WO2006128341A1 - Varistance zno stratifiee produite au moyen d'un materiau nanometrique et son procede de fabrication - Google Patents

Varistance zno stratifiee produite au moyen d'un materiau nanometrique et son procede de fabrication Download PDF

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WO2006128341A1
WO2006128341A1 PCT/CN2006/000300 CN2006000300W WO2006128341A1 WO 2006128341 A1 WO2006128341 A1 WO 2006128341A1 CN 2006000300 W CN2006000300 W CN 2006000300W WO 2006128341 A1 WO2006128341 A1 WO 2006128341A1
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zno
nano
silver
palladium
varistor
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PCT/CN2006/000300
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English (en)
Chinese (zh)
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Chengxaing Lv
Lanyi Wang
Zhigang Jing
Hui Du
Jinxiu Zhang
Shuzhou Wei
Yalin Wang
Shenfei Zheng
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Henan Jinguan Wangma Information Industrial Co., Ltd
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Publication of WO2006128341A1 publication Critical patent/WO2006128341A1/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
    • H01C7/112—ZnO type
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B18/00—Layered products essentially comprising ceramics, e.g. refractory products
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    • 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
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Definitions

  • Multi-layer chip ZnO varistor prepared by nano material and manufacturing method thereof
  • the invention relates to a multilayer chip varistor, in particular to a multi-layer chip ZnO varistor prepared by nano material; the invention also relates to a multilayer chip ZnO varistor prepared by the nano material A method of manufacturing a resistor. Background technique
  • the varistor can be divided into high temperature firing and low temperature firing according to the sintering temperature: high temperature firing becomes 1150 ° C ⁇ 1250 ° C; low temperature firing becomes about 900 ° low temperature section.
  • the conventional multi-layer chip ZnO varistor porcelain has a firing temperature of more than 1150 ⁇ , so it is necessary to use an expensive electrode slurry having a high precious metal content such as silver palladium, silver platinum, etc., and the cost is high.
  • the internal electrode used for high-temperature sintering is a 70% silver/30% palladium internal electrode, even with pure palladium or a pure platinum internal electrode, the precious metal has a high rhyme content, and the cost of the internal electrode is high, so the production cost is high.
  • the "manufacture of a zinc oxide varistor" patent proposes that a trace additive such as antimony trioxide and antimony trioxide is pre-fired at 350 ° C to 730 ° C to achieve co-firing with a pure silver internal electrode.
  • An object of the present invention is to provide a multilayer chip ZnO varistor which is prepared by using a nano material having low production cost and high reliability.
  • Another object of the present invention is to provide a method of manufacturing a multilayer chip ZnO varistor prepared by the above nanomaterial.
  • the first object of the present invention is achieved by the following technical solutions.
  • the multi-layer chip ZnO varistor prepared by the nano material of the invention is formed by staggering and arranging ZnO ceramic material and internal electrode layer, wherein: the main material of the ZnO ceramic material is The ZnO nanopowder having an average particle diameter of 1 to 99 faces is added with 3 to 8 % by mole of a nano powder additive, and the inner electrode layer is a palladium/silver inner electrode layer, wherein the proportion of palladium accounts for palladium/ The weight of the silver electrode is 11 ⁇ 25 %, and the proportion of silver is 75 ⁇ 89 % of the weight of the palladium / 4 ⁇ internal electrode.
  • the ZnO ceramic material and the palladium/silver inner electricity layer are staggered and arranged at 950 ⁇ 1100 °C. Sintered within the temperature range. Due to the use of ZnO nanopowders, the microstructure uniformity of the product is greatly improved, and the pressure sensitivity is improved. The important index of the flow capacity of the resistor is particularly advantageous; since the preciousness is greatly reduced in the palladium/silver inner electrode, the defect that the varistor reliability is poor due to the easy migration of silver ions in the inner electrode of the pure silver is overcome. It is better compatible to solve the two problems of low temperature co-firing of porcelain and electrode and improve product performance, and does not add any form of toxic element-lead in porcelain.
  • the nano powder additive may be added to the ZnO ceramic material, and the particle shape of the nano powder additive is spherical or approximately spherical, and the average particle diameter is It is l ⁇ 99nra, preferably 30 ⁇ 50, and the nano powder additive is mainly composed of Bi 2 0 3 , Sb 2 0 3 , MnC0 3 , Si0 2 , Cr 2 0 3 , Co 3 0 4 , Ni 2 0 3 Any combination of five or more.
  • the proportion of the nano powder additive in the ZnO ceramic material is 3 to 8% (molar percentage), wherein the nano Bi 2 0 3 0.
