KR101161924B1 - ZnO-based varistor composition - Google Patents

ZnO-based varistor composition Download PDF

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KR101161924B1
KR101161924B1 KR1020090079746A KR20090079746A KR101161924B1 KR 101161924 B1 KR101161924 B1 KR 101161924B1 KR 1020090079746 A KR1020090079746 A KR 1020090079746A KR 20090079746 A KR20090079746 A KR 20090079746A KR 101161924 B1 KR101161924 B1 KR 101161924B1
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zno
varistor
composition
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KR20110022237A (en
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홍연우
신효순
여동훈
노상섭
홍경표
정준환
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한국세라믹기술원
주식회사 아모텍
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Priority to KR1020090079746A priority Critical patent/KR101161924B1/en
Priority to US13/392,310 priority patent/US8865028B2/en
Priority to JP2012526658A priority patent/JP5665870B2/en
Priority to PCT/KR2010/005747 priority patent/WO2011025283A2/en
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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
    • 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
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    • 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
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    • 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
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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
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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
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    • 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
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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
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    • 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

Abstract

본 발명은 산화아연(ZnO)을 주성분으로 하며, 칼슘(Ca)을 함유한 화합물을 부성분으로 포함하는 것을 특징으로 하는 ZnO계 바리스터 조성물에 관한 것이다. 상기 바리스터 조성물은 항복전압, 누설전류, 비선형계수, 클램핑 전압비, 써어지 흡수능, 열화특성 등의 면에서 우수하며, 특히, Bi2O3를 포함하지 않기 때문에 우수한 EDS(Electro-Static Discharge) 특성을 제공한다. 또한, 환경규제 성분인 Sb2O3를 포함하지 않으므로 우수한 작업안전성을 제공하며, 고온소결이 요구되어 제조원가 상승을 야기하는 Pr계 성분을 포함하지 않으므로 낮은 제조단가로 제조될 수 있다.The present invention relates to a ZnO-based varistor composition comprising zinc oxide (ZnO) as a main component and comprising a compound containing calcium (Ca) as a subcomponent. The varistor composition is excellent in terms of breakdown voltage, leakage current, nonlinear coefficient, clamping voltage ratio, surge absorption capacity, deterioration characteristics, and the like, and particularly, does not include Bi 2 O 3, thereby providing excellent EDS (Electro-Static Discharge) characteristics. to provide. In addition, since it does not include the environmental regulation component Sb 2 O 3 provides excellent work safety, and does not include a Pr-based component that requires high temperature sintering to increase the manufacturing cost can be manufactured at a low manufacturing cost.

ZnO, Ca, 바리스터, EDS, 안전성 ZnO, Ca, Varistor, EDS, Safety

Description

ＺｎＯ계 바리스터 조성물{ZnO-based varistor composition}ZnO-based varistor composition {ZnO-based varistor composition}

본 발명은 바리스터 조성물에 관한 것으로서, 특히 산화아연(ZnO)을 주성분으로 하며, 칼슘(Ca)을 함유한 화합물을 부성분으로 포함하는 ZnO계 바리스터 조성물에 관한 것이다. The present invention relates to a varistor composition, and more particularly, to a ZnO-based varistor composition containing zinc oxide (ZnO) as a main component and containing a compound containing calcium (Ca) as a subcomponent.

바리스터의 재료 조성계로는 SiC계 재료, SrTiO3계 재료, ZnO를 주성분으로 하는 ZnO-Bi계 재료 및ZnO-Pr계 재료가 잘 알려져 있다. 특히, ZnO-Bi계 재료나 ZnO-Pr계 재료로 형성된 ZnO계 바리스터는, SiC계 바리스터나 SrTiO3계 바리스터에 비해서 전압 비선형성이 뛰어나고 서지(serge) 전류내량이 양호하기 때문에, 서지 전류에서 전자기기를 보호하는 능력이 우수하여 서지 방호(防護)소자의 재료로 많이 사용되고 있다.As the material composition system of the varistor, SiC-based materials, SrTiO 3 -based materials, ZnO-Bi-based materials and ZnO-Pr-based materials having ZnO as a main component are well known. Particularly, ZnO-based varistors formed of ZnO-Bi-based or ZnO-Pr-based materials have better voltage nonlinearity and better surge current resistance than SiC-based and SrTiO 3- based varistors. Due to its excellent ability to protect equipment, it is widely used as a material for surge protection devices.

ZnO계 바리스터 중 ZnO-Bi계 바리스터는 Bi2O3, Sb2O3, Mn, Co, Ni, Cr, glass frit, Al, K등의 성분으로 구성된다. 그런데, 상기 성분 중Bi2O3는EDS(Electro-Static Discharge) 내성이 약하기 때문에, 이를 포함하는 ZnO-Bi계 바 리스터도 EDS 특성이 좋지 못한 단점을 갖는다. 또한, 상기 성분 중 Sb2O3는 발암물질로 분류되어 농도가 규제되고 있기 때문에, 이를 포함하는 ZnO-Bi계 바리스터는 제조가 자유롭지 못하고, 제조 작업시 작업자의 안전을 확보해야 하는 단점을 갖는다. Among the ZnO-based varistors, ZnO-Bi-based varistors are composed of Bi 2 O 3 , Sb 2 O 3 , Mn, Co, Ni, Cr, glass frit, Al, and K. By the way, Bi 2 O 3 of the components have a weak EDS (Electro-Static Discharge) resistance, ZnO-Bi-based varistors containing the same also has the disadvantage of poor EDS characteristics. In addition, since Sb 2 O 3 is classified as a carcinogen and its concentration is regulated, ZnO-Bi-based varistors containing the same are not free to manufacture and have a disadvantage of ensuring safety of workers during manufacturing operations.

