JPH04299804A - Manufacture of varistor - Google Patents
Manufacture of varistorInfo
- Publication number
- JPH04299804A JPH04299804A JP3064402A JP6440291A JPH04299804A JP H04299804 A JPH04299804 A JP H04299804A JP 3064402 A JP3064402 A JP 3064402A JP 6440291 A JP6440291 A JP 6440291A JP H04299804 A JPH04299804 A JP H04299804A
- Authority
- JP
- Japan
- Prior art keywords
- varistor
- manufacturing
- firing
- oxygen
- abo3
- 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.)
- Withdrawn
Links
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 17
- 239000012298 atmosphere Substances 0.000 claims abstract description 20
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000001301 oxygen Substances 0.000 claims abstract description 19
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 19
- 239000011230 binding agent Substances 0.000 claims abstract description 11
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 7
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 7
- 239000002994 raw material Substances 0.000 claims abstract description 4
- 238000010304 firing Methods 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 17
- 239000000203 mixture Substances 0.000 claims description 4
- 238000000465 moulding Methods 0.000 claims description 3
- 239000000463 material Substances 0.000 abstract description 4
- 239000006185 dispersion Substances 0.000 abstract 1
- 230000000452 restraining effect Effects 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 6
- 239000004065 semiconductor Substances 0.000 description 6
- 238000010405 reoxidation reaction Methods 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 229910052573 porcelain Inorganic materials 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 229910052691 Erbium Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 229910052777 Praseodymium Inorganic materials 0.000 description 1
- 229910052772 Samarium Inorganic materials 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 229910002370 SrTiO3 Inorganic materials 0.000 description 1
- 229910052775 Thulium Inorganic materials 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 239000000306 component Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
Landscapes
- Apparatuses And Processes For Manufacturing Resistors (AREA)
- Thermistors And Varistors (AREA)
Abstract
Description
【０００１】0001
【産業上の利用分野】本発明は、バリスタの製造方法に
関し、更に詳細には、ＡＢＯ３（Ａ：Ｓｒ，Ｂａ，Ｃａ
，Ｍｇ，Ｂ：Ｔｉ，Ｚｒ）を主成分とするバリスタの製
造方法に関するものである。[Industrial Field of Application] The present invention relates to a method for manufacturing a varistor, and more particularly to a method for manufacturing a varistor.
, Mg, B:Ti, Zr) as main components.
【０００２】0002
【従来の技術】従来、上記ＡＢＯ３（Ａ：Ｓｒ，Ｂａ，
Ｃａ，Ｍｇ，Ｂ：Ｔｉ，Ｚｒ）を主成分とするバリスタ
は、ＳｒＴｉＯ３系バリスタと同様還元再酸化型のもの
であり、従ってその製造は、主成分、添加剤、バインダ
を含む成形体を脱バインダ焼成した後、水素含有雰囲気
あるいは窒素雰囲気中にて還元焼成を行い、半導体化し
た焼結体を得、次いで大気雰囲気を含む酸素含有雰囲気
中で再酸化焼成を行いバリスタ特性を有する還元再酸化
型半導体磁器素子を得ることによって行われていた。[Prior Art] Conventionally, the above ABO3 (A: Sr, Ba,
Varistors whose main components are Ca, Mg, B:Ti, Zr) are of the reduction and reoxidation type, similar to SrTiO3-based varistors, and therefore, their production involves removing the molded body containing the main components, additives, and binders. After firing the binder, reduction firing is performed in a hydrogen-containing atmosphere or nitrogen atmosphere to obtain a semiconductor sintered body, and then reoxidation firing is performed in an oxygen-containing atmosphere including the air atmosphere to obtain a reduced and reoxidized product with varistor properties. This was done by obtaining type semiconductor ceramic elements.
【０００３】0003
【発明が解決しようとする課題】以上のようなバリスタ
の製造方法においては、脱バインダ焼成、還元焼成、再
酸化焼成の３回の焼成を行わなければならず、また再酸
化焼成における温度の変化、炉内温度のバラツキにより
、そのバリスタ電圧が変化し、一定品質のものが得にく
く、量産時における安定化が困難であるという問題があ
った。[Problems to be Solved by the Invention] In the method for manufacturing varistors as described above, firing must be performed three times: binder removal firing, reduction firing, and reoxidation firing, and temperature changes during reoxidation firing There was a problem in that the varistor voltage changed due to variations in the temperature inside the furnace, making it difficult to obtain a product of constant quality and making it difficult to stabilize it during mass production.