  • a method for manufacturing a multilayer chip ZnO varistor prepared by the above nano material comprising the following steps:
  • step (9) repeating step (4) to form a protective layer on the ceramic film strip;
  • the green body after debinding is fired at a temperature of 950-1100 °C.
  • the calcined chip varistor tile is added to the ball mill to grind the ball to eliminate the acute angle of the varistor, and the chamfering process is performed.
  • the varistor ceramic coated with the terminal electrode is subjected to silver burning treatment.
  • Said step (1) the ingredients, in 92-- adding 3-8% (mole percent) 97% (mole percent) of other nano ZnO powder composed of a metal powder additive, the nanomaterial
  • the particle morphology is spherical or nearly spherical, and can be any of the following three compositions: (1) From a single ZnO nanopowder and a single nanopowder additive Bi 2 0 3 , Sb 2 0 3 , MnC0 3 , a composition of five or more combinations of S i0 2 , Cr 2 0 3 , Co 3 0 4 , Ni 2 0 3 oxides; (2) synthesized by chemical synthesis or other methods Composition of a composite nano-oxide powder mainly containing Zn and any five or more combinations of Zn and Bi, Sb, Mn, S i, Cr, Co, Ni elements; (3) from a single ZnO Nano-powder and composite nano-oxide additive powder containing any five or more of Bi, Sb, Mn, Si, Cr
  • the nano-powder additive has a spherical or nearly spherical shape, an average particle size of 1 to 99 nra, preferably 30 to 50, and the nano powder additive is mainly composed of Bi 2 0 3 , Sb 2 0 3 , and MnC0 3 . , S i0 2 , Any five or more of Cr 2 0 3 , Co 3 0 4 , and Ni 2 0 3 are combined.
  • the nano powder additive accounts for 3 to 8% (mole percent) in the ZnO ceramic material, wherein the nano Bi 2 0 3 0.
  • the step (3) is to defoam a ceramic film tape having a uniform thickness of 5 to 50 ⁇ m.
  • the step (4) is to pre-press a part of the ceramic film tape in the step (3) into a protective layer of 3-20 times the thickness of the single-layer ceramic film tape.
  • the internal electrode in the step (5) is a palladium/silver inner electrode, wherein the proportion of palladium accounts for 11 to 25% of the weight of the palladium/silver inner electrode, and the proportion of silver accounts for 75 to 89% of the weight of the palladium/iridium internal electrode. .
  • the step (6) is formed by coating a palladium/silver inner electrode in the step (5) with a ceramic film tape and pressing it slightly.
  • the step (12) is preferably sintered at a temperature ranging from 960 to 1060 °C.
  • Nanomaterials are a new high-performance material. It is generally considered that nanometers refer to any one-dimensional length of less than 100 legs in three dimensions, and many excellent properties are exhibited due to their nano-size effects, such as nanomagnetic materials having a large magnetic susceptibility.
  • the use of nanomaterials to prepare electronic components can greatly improve the performance of electronic components. For sensitive components prepared with nanomaterials, the sensitivity is much higher than that of ordinary materials; nanomaterials also have the advantages of lowering the sintering temperature of ceramics and improving the brittleness of ceramic products. For multi-layer chip ZnO varistors, the use of nano-materials can greatly reduce the sintering temperature, and low-temperature electrode materials can be used, which greatly reduces the cost of the product.
  • the ZnO varistor film is required to be more uniform and uniform, and the powder particles are finer and more uniform.
  • the application of nanomaterials is beneficial to obtain a uniform ZnO varistor film. Therefore, the preparation of chip components using nanomaterials is an effective way to obtain high performance, low cost devices. W
  • the advantages of the present invention are as follows: (1) The use of ZnO nanopowder greatly improves the microstructure uniformity of the product, and is particularly advantageous for improving the flow capacity of the varistor. (2) The use of nano-powders with a small particle size allows the preparation of a lower temperature without changing the conventional formulation and without adding toxic elemental lead.
  • Fig. 1 is a schematic view showing the structure of a multilayer chip ZnO varistor prepared by the nanomaterial of the present invention
  • Fig. 2 is a flow chart showing the manufacturing method of the present invention. detailed description
  • the structure shown in Figure 1, the manufacturing method flow shown in Figure 2, and the nano-ZnO powder with an average particle size of 99 and various nano-powders with an average particle size of 99 legs are accurately weighed according to Formulation Table 1.
  • the oxide of the additive put the weighed material into the ball mill and add the appropriate amount of bismuth benzene, binder, dispersant and zirconium ball, ball milling for 12 hours to obtain the casting slurry, and then casting the thickness to 25 microns.