한편, ZnO계 바리스터 중 ZnO-Pr계 바리스터는 전압 비선형성은 양호하나, ZnO-Bi계 바리스터에 비해서 누설전류가 크다는 결점이 있으며, 귀금속 계열의 원료인Pr계 성분을 포함하고 있고 고온소결(1200℃ 이상)이 요구되어 고가의 성분(Pd 등)을 다량 사용하므로 제조 비용이 높다는 단점이 있다.On the other hand, ZnO-Pr-based varistors of ZnO-based varistors have a good voltage nonlinearity, but have a drawback in that leakage current is larger than that of ZnO-Bi-based varistors. There is a disadvantage in that the manufacturing cost is high because a large amount of expensive components (Pd, etc.) are used.

본 발명은, 종래기술의 상기와 같은 문제를 해결하기 위한 것으로서, 바리스터의 EDS(Electro-Static Discharge) 특성에 부정적인 영향을 미치는 성분, 환경규제 성분 및 고온소결이 요구되어 제조원가의 상승을 야기하는 성분을 대체하는 새로운 성분들로 구성되어, EDS 특성 등 바리스터에 요구되는 전반적인 물성이 우수하며, 제조시 작업안전성이 우수하며, 생산단가가 낮은 경제성 있는 바리스터 조성물을 제공하는 것을 목적으로 한다. The present invention is to solve the above problems of the prior art, a component that negatively affects the electro-static discharge (EDS) characteristics of the varistors, environmental regulatory components and components that require high temperature sintering to increase the manufacturing cost It is composed of new ingredients to replace the, the overall physical properties required for varistors such as EDS characteristics, excellent work safety during manufacturing, and to provide an economical varistor composition with a low production cost.

본 발명은, ZnO계 바리스터 조성물에 있어서, Bi2O3, Sb2O3 및 Pr6O11을 포함하지 않으며, Ca, Co, Cr 및 La를 포함하는 것을 특징으로 하는 ZnO계 바리스터 조성물을 제공한다. The present invention provides a ZnO-based varistor composition, wherein the ZnO-based varistor composition does not include Bi 2 O 3 , Sb 2 O 3, and Pr 6 O 11 , but includes Ca, Co, Cr, and La. do.

상기 ZnO계 바리스터 조성물은, 조성물에 포함되는 총 금속원자를 기준으로 Zn 90~98 at%, Ca 0.2~9 at%, Co 0.2~5 at%, Cr 0.05~3 at% 및 La 0.05~3 at%를 포함하는 것을 특징으로 한다.The ZnO-based varistor composition, Zn 90 ~ 98 at%, Ca 0.2 ~ 9 at%, Co 0.2 ~ 5 at%, Cr 0.05 ~ 3 at% and La 0.05 ~ 3 at based on the total metal atoms contained in the composition It is characterized by including the%.

본 발명은 또한,The present invention also provides

ZnO에, Bi2O3, Sb2O3 및 Pr6O11을 포함하지 않으며 Ca, Co, Cr 및 La를 포함하는 성분을 혼합하고, 분쇄 및 하소하여 하소분말을 제조하는 단계; Preparing a calcined powder by mixing, pulverizing and calcining ZnO with components not including Bi 2 O 3 , Sb 2 O 3, and Pr 6 O 11, and including Ca, Co, Cr, and La;

상기 하소분말에 바인더를 넣고 성형한 후 소결하는 단계; 및Inserting a binder into the calcined powder, shaping and sintering; And

상기 소결하는 단계에서 제조된 소결체에 전극을 도포하고 패키지 처리를 하는 단계를 포함하는 것을 특징으로 하는 ZnO계 바리스터의 제조 방법을 제공한다.It provides a method for producing a ZnO-based varistor comprising the step of applying an electrode to the sintered body produced in the sintering step and package processing.

본 발명은 또한,The present invention also provides

상기의 바리스터 조성물로 제조된 ZnO계 바리스터를 포함하는 것을 특징으로 하는 전기소자를 제공한다.It provides an electrical device comprising a ZnO-based varistor made of the varistor composition described above.

본 발명의 바리스터 조성물은 항복전압, 누설전류, 비선형계수, 클램핑 전압비, 써어지 흡수능, 열화특성 등의 면에서 우수하며, 특히, Bi2O3를 포함하지 않기 때문에 우수한 EDS 특성을 제공한다. 또한, 환경규제 성분인 Sb2O3를 포함하지 않으므로 우수한 작업안전성을 제공하며, 고온소결이 요구되어 제조원가의 상승을 야기하는 Pr계 성분을 포함하지 않으므로 낮은 제조단가로 제조될 수 있다. The varistor composition of the present invention is excellent in terms of breakdown voltage, leakage current, nonlinear coefficient, clamping voltage ratio, surge absorption capacity, deterioration characteristics, and the like, and in particular, provides excellent EDS characteristics because it does not contain Bi 2 O 3 . In addition, it does not include the environmental regulation component Sb 2 O 3 provides excellent work safety, and does not include a Pr-based component that requires high temperature sintering to increase the manufacturing cost can be manufactured at a low manufacturing cost.

본 발명은, ZnO계 바리스터 조성물에 있어서, Bi2O3, Sb2O3 및 Pr6O11을 포함하지 않으며, Ca, Co, Cr 및 La를 포함하는 것을 특징으로 하는 ZnO계 바리스터 조성물에 관한 것이다.The present invention relates to a ZnO-based varistor composition, wherein the ZnO-based varistor composition does not include Bi 2 O 3 , Sb 2 O 3, and Pr 6 O 11 , but contains Ca, Co, Cr, and La. will be.

