressing and/or dry pressing along the radial direction of the green body, specifically:
  • a rod-shaped resistor blank is pressed separately along the radial direction of the blank by dry pressing;
  • first preform by dry pressing, and then press into a rod-shaped resistor body by isostatic pressing.
  • the isostatic pressing method includes dry bag forming and wet bag forming.
  • the molding pressure of the dry pressing method is 30-100 MPa
  • the molding pressure of the isostatic pressing method is 50-200 MPa.
  • sintering the rod-shaped resistor green body to obtain the rod-shaped resistor semi-finished product is specifically: placing the rod-shaped resistor green body on the supporting surface of the refractory supporting structure For sintering, the refractory supporting structure positions the rod-shaped resistor green body.
  • the supporting surface of the refractory supporting structure is a V-shaped groove surface or a U-shaped groove surface or a plane.
  • an insulating coating is applied on the surrounding surface, and the two ends are ground, and the insulating coating is organic polymer or inorganic glass.
  • the present invention also provides a nonlinear metal oxide rod-shaped resistor, which is prepared by the preparation method described in any of the above items, and the shape of the section perpendicular to the axial direction of the nonlinear metal oxide rod-shaped resistor is be circular, elliptical or polygonal.
  • the circular section diameter or the circumscribed circle diameter of the section of the non-linear metal oxide rod resistor is 20 mm to 80 mm.
  • the aspect ratio of the nonlinear metal oxide rod resistor is not less than 2.
  • the method for preparing a nonlinear metal oxide rod-shaped resistor provided by the present application, the steps include: S100, making a rod-shaped resistor green body by isostatic pressing or dry pressing along the radial direction; S200, The rod-shaped resistor body is sintered to obtain a semi-finished rod-shaped resistor; S300, spraying aluminum electrodes on both ends of the semi-finished rod-shaped resistor to obtain a non-linear metal oxide rod-shaped resistor.
  • the green body is formed by isostatic pressing and/or pressed along the radial direction of the green body to form a rod-shaped resistor green body, and finally a non-linear metal oxide body with a relatively large height and diameter is obtained.
  • the linear metal oxide rod-shaped resistor can not only form a rod-shaped green body more easily, but also make the density of the pressed rod-shaped resistor green body more uniform.
  • the use of cold isostatic pressing can make the green body uniform in all directions, so it can also be pressed into a nonlinear metal oxide rod-shaped resistor with a large height-to-diameter ratio and uniform density.
  • the present invention compared with the existing "vertical firing" method for sintering rod-shaped resistors, due to gravity and high-temperature load softening, the lower part of the rod-shaped resistors will be greatly deformed. Therefore, the present invention adopts Design a refractory support structure with a V-shaped groove surface or a U-shaped groove surface or a plane, and lay the non-linear metal oxide rod-shaped resistor body flat on the refractory support structure to reduce the deformation caused by sintering.
  • the method provided by the invention can obtain a nonlinear metal oxide rod-shaped resistor with a large height-to-diameter ratio. Compared with the existing resistor sheet, it greatly reduces the workload of glazing, painting, grinding, and aluminum spraying assembly, and also reduces the The amount of grinding produced during the grinding process can improve the utilization rate of raw materials.
  • the non-linear metal oxide rod-shaped resistor provided by the present invention can simplify the structure of the arrester due to the large height-to-diameter ratio of the non-linear metal oxide rod-shaped resistor, reduce the workload such as matching and grouping, and improve the production efficiency of the arrester.
  • a nonlinear metal oxide rod resistor can be a lightning arrester.
  • FIG. 1 is a schematic flow diagram of a method for preparing a nonlinear metal oxide rod-shaped resistor provided by an embodiment of the present invention
  • FIG. 2 is a schematic structural diagram of a nonlinear metal oxide rod resistor provided by an embodiment of the present invention
  • FIG. 3 is a schematic structural diagram of a second nonlinear metal oxide rod resistor provided by an embodiment of the present invention.
  • FIG. 4 is a schematic structural diagram of a third nonlinear metal oxide rod resistor provided by an embodiment of the present invention.
  • FIG. 5 is a schematic structural diagram of a fourth nonlinear metal oxide rod resistor provided by an embodiment of the present invention.
  • Fig. 6 is a schematic diagram of the use of the refractory load-bearing structure used in the sintering process in the preparation method of a nonlinear metal oxide rod-shaped resistor provided by the embodiment of the present invention