  • a ceramic film tape a ten-layer ceramic film tape is slightly pressurized to obtain a film protective layer a having a thickness of about 250 ⁇ m, and an alloy internal electrode b having a weight ratio of 75% silver and 25% palladium is printed on the film protective layer a, After lamination, another layer of internal electrodes is printed in a misaligned manner until the effective layer c is 8 layers. After the isostatic water pressure, the green bodies having a size of 1.0 ⁇ 0.5 mm after sintering are cut, and the green bodies are placed in a dedicated set.
  • the structure shown in Figure 1, the manufacturing method flow shown in Figure 2, and the nanometer ZnO powder with an average particle size of 1 nm and various nano-powder additives with an average particle diameter of 1 nm were accurately weighed according to Formulation Table 2.
  • the oxide put the weighed material into the ball mill and add the appropriate amount of xylene, binder, dispersant and zirconium ball, ball mill for 12 hours to obtain the casting slurry, and then cast the ceramic with a thickness of 25 microns.
  • Membrane tape ten layers of ceramic film tape are slightly pressed to obtain a film protective layer a having a thickness of about 250 ⁇ m, and an alloy internal electrode b having a weight ratio of 89% silver and 11% palladium is printed on the film protective layer a, laminated Then, another layer of internal electrodes is printed by dislocation, until the effective layer c is 8 layers, and after sintering by isostatic water pressure, the sintering is performed.
  • the green material with a size of 1.
  • ⁇ 0.5mm is placed in a special set on a special setter, and the temperature is slowly raised (30 °C / hr) to 35 (TC is kept for 3 hours, then slowly Warming (30 °C / hr) to 550 °C for 5 hours, after finishing the glue, heat at 950 °C for 2 hours, and then apply the terminal electrode d, to obtain ⁇ is 1 ( ⁇ , nonlinear coefficient is 23, leak Multi-layer chip ZnO varistor made of nano material with a current of 0.7 microamperes.
  • the manufacturing process shown in Figure 1 accurately weighed the prepared Zn and Bi, Sb, Mn, Si, Cr, and the average particle size of 40, as specified in Formulation Table 3.
  • Co, Ni, A 1 and other composite nano-oxide powder put the weighed material into the ball mill and add appropriate amount of xylene, binder, dispersant and zirconium ball, ball milling for 12 hours to obtain the casting slurry.
  • a ceramic film tape having a thickness of 25 ⁇ m is cast, and a ten-layer ceramic film tape is slightly pressurized to obtain a film protective layer a having a thickness of about 250 ⁇ m, and a printing weight ratio of 85% is obtained on the film protective layer a.
  • 15% palladium alloy internal electrode b after lamination, another layer of internal electrodes is printed by dislocation, until the effective layer c is 8 layers, after the isostatic water pressure, the sintered green body with a size of 1.0x 0.5mm is cut out.
  • Multi-layer chip ZnO varistor made of nano material with a leakage current of 1.7 ⁇ A.
  • Example 3 Formulation Table Material name ZnO ⁇ 203 Sb203 ⁇ 203 Si02 Co304 Cr203 MnC03 A1203 ratio (molar
  • the ten-layer ceramic film strip is slightly pressurized to obtain a film protective layer a having a thickness of about 250 ⁇ m, and an alloy internal electrode b having a weight ratio of 85% silver and 15% palladium is printed on the protective layer a of the film, after lamination Displacement of another layer of internal electrodes until the effective layer c is 8 layers, after the isostatic water pressure, the green bodies having a size of 1.0 0 x 0. 5 mm are cut out, and the green bodies are placed on a dedicated setter.
  • Multilayer chip ZnO varistor prepared from 4 microamps of nanomaterials. Table 4, Example 4 Recipe Table
  • the average particle size of various oxide materials are 5 Below the micron.
  • the weighed material was placed in a stirring ball mill, and an appropriate amount of deionized water and zirconium balls were added, and the material having an average particle diameter of 0.50 ⁇ m was obtained by ball milling for 6 hours.
  • After the ball-milled material is dried in a stainless steel plate for about 10 hours at 12 CTC, an appropriate amount of diterpene benzene, a binder, a dispersant and a zirconium ball are added in an appropriate amount, and the ball is ground for 24 hours to obtain a uniform and stable casting. Slurry.
  • a ceramic film tape having a thickness of 25 ⁇ m is cast, and a ten-layer ceramic film tape is slightly pressurized to obtain a film protective layer a having a thickness of about 250 ⁇ m, and a printing weight ratio of 70% silver, 30 is applied on the film protective layer a.
  • the inner electrode b of the palladium alloy is laminated, and then the other inner electrode is printed by dislocation, until the effective layer c is 8 layers. After the isostatic water pressure, the green body having a size of 1.0 ⁇ 0.5 mm after sintering is cut out.
  • the green body is placed in a special set on the furnace, and the temperature is raised (30 °C / hr) to 350 °C for 3 hours, then slowly heated (30 °C / hr) to 550. After incubating for 5 hours at °C, after finishing the glue, it was kept at 115CTC for 2 hours, and then the terminal electrode d was applied to obtain a conventional material (non-nano material) with V lraA of 8V, a nonlinear coefficient of 22, and a leakage current of 1.8 ⁇ A.
  • a multilayer chip ZnO varistor prepared.