본 발명의 ZnO계 바리스터 조성물은, 조성물에 포함되는 총 금속원자를 기준으로 Zn 90~98 at%, Ca 0.2~9 at%, Co 0.2~5 at%, Cr 0.05~3 at% 및 La 0.05~3 at%를 포함하는 것이 바람직하며, 더욱 바람직하게는, 조성물에 포함되는 총 금속원자를 기준으로 Zn 92~98 at%, Ca 0.2~4 at%, Co 0.2~2.5 at%, Cr 0.05~1 at% 및 La 0.05~0.4 at%를 포함하는 것이 좋다. ZnO-based varistor composition of the present invention, Zn 90 ~ 98 at%, Ca 0.2 ~ 9 at%, Co 0.2 ~ 5 at%, Cr 0.05 ~ 3 at% and La 0.05 ~ based on the total metal atoms contained in the composition It is preferable to include 3 at%, more preferably, Zn 92 ~ 98 at%, Ca 0.2 ~ 4 at%, Co 0.2 ~ 2.5 at%, Cr 0.05 ~ 1 based on the total metal atoms included in the composition It is preferable to include at% and La 0.05 to 0.4 at%.

상기에서 Ca가 상기와 같은 함량 범위로 포함되는 경우에, 바리스터에 요구되는 물성이 우수한 조성물을 얻을 수 있으며, 특히 비선형성이 우수한 조성물이 얻어진다. 특히, Ca가 0.5~4.0 at%로 첨가되는 경우에 더욱 바람직한 특성이 얻어진다. When Ca is included in the above content range, a composition having excellent physical properties required for the varistor can be obtained, and in particular, a composition having excellent nonlinearity is obtained. In particular, more preferable properties are obtained when Ca is added at 0.5 to 4.0 at%.

상기에서 Co가 상기와 같은 함량 범위로 포함되는 경우에, 비선형성이 우수한 조성물이 얻어진다. 특히, Co가 0.2~2.5 at%로 첨가되는 경우에 더욱 바람직한 비선형성이 얻어진다.When Co is included in the above content range, a composition having excellent nonlinearity is obtained. In particular, more preferable nonlinearity is obtained when Co is added at 0.2 to 2.5 at%.

또한, 상기에서 Cr이 상기와 같은 함량 범위로 포함되는 경우에, 비저항 면에서 우수한 조성물이 얻어진다. 상기에서 Cr이 상한 값을 초과하는 경우에는 비선형성이 저하되는 문제가 발생된다. 더 나아가서, Cr이 0.05~1.0 at%로 첨가되는 경우에 더욱 바람직한 비저항이 얻어진다. In addition, in the case where Cr is included in the above content range, an excellent composition in terms of resistivity is obtained. In the above, when Cr exceeds the upper limit, a problem arises in that the nonlinearity is lowered. Furthermore, more preferable specific resistance is obtained when Cr is added at 0.05-1.0 at%.

또한, 상기에서 La가 상기와 같은 함량 범위로 포함되는 경우에, 비저항 면에서 우수한 조성물이 얻어진다. 상기에서 La가 상한 값을 초과하는 경우에는 비선형성이 저하되는 문제가 발생된다. 더 나아가서, La가 0.05~0.4 at%로 첨가되는 경우에 더욱 바람직한 비저항이 얻어진다. In addition, when La is included in the above content range, a composition excellent in resistivity is obtained. In the above, when La exceeds the upper limit, a problem arises in that the nonlinearity is lowered. Furthermore, more preferable specific resistance is obtained when La is added at 0.05 to 0.4 at%.

본 발명의 ZnO계 바리스터 조성물은 상기 Zn, Ca, Co, Cr 및 La 성분 외에 조성물에 포함되는 총 금속원자를 기준으로 다른 금속원자를 0.01~30 at%의 범위에서 더 포함할 수 있다. 상기 다른 금속원자로는 Mg, Mn, Al, Zr, Li, Na, K, Ga 등을 들 수 있다.ZnO-based varistor composition of the present invention may further include other metal atoms in the range of 0.01 ~ 30 at% based on the total metal atoms included in the composition in addition to the Zn, Ca, Co, Cr and La components. The other metal atoms include Mg, Mn, Al, Zr, Li, Na, K, Ga and the like.

본 발명의 ZnO계 바리스터 조성물에 Zn은 ZnO로 첨가되며; Ca는 CaCO3, CaO 등으로 이루어진 군으로부터 선택되는 1종 또는 2종 이상의 혼합 형태로 첨가될 수 있으며; Co는 Co3O4, CoO 등으로 이루어진 군으로부터 선택되는 1종 또는 2종 이상의 혼합 형태로 첨가될 수 있으며; Cr은 Cr2O3 등으로 이루어진 군으로부터 선택하여 첨가할 수 있으며; La는 La2O3 등으로 이루어진 군으로부터 선택하여 첨가할 수 있다.Zn is added as ZnO to the ZnO-based varistor composition of the present invention; Ca may be added in one or two or more mixed forms selected from the group consisting of CaCO 3 , CaO, and the like; Co may be added in one or two or more mixed forms selected from the group consisting of Co 3 O 4 , CoO, and the like; Cr can be selected and added from the group consisting of Cr 2 O 3 and the like; La can be selected and added from the group consisting of La 2 O 3 and the like.

본 발명은 또한,The present invention also provides

ZnO에, Bi2O3, Sb2O3 및 Pr6O11을 포함하지 않으며 Ca, Co, Cr 및 La를 포함하는 성분을 혼합하고, 분쇄 및 하소하여 하소분말을 제조하는 단계; Preparing a calcined powder by mixing, pulverizing and calcining ZnO with components not including Bi 2 O 3 , Sb 2 O 3, and Pr 6 O 11, and including Ca, Co, Cr, and La;

상기 하소분말에 바인더를 넣고 성형한 후 소결하는 단계; 및Inserting a binder into the calcined powder, shaping and sintering; And

상기 소결하는 단계에서 제조된 소결체에 전극을 도포하고 패키지 처리를 하는 단계를 포함하는 것을 특징으로 하는 ZnO계 바리스터의 제조 방법에 관한 것이다.It relates to a method of manufacturing a ZnO-based varistor comprising the step of applying an electrode to the sintered body produced in the sintering step and package processing.

상기 제조방법은 신규한 조성을 사용하는 것을 제외하고는 이 분야에 공지 된 방법을 채용하여 실시할 수 있다.The manufacturing method may be carried out by employing a method known in the art, except for using a novel composition.