  • FIG. 7 is a schematic diagram of the use of the refractory load-bearing structure used in the sintering process in another method for preparing a nonlinear metal oxide rod-shaped resistor provided by the embodiment of the present invention
  • FIG. 8 is a schematic diagram of the use of the refractory load-bearing structure used in the sintering process in another method for manufacturing a nonlinear metal oxide rod-shaped resistor provided by an embodiment of the present invention.
  • 1 is a rod-shaped resistor blank
  • 2 is a refractory bearing structure
  • 21 is a V-shaped groove surface
  • 22 is a U-shaped groove surface
  • 23 is a plane.
  • the invention provides a preparation method of a nonlinear metal oxide rod-shaped resistor, which can obtain a nonlinear metal oxide rod-shaped resistor with a large ratio of height and diameter, and can improve the production efficiency of the arrester when applied to the arrester.
  • the invention also provides a non-linear metal oxide rod-shaped resistor obtained by the preparation method, which improves the production efficiency of the arrester.
  • the embodiment of the present invention provides a method for preparing a nonlinear metal oxide rod resistor (hereinafter referred to as rod resistor), which includes the following steps:
  • Step S100 performing isostatic pressing molding on the green body or dry pressing along the radial direction of the green body to form a rod-shaped resistor green body 1, wherein the green body is formed by spraying and granulating powder, and granulated Materials can be prepared according to methods well known to those skilled in the art;
  • Step S200 sintering the rod-shaped resistor green body 1 to obtain a semi-finished rod-shaped resistor
  • Step S300 spraying aluminum electrodes on both ends of the semi-finished rod-shaped resistor to obtain a rod-shaped resistor.
  • the material for electrode spraying is selected according to the different materials of metal oxides used in the green body. For example, if the metal oxide is a mixture of zinc oxide, bismuth oxide and antimony oxide, the material of the electrode spraying can be aluminum.
  • the green body is pressed and formed along the radial direction of the green body to form a rod-shaped resistor green body 1.
  • sheet the present application not only makes it easier to form a rod-shaped green body with a relatively large height-to-diameter ratio, but also makes the density of the pressed rod-shaped resistor green body 1 more uniform.
  • the use of isostatic pressing can make the green body uniformly stressed in all directions, so it can also be pressed into a rod-shaped resistor with a relatively large height and diameter and uniform density.
  • the rod-shaped resistor green body is pressed by the isostatic pressing method and/or the dry pressing method along the radial direction of the green body.
  • the dry pressing method can be used alone along the radial direction
  • the green body can be pressed and formed; the green body can also be pressed and formed by isostatic pressing alone; it can also be preformed by dry pressing and then finally pressed by isostatic pressing.
  • the isostatic pressing method can make the green body uniformly stressed in all directions, so the density will be more uniform when pressing the rod-shaped resistor with a large ratio of height to diameter.
  • the isostatic pressing method includes a dry bag forming method and a wet bag forming method.
  • the dry bag forming method facilitates automatic production.
  • the forming pressure of the dry pressing forming method is 30MPa-100MPa, and the forming pressure of the isostatic pressing forming method is 50MPa-200MPa.
  • the appropriate forming pressure is selected according to actual needs, and is not limited to this embodiment. Pressure range listed.
  • the sintering of the rod-shaped resistor green body 1 in step S200 is specifically: placing the rod-shaped resistor green body 1 flat on the refractory supporting structure 2 Sintering is carried out on the supporting surface, and the rod-shaped resistor green body 1 is positioned on the supporting surface. Specifically, the axis of the rod-shaped resistor blank 1 is placed horizontally, and the rod-shaped resistor blank 1 is placed on the supporting surface, and the supporting surface is positioned in contact with the surface of the rod-shaped resistor blank 1 to prevent the rod-shaped resistor from Green body 1 rolls or slides. In the prior art, the resistor green body is sintered with the axis vertically placed.
  • the sintering of the rod-shaped resistor green body 1 in this embodiment is carried out by laying flat on the refractory supporting structure 2 to reduce the deformation caused by sintering.
  • the supporting surface of the refractory supporting structure 2 is a V-shaped groove surface 21 or a U-shaped groove surface 22 or a plane 23 .