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  • Microelectronics & Electronic Packaging (AREA)
  • Ceramic Engineering (AREA)
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  • Physics & Mathematics (AREA)
  • Electromagnetism (AREA)
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Abstract

L'invention concerne une varistance ZnO stratifiée produite au moyen d'un matériau nanométrique. Ladite varistance est obtenue par stratification et frittage configurés par stratification de couches de céramique ZnO produites au moyen d'un matériau nanométrique et des couches d'électrodes internes, la forme des particules du matériau principal de la céramique ZnO étant sphérique ou approximativement sphérique, la taille moyenne des particules de la poudre nanométrique de ZnO étant de 1 à 99 nm, une addition de poudre nanométrique dans laquelle la forme des particules est sphérique ou approximativement sphérique étant ajoutée en une quantité de 3 à 8 % en mole, lesdites couches d'électrodes internes étant des couches d'électrodes internes en palladium et argent, la teneur en palladium étant de 11 à 25 % en poids, la teneur en argent étant de 75 à 89 % en poids, lesdites couches de céramique ZnO et lesdites couches d'électrodes internes en palladium et argent étant stratifiées alternativement et frittées à une température de 950 à 1100 °C. L'invention concerne également un procédé de fabrication d'une varistance ZnO laminée. Le coefficient non linéaire a de la varistance ZnO stratifiée dans la spécification 1005 produite par l'invention est supérieure à 20, et le courant de fuite IL est inférieur à 2,0 µA.
PCT/CN2006/000300 2005-06-03 2006-03-01 Varistance zno stratifiee produite au moyen d'un materiau nanometrique et son procede de fabrication WO2006128341A1 (fr)

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CN200510017658.4 2005-06-03

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CN115073163A (zh) * 2022-07-01 2022-09-20 深圳振华富电子有限公司 片式压敏电阻器及其制备方法和应用

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Publication number Priority date Publication date Assignee Title
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CN103086710B (zh) * 2013-01-18 2014-08-27 西安恒翔电子新材料有限公司 一种宽梯度范围的氧化锌压敏电阻专用瓷粉及其制备方法
CN103310928B (zh) * 2013-06-14 2016-03-30 北京捷安通达科贸有限公司 Mov陶瓷片及其电极浆料的印刷方法
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CN103496970A (zh) * 2013-09-29 2014-01-08 陈锐群 一种压敏陶瓷材料及其制备方法
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CN105198402B (zh) * 2015-09-15 2018-01-02 湖南双创部落信息咨询服务有限责任公司 一种纳米氧化锌压敏电阻材料及其制备方法
CN106630998B (zh) * 2016-11-23 2019-05-03 华北科技学院 一种安全环保的非线性压敏电阻器及其应用
CN109727740B (zh) * 2018-12-29 2021-11-23 肇庆鼎晟电子科技有限公司 一种高精度高可靠性叠层热敏电阻芯片及其制作方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH1012406A (ja) * 1996-06-18 1998-01-16 Marcon Electron Co Ltd 積層セラミックバリスタ
CN1564270A (zh) * 2004-04-05 2005-01-12 广州新日电子有限公司 低温烧结ZnO多层片式压敏电阻器及其制造方法
CN1571078A (zh) * 2004-05-13 2005-01-26 上海大学 高通流纳米复合材料避雷器阀片的制备方法

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH1012406A (ja) * 1996-06-18 1998-01-16 Marcon Electron Co Ltd 積層セラミックバリスタ
CN1564270A (zh) * 2004-04-05 2005-01-12 广州新日电子有限公司 低温烧结ZnO多层片式压敏电阻器及其制造方法
CN1571078A (zh) * 2004-05-13 2005-01-26 上海大学 高通流纳米复合材料避雷器阀片的制备方法

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115073163A (zh) * 2022-07-01 2022-09-20 深圳振华富电子有限公司 片式压敏电阻器及其制备方法和应用
CN115073163B (zh) * 2022-07-01 2023-09-01 深圳振华富电子有限公司 片式压敏电阻器及其制备方法和应用

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