본 발명은 또한, 상기의 바리스터 조성물로 제조된 ZnO계 바리스터를 포함하는 것을 특징으로 하는 전기소자를 제공한다. The present invention also provides an electrical device comprising a ZnO-based varistor made of the varistor composition described above.

이하에서, 실시예를 통하여 본 발명을 보다 상세히 설명한다. 그러나, 하기의 실시예는 본 발명을 더욱 구체적으로 설명하기 위한 것으로서, 본 발명의 범위가 하기의 실시예에 의하여 한정되는 것은 아니다. 하기의 실시예는 본 발명의 범위 내에서 당업자에 의해 적절히 수정, 변경될 수 있다. Hereinafter, the present invention will be described in more detail with reference to Examples. However, the following examples are intended to illustrate the present invention more specifically, but the scope of the present invention is not limited by the following examples. The following examples can be appropriately modified and changed by those skilled in the art within the scope of the present invention.

실시예1: 적층형 바리스터의 제조Example 1 Preparation of Stacked Varistors

주성분인 ZnO 분말 93.7843g(Zn 96.6 at%), CaCO3 4.7022g(Ca 2.0 at%), Co3O4 0.9487g(Co 1.0 at%), Cr2O3 0.1796g(Cr 0.2 at%) 및 La2O3 0.3851g(La 0.2 at%)을 칭량하여, 상기 칭량물을 상기 칭량물 중량의 3배의 이온교환수와 함께 부분 안정화 지르코니아(PSZ)가 포함된 볼 밀에 투입하여 혼합하고, 분쇄하였다. 그런 다음, 탈수?건조처리를 행하여 조립분을 제조하고, 얻어진 조립분을 대기 중에서 700℃의 온도에서 2시간 동안 하소처리하고 충분히 분쇄하여 하소분말을 제조하였다. ZnO powder 93.7843g (Zn 96.6 at%), CaCO 3 4.7022g (Ca 2.0 at%), Co 3 O 4 0.9487g (Co 1.0 at%), Cr 2 O 3 0.1796g (Cr 0.2 at%) 0.3851 g La 2 O 3 (La 0.2 at%) was weighed, and the weighed material was added to a ball mill containing partially stabilized zirconia (PSZ) with ion-exchanged water three times the weight of the weighed material, and mixed, Pulverized. Thereafter, dehydration and drying were performed to prepare granulated powder. The granulated powder thus obtained was calcined at a temperature of 700 ° C. for 2 hours in the air, and then sufficiently ground to prepare calcined powder.

이어서, 가소분말에 유기바인더로서 BM2(SEKISUI 사제) 및 BM-SZ(SEKISUI 사제), 유기가소제로서 디옥틸 프탈레이트(DOP), 유기용제로서 톨루엔 및 에탄올을 소정량 첨가하고, 습식 분쇄해 세라믹 시트 형성용 슬러리를 제조하였다.Subsequently, BM2 (manufactured by SEKISUI) and BM-SZ (manufactured by SEKISUI) and dioctyl phthalate (DOP) as an organic plasticizer, and toluene and ethanol as an organic solvent were added to the calcined powder, followed by wet grinding to form a ceramic sheet. A slurry was prepared.

다음으로, 닥터 블레이드법을 사용해, 이 슬러리를 PET필름(폴리에틸렌 텔레프탈레이트) 상에 두께 약 25μm의 시트 모양으로 형성한 후, 소정 치수로 절단해 다수의 세라믹 시트를 형성하였다.Next, using the doctor blade method, the slurry was formed on a PET film (polyethylene telephthalate) into a sheet shape having a thickness of about 25 μm, and then cut into predetermined dimensions to form a plurality of ceramic sheets.

다음으로, Pd 페이스트를 상기 세라믹 시트의 표면에 스크린 인쇄하고, 각 세라믹 시트의 1단면으로부터 연신하고, 타단은 세라믹 시트 상에 위치하도록 장방형으로 전극 패턴을 형성하였다. 그리고, 이와 같이 전극 패턴이 형성된 세라믹 시트를 적층하고, 이들 적층된 세라믹 시트를 전극 패턴이 형성되지 않은 세라믹 시트(보호층)에 끼워 넣어 압착해서 적층체를 형성하였다.Next, the Pd paste was screen printed on the surface of the ceramic sheet, stretched from one end surface of each ceramic sheet, and an electrode pattern was formed in a rectangle so that the other end was located on the ceramic sheet. And the ceramic sheet in which the electrode pattern was formed was laminated | stacked in this way, these laminated ceramic sheets were sandwiched and crimped | bonded by the ceramic sheet (protective layer) in which the electrode pattern was not formed, and the laminated body was formed.

상기 얻어진 적층체를 세로 1.6mm, 가로 0.8mm로 절단해서 Zr Saggar에 수용하고, 공기 중에서 400℃의 온도에서 탈바인더 처리를 행한 후, 공기 중에서 1200℃의 온도에서 3시간 소성해 세라믹 소결체를 제작하였다. 그런 다음, Ag 페이스트를 준비하고, Ag페이스트를 세라믹 소결체의 양단에 도포한 다음, 800℃의 온도에서 소부처리 하고 외부 전극을 형성하여 적층형 바리스터를 제작하였다.The obtained laminate was cut into 1.6 mm long and 0.8 mm wide, accommodated in Zr Saggar, subjected to binder removal at 400 ° C. in air, and then calcined at 1200 ° C. in air for 3 hours to produce a ceramic sintered body. It was. Then, Ag paste was prepared, Ag paste was applied to both ends of the ceramic sintered body, and then baked at a temperature of 800 ° C. to form an external electrode to prepare a laminated varistor.