  • the V-shaped groove surface 21 , the U-shaped groove surface 22 and the plane 23 are selected according to the cross-sectional shape of the rod-shaped resistor blank 1 .
  • a refractory supporting structure 2 with a V-shaped groove surface or a U-shaped groove surface can be selected, and both the V-shaped groove surface 21 and the U-shaped groove surface 22 can be positioned
  • the surface of the rod-shaped resistor body 1 with a polygonal cross-section can be placed flat on the plane 23, and it is not easy to roll over.
  • an appropriate supporting surface can be selected according to different cross-sectional shapes of the rod-shaped resistor blank 1 , it is not limited to the shapes listed in this embodiment.
  • step S300 before spraying aluminum electrodes on both ends of the rod-shaped resistor semi-finished product, an insulating coating is applied on the surrounding surface, and the two ends are ground, and the insulating coating is organic polymer or Inorganic glass, specifically, the insulating coating can be epoxy resin or lead-free or lead-containing low-temperature glass. Both ends are ground to make the size and shape of the semi-finished rod resistance more accurate.
  • this application only needs to grind the two ends of a rod-shaped resistor, which greatly reduces the grinding process during the grinding process Quantity, improve the utilization rate of raw materials, save raw materials, reduce costs, and improve the preparation efficiency.
  • the embodiment of the present invention also provides a rod-shaped resistor prepared by this preparation method, the rod-shaped resistor is perpendicular to the axis
  • the shape of the cross-section is circular, polygonal or elliptical.
  • the rod-shaped resistors are obtained by the preparation method in this application, compared with the existing disc-shaped or ring-shaped resistors, since the height-diameter ratio of the rod-shaped resistors is relatively large, it is molded with each existing resistor , grinding and aluminum spraying process, this application greatly reduces the glazing, painting, grinding, aluminum spraying assembly workload, reduces the amount of grinding produced in the grinding process, improves the utilization rate of raw materials, and saves raw materials The production efficiency of the arrester is improved.
  • the diameter of the circumscribed circle of the cross-section perpendicular to the axial direction of the rod-shaped resistor is 20 mm to 80 mm.
  • the diameter of the circumscribed circle is the diameter of the circular cross-section.
  • the diameter of the polygonal cross-section is the circumcircle diameter, and for the ellipse, the circumcircle diameter is the major axis diameter.
  • the aspect ratio of the rod-shaped resistor is not less than 2, wherein the aspect ratio refers to the ratio of the height of the rod-shaped resistor to the diameter of the circumscribed circle of the section.
  • rod-shaped resistors The preparation of rod-shaped resistors will be illustrated below by taking regular quadrangular prism resistors as an example.
  • Press dry bag forming method to press 30 square prism resistors whose base length is 30mm and height is 60mm, and the molding pressure is 50MPa;
  • Press dry bag forming method to press 30 square prism resistors whose base length is 30mm and height is 90mm, and the molding pressure is 80MPa;
  • Press dry bag forming method to press 30 square prism resistors whose base length is 30mm and height is 120mm, and the molding pressure is 100MPa;
  • Preform by dry pressing method firstly, then use wet bag forming method to press 30 regular square prism resistors whose base length is 30mm and height is 60mm, and the molding pressure is 50MPa;
  • Preform by dry pressing method firstly, then use wet bag forming method to press 30 regular square prism resistors with bottom side length 30mm and height 90mm, molding pressure is 80MPa;
  • the maximum density of the rod-shaped resistors pressed by the dry pressing method is 5.65g/cm 3
  • the density of the rod-shaped resistors pressed by the two isostatic pressing methods is about 5.71g/cm 3 . It can be seen that under the same molding pressure, the rod-shaped resistors pressed by the isostatic pressing method have a higher density than the rod-shaped resistors pressed by the dry pressing method.
  • Rod resistors are sintered by different sintering methods.
  • Sinter 30 regular quadrangular prism resistors with a side length of 30 mm and a length of 120 mm in a vertical manner.
  • Press dry bag forming method to press 30 regular quadrangular prism resistors whose base length is 30mm and height is 120mm, and the molding pressure is 50MPa;
  • Press dry bag forming method to press 30 square prism resistors whose base length is 30mm and height is 120mm, and the molding pressure is 80MPa;
  • Preform by dry pressing method first, then use isostatic pressing method to press 30 regular rectangular prism resistors with bottom surface side length 30mm and height 120mm, molding pressure is 50MPa;