상기의 방법으로 제작된 바리스터 소자의 바리스터 전압(V1mA) 및 비직선지수(α), 전기적 유전손실계수(tanδ) 등을 측정하고, 이를 도1에 나타내었다. 상기에서 제조된 세라믹 시트의 SEM 이미지를 도2에 나타내었다. Varistor voltage (V1mA), nonlinearity index (α), electrical dielectric loss coefficient (tanδ), and the like of the varistor device manufactured by the above method were measured and shown in FIG. 1. An SEM image of the ceramic sheet prepared above is shown in FIG. 2.

도1에서 확인되는 바와 같이, 본 발명의 바리스터 조성물은 비선형성이 우수하며, 바리스터 전압이 높을 뿐만 아니라 유전 손실계수도 적정 값을 나타내어 우수한 특성을 나타내었다. 특히, Ca가 2.0 at%로 포함되는 경우에, 비선형 계수가 100으로 매우 높은 값을 나타내었다As shown in Figure 1, the varistor composition of the present invention is excellent in non-linearity, not only the varistor voltage is high but also the dielectric loss coefficient exhibited an appropriate value exhibited excellent characteristics. In particular, when Ca is included at 2.0 at%, the nonlinear coefficient is very high as 100.

실시예2 내지 4: 적층형 바리스터의 제조Examples 2 to 4: Preparation of Laminated Varistors

파우더 조성을 하기 표1과 같이 변경한 것을 제외하고는 상기 실시예1과 동일한 방법으로 적층형 바리스터를 제작하였다.A laminated varistor was manufactured in the same manner as in Example 1, except that the powder composition was changed as in Table 1 below.

조성Furtherance POWDERPOWDER ZnOZnO CaCO3 CaCO 3 Co3O4 Co 3 O 4 Cr2O3 Cr 2 O 3 La2O3 La 2 O 3 At%At% Zn
98.6-x at%Zn
98.6-x at% Ca x:0.5~3.0 at%Ca x: 0.5-3.0 at% Co 1.0 at%Co 1.0 at% Cr 0.2 at%Cr 0.2 at% La 0.2 at%La 0.2 at% 실시예2Example 2 Ca 0.5 at%Ca 0.5 at% 97.2538g 97.2538 g 1.2006g 1.2006g 0.9689g 0.9689 g 0.1835g 0.1835 g 0.3933g 0.3933 g 실시예3Example 3 Ca 1.0 at%Ca 1.0 at% 96.0810g 96.0810 g 2.3842g2.3842g 0.9621g 0.9621 g 0.1822g 0.1822 g 0.3905g 0.3905 g 실시예4Example 4 Ca 3.0 at%Ca 3.0 at% 91.5506g91.5506 g 6.9567g 6.9567 g 0.9357g 0.9357 g 0.1772g 0.1772 g 0.3798g0.3798 g

상기의 방법으로 제작된 바리스터 소자의 바리스터 전압(V1mA) 및 비직선지수(α), 전기적 유전손실계수(tanδ) 등을 측정하고, 이를 도1에 나타내었다. 상기에서 제조된 세라믹 시트의 SEM 이미지를 도2에 나타내었다. Varistor voltage (V1mA), nonlinearity index (α), electrical dielectric loss coefficient (tanδ), and the like of the varistor device manufactured by the above method were measured and shown in FIG. 1. An SEM image of the ceramic sheet prepared above is shown in FIG. 2.

실시예5 내지 9: 적층형 바리스터의 제조Examples 5 to 9: Preparation of Stacked Varistors

파우더 조성을 하기 표2와 같이 변경한 것을 제외하고는 상기 실시예1과 동일한 방법으로 적층형 바리스터를 제작하였다.A laminated varistor was manufactured in the same manner as in Example 1, except that the powder composition was changed as in Table 2 below.


성분
ingredient
POWDERPOWDER ZnZn CaCa CoCo CrCr LaLa 97.6-x at%97.6-x at% 2.0 at%2.0 at% x:0.5~5.0 at%x: 0.5 ~ 5.0 at% 0.2 at%0.2 at% 0.2 at%0.2 at% 실시예5Example 5 97.1 at%97.1 at% 2.0 at%2.0 at% 0.5 at%0.5 at% 0.2 at%0.2 at% 0.2 at%0.2 at% 실시예6Example 6 95.6 at%95.6 at% 2.0 at%2.0 at% 2.0 at%2.0 at% 0.2 at%0.2 at% 0.2 at%0.2 at% 실시예7Example 7 94.6 at%94.6 at% 2.0 at%2.0 at% 3.0 at%3.0 at% 0.2 at%0.2 at% 0.2 at%0.2 at% 실시예8Example 8 93.6 at%93.6 at% 2.0 at%2.0 at% 4.0 at%4.0 at% 0.2 at%0.2 at% 0.2 at%0.2 at% 실시예9Example 9 92.6 at%92.6 at% 2.0 at%2.0 at% 5.0 at%5.0 at% 0.2 at%0.2 at% 0.2 at%0.2 at%

상기의 방법으로 제작된 바리스터 소자의 바리스터 전압(V1mA) 및 비직선지수(α), 누설전류, 밀도 등을 측정하고, 이를 하기 표3에 나타내었다. Varistor voltage (V1mA), nonlinear index (α), leakage current, density, etc. of the varistor device manufactured by the above method were measured, and the results are shown in Table 3 below.

성분ingredient 밀도
(g/cm3)density
(g / cm 3) Vn
(V/cm)Vn
(V / cm) αα IL
(μA/cm2)I L
(μA / cm 2 ) 실시예5Example 5 Co 0.5 at%Co 0.5 at% 94.394.3 40284028 6868 0.250.25 실시예1Example 1 Co 1.0 at%Co 1.0 at% 94.394.3 42814281 7878 0.180.18 실시예6Example 6 Co 2.0 at%Co 2.0 at% 93.993.9 45754575 6666 0.230.23 실시예6Example 6 Co 3.0 at%Co 3.0 at% 93.193.1 43864386 2828 0.300.30 실시예7Example 7 Co 4.0 at%Co 4.0 at% 93.593.5 43734373 3535 0.250.25 실시예8Example 8 Co 5.0 at%Co 5.0 at% 93.993.9 48524852 5454 0.360.36

상기 표3에서 확인되는 바와 같이, 본 발명의 바리스터 조성물은 비선형성이 우수하며, 바리스터 전압이 높을 뿐만 아니라 누설전류도 낮은 값을 나타내며, 밀도도 높아서 우수한 특성을 보였다. As shown in Table 3, the varistor composition of the present invention is excellent in nonlinearity, not only has a high varistor voltage but also a low leakage current, and has a high density, thereby showing excellent characteristics.

실시예10 내지 14: 적층형 바리스터의 제조Examples 10 to 14 Preparation of Stacked Varistors

파우더 조성을 하기 표4와 같이 변경한 것을 제외하고는 상기 실시예1과 동일한 방법으로 적층형 바리스터를 제작하였다.A laminated varistor was manufactured in the same manner as in Example 1, except that the powder composition was changed as in Table 4 below.


성분
ingredient
POWDERPOWDER ZnZn CaCa CoCo CrCr LaLa 96.8-x at%96.8-x at% 2.0 at%2.0 at% 1.0 at%1.0 at% x:0.1~3.0 at%x: 0.1-3.0 at% 0.2 at%0.2 at% 실시예10Example 10 96.7 at%96.7 at% 2.0 at%2.0 at% 1.0 at%1.0 at% 0.1 at%0.1 at% 0.2 at%0.2 at% 실시예11Example 11 96.3 at%96.3 at% 2.0 at%2.0 at% 1.0 at%1.0 at% 0.5 at%0.5 at% 0.2 at%0.2 at% 실시예12Example 12 95.8 at%95.8 at% 2.0 at%2.0 at% 1.0 at%1.0 at% 1.0 at%1.0 at% 0.2 at%0.2 at% 실시예13Example 13 94.8 at%94.8 at% 2.0 at%2.0 at% 1.0 at%1.0 at% 2.0 at%2.0 at% 0.2 at%0.2 at% 실시예14Example 14 93.8 at%93.8 at% 2.0 at%2.0 at% 1.0 at%1.0 at% 3.0 at%3.0 at% 0.2 at%0.2 at%

상기의 방법으로 제작된 바리스터 소자의 바리스터 전압(V1mA) 및 비직선지수(α), 전기적 유전손실계수(tanδ), 비저항 등을 측정하고, 이를 도3에 나타내었다. 도3에서 확인되는 바와 같이, 본 발명의 바리스터 조성물은 비선형성이 우수하며, 유전 손실계수 및 비저항 값도 적정 값을 나타내어 우수한 특성을 나타내었다. Varistor voltage (V1mA), nonlinear index (α), electrical dielectric loss coefficient (tanδ), resistivity, and the like of the varistor device manufactured by the above method were measured, and the results are shown in FIG. As can be seen in Figure 3, the varistor composition of the present invention is excellent in nonlinearity, the dielectric loss coefficient and the specific resistance value also exhibited the appropriate value exhibited excellent characteristics.

실시예15 내지 19: 적층형 바리스터의 제조Examples 15-19 Preparation of Stacked Varistors

파우더 조성을 하기 표5와 같이 변경한 것을 제외하고는 상기 실시예1과 동일한 방법으로 적층형 바리스터를 제작하였다.A laminated varistor was manufactured in the same manner as in Example 1, except that the powder composition was changed as in Table 5 below.


성분
ingredient
POWDERPOWDER ZnZn CaCa CoCo CrCr LaLa 96.8-x at%96.8-x at% 2.0 at%2.0 at% 1.0 at%1.0 at% 0.2 at%0.2 at% x:0.1~3.0 at%x: 0.1-3.0 at% 실시예15Example 15 96.7 at%96.7 at% 2.0 at%2.0 at% 1.0 at%1.0 at% 0.2 at%0.2 at% 0.1 at%0.1 at% 실시예16Example 16 96.3 at%96.3 at% 2.0 at%2.0 at% 1.0 at%1.0 at% 0.2 at%0.2 at% 0.5 at%0.5 at% 실시예17Example 17 95.8 at%95.8 at% 2.0 at%2.0 at% 1.0 at%1.0 at% 0.2 at%0.2 at% 1.0 at%1.0 at% 실시예18Example 18 94.8 at%94.8 at% 2.0 at%2.0 at% 1.0 at%1.0 at% 0.2 at%0.2 at% 2.0 at%2.0 at% 실시예19Example 19 93.8 at%93.8 at% 2.0 at%2.0 at% 1.0 at%1.0 at% 0.2 at%0.2 at% 3.0 at%3.0 at%

상기의 방법으로 제작된 바리스터 소자의 바리스터 전압(V1mA) 및 비직선지수(α), 전기적 유전손실계수(tanδ), 비저항 등을 측정하고, 이를 도4에 나타내었다. 도4에서 확인되는 바와 같이, 본 발명의 바리스터 조성물은 비선형성, 유전 손실계수 값 및 비저항 등에 있어서 바람직한 값을 나타내었다.The varistor voltage (V1mA), the nonlinear index (α), the electrical dielectric loss coefficient (tanδ), the resistivity, and the like of the varistor device manufactured by the above method were measured and shown in FIG. 4. As shown in FIG. 4, the varistor composition of the present invention exhibited preferable values in nonlinearity, dielectric loss coefficient value, and resistivity.

실시예20 내지 24: 적층형 바리스터의 제조Examples 20-24 Preparation of Stacked Varistors

파우더 조성을 하기 표6과 같이 변경한 것을 제외하고는 상기 실시예1과 동일한 방법으로 적층형 바리스터를 제작하였다.A laminated varistor was manufactured in the same manner as in Example 1, except that the powder composition was changed as in Table 6 below.