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  • Engineering & Computer Science (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Manufacturing & Machinery (AREA)
  • Physics & Mathematics (AREA)
  • Electromagnetism (AREA)
  • Thermistors And Varistors (AREA)
  • Apparatuses And Processes For Manufacturing Resistors (AREA)

Abstract

La présente demande divulgue une résistance en forme de tige en oxyde métallique non linéaire et un procédé de préparation associé. La forme de la résistance en forme de tige en oxyde métallique non linéaire est un cylindre, une colonne elliptique ou un prisme polygonal, et présente un rapport d'aspect important. Les étapes principales du procédé de préparation consistent : S100, à former un flan de résistance en forme de tige au moyen d'un pressage isostatique et/ou d'un pressage à sec le long de la direction radiale du flan ; S200, à fritter le flan de résistance en forme de tige afin d'obtenir une résistance en forme de tige semi-finie ; et S300, à pulvériser des électrodes d'aluminium sur les deux extrémités de la résistance en forme de tige semi-finie, afin d'obtenir une résistance en forme de tige en oxyde métallique non linéaire. Le procédé de préparation peut être utilisé pour la fabrication d'une résistance en oxyde métallique non linéaire présentant un rapport d'aspect important. Par rapport aux feuilles de résistance rondes ou toroïdales existantes, la charge du travail de moulage, de meulage, de pulvérisation d'aluminium et similaires est réduite, le taux d'utilisation des matières premières est amélioré, et des matières premières sont économisées ; en même temps, les structures des parafoudres et le travail d'assemblage sont simplifiés, et l'efficacité de production des parafoudres est améliorée.
PCT/CN2022/099125 2021-06-29 2022-06-16 Résistance en forme de tige en oxyde métallique non linéaire et procédé de préparation associé WO2023273901A1 (fr)

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CN202110727714.2 2021-06-29
CN202110727714.2A CN113363034B (zh) 2021-06-29 2021-06-29 一种非线性金属氧化物棒形电阻及其制备方法

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Citations (4)

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US4729053A (en) * 1985-02-07 1988-03-01 Bbc Brown, Boveri & Company, Limited Process for the production of a lightning arrester and products produced thereby
JP2001348269A (ja) * 2000-06-02 2001-12-18 Osaka Prefecture 酸化亜鉛磁器組成物とその製造方法および酸化亜鉛バリスタ
US6342828B1 (en) * 1997-01-16 2002-01-29 Asea Brown Boveri Ag Resistor which is designed in the form of a column and is resistant to high current in particular a varistor on a metal-oxide base, and method for producing such a resistor
CN108117380A (zh) * 2017-12-14 2018-06-05 上海卡贝尼精密陶瓷有限公司 一种超长氧化铝陶瓷圆棒的成型烧结方法

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US4031498A (en) * 1974-10-26 1977-06-21 Kabushiki Kaisha Meidensha Non-linear voltage-dependent resistor
US8117739B2 (en) * 2004-01-23 2012-02-21 Cooper Technologies Company Manufacturing process for surge arrester module using pre-impregnated composite
CN101700976B (zh) * 2009-11-20 2012-05-23 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
CN104143401B (zh) * 2014-07-24 2017-08-11 广东风华高新科技股份有限公司 超微型环形压敏电阻烧结装置
CN106673660B (zh) * 2016-12-09 2019-12-17 中国科学院上海硅酸盐研究所 一种液相烧结SiC非线性电阻陶瓷及其制备方法
CN106699158B (zh) * 2017-01-18 2019-12-03 广州新莱福磁电有限公司 一种高精度ntc热敏电阻芯片的制造方法
CN209969558U (zh) * 2019-01-19 2020-01-21 广东博杰特新材料科技有限公司 一种湿袋式冷等静压成型模具

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4729053A (en) * 1985-02-07 1988-03-01 Bbc Brown, Boveri & Company, Limited Process for the production of a lightning arrester and products produced thereby
US6342828B1 (en) * 1997-01-16 2002-01-29 Asea Brown Boveri Ag Resistor which is designed in the form of a column and is resistant to high current in particular a varistor on a metal-oxide base, and method for producing such a resistor
JP2001348269A (ja) * 2000-06-02 2001-12-18 Osaka Prefecture 酸化亜鉛磁器組成物とその製造方法および酸化亜鉛バリスタ
CN108117380A (zh) * 2017-12-14 2018-06-05 上海卡贝尼精密陶瓷有限公司 一种超长氧化铝陶瓷圆棒的成型烧结方法

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