성분
ingredient
POWDERPOWDER ZnZn CaCa CoCo CrCr LaLa AlAl 96.6-x at%96.6-x at% 2.0 at%2.0 at% 1.0 at%1.0 at% 0.2 at%0.2 at% 0.2 at%0.2 at% x:0.01~0.20 at%x: 0.01-0.20 at% 실시예20Example 20 96.59 at%96.59 at% 2.0 at%2.0 at% 1.0 at%1.0 at% 0.2 at%0.2 at% 0.2 at%0.2 at% 0.01 at%0.01 at% 실시예21Example 21 96.58 at%96.58 at% 2.0 at%2.0 at% 1.0 at%1.0 at% 0.2 at%0.2 at% 0.2 at%0.2 at% 0.02 at%0.02 at% 실시예22Example 22 96.55 at%96.55 at% 2.0 at%2.0 at% 1.0 at%1.0 at% 0.2 at%0.2 at% 0.2 at%0.2 at% 0.05 at%0.05 at% 실시예23Example 23 96.50 at%96.50 at% 2.0 at%2.0 at% 1.0 at%1.0 at% 0.2 at%0.2 at% 0.2 at%0.2 at% 0.10 at%0.10 at% 실시예24Example 24 96.40 at%96.40 at% 2.0 at%2.0 at% 1.0 at%1.0 at% 0.2 at%0.2 at% 0.2 at%0.2 at% 0.20 at%0.20 at%

상기의 방법으로 제작된 바리스터 소자의 바리스터 전압(V1mA) 및 비직선지수(α), 전기적 유전손실계수(tanδ), 비저항 등을 측정하고, 이를 도5에 나타내었다. 도5에서 확인되는 바와 같이, 본 발명의 바리스터 조성물은 Al이 소량으로 함유되었을 때도 비선형성, 누설전류 및 비저항 등에 있어서 바람직한 값을 나타내었다.The varistor voltage (V1mA), the nonlinear index (α), the electrical dielectric loss coefficient (tanδ), the resistivity, and the like of the varistor device manufactured by the above method were measured, and the results are shown in FIG. 5. As can be seen from FIG. 5, the varistor composition of the present invention exhibited preferable values in nonlinearity, leakage current and specific resistance even when Al was contained in a small amount.

실시예25 내지 29: 적층형 바리스터의 제조Examples 25-29 Preparation of Stacked Varistors

파우더 조성을 하기 표7과 같이 변경한 것을 제외하고는 상기 실시예1과 동일한 방법으로 적층형 바리스터를 제작하였다.A laminated varistor was manufactured in the same manner as in Example 1, except that the powder composition was changed as in Table 7 below.


성분
ingredient
POWDERPOWDER ZnZn CaCa CoCo CrCr LaLa ZrZr 96.6-x at%96.6-x at% 2.0 at%2.0 at% 1.0 at%1.0 at% 0.2 at%0.2 at% 0.2 at%0.2 at% x:0.1~3.0 at%x: 0.1-3.0 at% 실시예25Example 25 96.5 at%96.5 at% 2.0 at%2.0 at% 1.0 at%1.0 at% 0.2 at%0.2 at% 0.2 at%0.2 at% 0.1 at%0.1 at% 실시예26Example 26 96.1 at%96.1 at% 2.0 at%2.0 at% 1.0 at%1.0 at% 0.2 at%0.2 at% 0.2 at%0.2 at% 0.5 at%0.5 at% 실시예27Example 27 95.6 at%95.6 at% 2.0 at%2.0 at% 1.0 at%1.0 at% 0.2 at%0.2 at% 0.2 at%0.2 at% 1.0 at%1.0 at% 실시예28Example 28 94.6 at%94.6 at% 2.0 at%2.0 at% 1.0 at%1.0 at% 0.2 at%0.2 at% 0.2 at%0.2 at% 2.0 at%2.0 at% 실시예29Example 29 93.6 at%93.6 at% 2.0 at%2.0 at% 1.0 at%1.0 at% 0.2 at%0.2 at% 0.2 at%0.2 at% 3.0 at%3.0 at%

상기의 방법으로 제작된 바리스터 소자의 바리스터 전압(V1mA) 및 비직선지수(α), 전기적 유전손실계수(tanδ), 비저항 등을 측정하고, 이를 도6에 나타내었다. 도6에서 확인되는 바와 같이, 본 발명의 바리스터 조성물은 Zr이 소량으로 함유되었을 때도 비선형성, 누설전류 및 비저항 등에 있어서 바람직한 값을 나타내었다.Varistor voltage (V1mA), nonlinear index (α), electrical dielectric loss coefficient (tanδ), resistivity, and the like of the varistor device manufactured by the above method were measured, and the results are shown in FIG. As can be seen from FIG. 6, the varistor composition of the present invention exhibited preferable values in nonlinearity, leakage current and specific resistance even when Zr was contained in a small amount.

실시예30 내지 34: 적층형 바리스터의 제조Examples 30-34 Preparation of Stacked Varistors

소결온도와 소결시간을 하기 표8과 같이 변경한 것을 제외하고는 실시예1과 동일한 방법으로 적층형 바리스터를 제작하였다.A laminated varistor was manufactured in the same manner as in Example 1, except that the sintering temperature and the sintering time were changed as shown in Table 8 below.

소결온도(℃)Sintering Temperature (℃) 소결시간(h)Sintering time (h) 밀도
(g/cm3)density
(g / cm 3) Vn
(V/cm)Vn
(V / cm) αα IL
(μA/cm2)I L
(μA / cm 2 ) 실시예30Example 30 11001100 33 89.889.8 -- -- -- 실시예1Example 1 12001200 33 94.394.3 42814281 7878 0.180.18 실시예31Example 31 13001300 33 97.397.3 10091009 4141 77 실시예32Example 32 13501350 33 96.796.7 745745 1818 3636 실시예33Example 33 12001200 1One 92.892.8 48364836 5151 0.310.31 실시예34Example 34 12001200 55 96.696.6 28222822 4646 0.280.28

상기 표8에서 확인되는 바와 같이, 본 발명의 바리스터 조성물은 1200℃에서 3시간 동안 소결하는 경우에 밀도, 전압, 비선형성 및 누설전류의 면에서 가장 바람직한 특성을 나타냈다.As confirmed in Table 8, the varistor composition of the present invention exhibited the most desirable properties in terms of density, voltage, nonlinearity and leakage current when sintered at 1200 ° C. for 3 hours.

도1은 본 발명의 실시예1 내지 4에서 제조된 ZnO계 바리스터의 특성을 평가한 그래프를 도시한 것이다.Figure 1 shows a graph evaluating the characteristics of the ZnO-based varistors prepared in Examples 1 to 4 of the present invention.

도2는 실시예1 및 2에서 제조된 ZnO계 바리스터의 SEM 이미지이다.FIG. 2 is an SEM image of ZnO-based varistors prepared in Examples 1 and 2. FIG.

도3은 본 발명의 실시예10 내지 14에서 제조된 ZnO계 바리스터의 특성을 평가한 그래프를 도시한 것이다.Figure 3 shows a graph evaluating the characteristics of the ZnO-based varistors prepared in Examples 10 to 14 of the present invention.

도4는 본 발명의 실시예15 내지 19에서 제조된 ZnO계 바리스터의 특성을 평가한 그래프를 도시한 것이다.Figure 4 shows a graph evaluating the characteristics of the ZnO-based varistors prepared in Examples 15 to 19 of the present invention.

도5는 본 발명의 실시예20 내지 24에서 제조된 ZnO계 바리스터의 특성을 평가한 그래프를 도시한 것이다.Figure 5 shows a graph evaluating the characteristics of the ZnO-based varistors prepared in Examples 20 to 24 of the present invention.

도6은 본 발명의 실시예25 내지 29에서 제조된 ZnO계 바리스터의 특성을 평가한 그래프를 도시한 것이다.Figure 6 shows a graph evaluating the characteristics of the ZnO-based varistors prepared in Examples 25 to 29 of the present invention.

Claims (6)

ZnO계 바리스터 조성물에 있어서, Bi2O3, Sb2O3 및 Pr6O11을 포함하지 않으며, Ca, Co, Cr 및 La를 포함하는 것을 특징으로 하는 ZnO계 바리스터 조성물. A ZnO-based varistor composition, which does not contain Bi 2 O 3 , Sb 2 O 3, and Pr 6 O 11, and contains Ca, Co, Cr, and La. 청구항1에 있어서, 조성물에 포함되는 총 금속원자를 기준으로 Zn 90~98 at%, Ca 0.2~9 at%, Co 0.2~5 at%, Cr 0.05~3 at% 및 La 0.05~3 at%를 포함하는 것을 특징으로 하는 ZnO계 바리스터 조성물. According to claim 1, Zn 90 ~ 98 at%, Ca 0.2 ~ 9 at%, Co 0.2 ~ 5 at%, Cr 0.05 ~ 3 at% and La 0.05 ~ 3 at% based on the total metal atoms contained in the composition ZnO-based varistor composition comprising a. 청구항2에 있어서, 상기 Zn, Ca, Co, Cr 및 La 성분 외에 조성물의 전체 원자량을 기준으로 다른 금속원자가 0.01~30 at%로 더 첨가되는 것을 특징으로 하는 ZnO계 바리스터 조성물.The ZnO-based varistor composition according to claim 2, wherein in addition to the Zn, Ca, Co, Cr, and La components, other metal atoms are added at 0.01 to 30 at% based on the total atomic weight of the composition. 청구항2에 있어서, 상기 조성물의 제조를 위하여 Zn은 ZnO로 첨가되고; Ca는 CaCO3 및 CaO 중에서 선택되는 1종 또는 2종 이상의 혼합 형태로 첨가되며; Co는 Co3O4 및 CoO 중에서 선택되는 1종 또는 2종 이상의 혼합 형태로 첨가되며; Cr은 Cr2O3로 첨가되며; La는 La2O3로 첨가되는 것을 특징으로 하는 ZnO계 바리스터 조성물.The method of claim 2, wherein Zn is added as ZnO for preparing the composition; Ca is added in the form of 1 type, or 2 or more types selected from CaCO 3 and CaO; Co is added in the form of 1 type, or 2 or more types selected from Co 3 O 4 and CoO; Cr is added as Cr 2 O 3 ; La is ZnO-based varistor composition, characterized in that the addition of La 2 O 3 . ZnO에, Bi2O3, Sb2O3 및 Pr6O11을 포함하지 않으며 Ca, Co, Cr 및 La를 포함하는 성분을 혼합하고, 분쇄 및 하소하여 하소분말을 제조하는 단계; Preparing a calcined powder by mixing, pulverizing and calcining ZnO with components not including Bi 2 O 3 , Sb 2 O 3, and Pr 6 O 11, and including Ca, Co, Cr, and La; 상기 하소분말에 바인더를 넣고 성형한 후 소결하는 단계; 및Inserting a binder into the calcined powder, shaping and sintering; And 상기 소결하는 단계에서 제조된 소결체에 전극을 도포하고 패키지 처리를 하는 단계를 포함하는 것을 특징으로 하는 ZnO계 바리스터의 제조 방법.The method of manufacturing a ZnO-based varistor comprising the step of applying an electrode to the sintered body produced in the step of sintering and package processing. 청구항 1의 바리스터 조성물로 제조된 ZnO계 바리스터를 포함하는 것을 특징으로 하는 전기소자. An electrical device comprising a ZnO-based varistor made of the varistor composition of claim 1.
KR1020090079746A 2009-08-27 2009-08-27 ZnO-based varistor composition KR101161924B1 (en)

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TWI425532B (en) * 2011-11-29 2014-02-01 Leader Well Technology Co Ltd Process for producing zno varistor with higher potential gradient and non-coefficient value

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