【０００４】そこで本発明は、簡略化された工程でバリ
スタを得ることのできるバリスタの製造方法を提供する
ことを目的とするものである。SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a method for manufacturing a varistor, which allows a varistor to be obtained through a simplified process.
【０００５】[0005]
【課題を解決するための手段】本発明は、ＡＢＯ３（Ａ
：Ｓｒ，Ｂａ，Ｃａ，Ｍｇ，Ｂ：Ｔｉ，Ｚｒ）を主成分
とするバリスタの製造方法において、前記ＡＢＯ３を主
成分とする原材料に原子価制御剤を添加し、これにバイ
ンダを加えて成形して形成した成形体を脱バインダ焼成
し、この後、酸素含有雰囲気中にて焼成して焼結体を得
ることを特徴とするものである。[Means for Solving the Problems] The present invention provides ABO3 (A
: Sr, Ba, Ca, Mg, B: Ti, Zr), a valence control agent is added to the raw material mainly composed of ABO3, a binder is added thereto, and molding is performed. The method is characterized in that the formed body is removed from the binder and fired, and then fired in an oxygen-containing atmosphere to obtain a sintered body.
【０００６】上記酸素含有雰囲気は、大気雰囲気を含む
ものとする。[0006] The above-mentioned oxygen-containing atmosphere includes atmospheric atmosphere.
【０００７】また、上記原子価制御剤としては、Ｙ，Ｌ
ａ，Ｃｅ，Ｐｒ，Ｎｄ，Ｓｍ，Ｅｒ，Ｔｍ，Ｎｂ，Ｔａ
，Ｗ等の元素の酸化物のうちの一種又は二種以上を用い
ることができる。[0007] Further, as the above-mentioned valence control agent, Y, L
a, Ce, Pr, Nd, Sm, Er, Tm, Nb, Ta
, W, and the like can be used.
【０００８】[0008]
【作用】ＡＢＯ３（Ａ：Ｓｒ，Ｂａ，Ｃａ，Ｍｇ，Ｂ：
Ｔｉ，Ｚｒ）である主成分に、原子価制御剤を添加した
組成物を酸素含有雰囲気中で焼成すると、得られた焼成
体は、グレイン内部が半導体化し、素地の表面および粒
界が絶縁化され、バリスタ特性を有するものとなる。[Action] ABO3 (A: Sr, Ba, Ca, Mg, B:
When a composition in which a valence control agent is added to the main components (Ti, Zr) is fired in an oxygen-containing atmosphere, the interior of the grains becomes semiconducting, and the surface and grain boundaries of the base material become insulating. and has varistor characteristics.
【０００９】これは、上記組成から成る成形体にあって
は、高温での焼成中、原子価制御剤の存在により、酸化
雰囲気中においても酸素欠陥が多く形成され、素地が半
導体化される。この半導体化された素地は、その後の降
温過程において、雰囲気中の酸素を吸収し、素地表面お
よび粒界が酸化され、その結果、バリスタ特性を有する
ようになる。[0009] In the molded body having the above composition, many oxygen defects are formed even in an oxidizing atmosphere due to the presence of the valence control agent during firing at a high temperature, and the base material becomes a semiconductor. During the subsequent cooling process, this semiconductor substrate absorbs oxygen in the atmosphere, the surface of the substrate and grain boundaries are oxidized, and as a result, it has varistor characteristics.
【００１０】本発明方法による場合、バリスタのバリス
タ電圧は、雰囲気中の酸素分圧および焼成時における降
温速度によりコントロールすることができる。According to the method of the present invention, the varistor voltage of the varistor can be controlled by the oxygen partial pressure in the atmosphere and the rate of temperature reduction during firing.
【００１１】[0011]
【実施例】以下、本発明の好ましい実施例によるバリス
タの製造方法について、比較例とともに説明する。[Example] A method for manufacturing a varistor according to a preferred embodiment of the present invention will be explained below along with a comparative example.
【００１２】先ず、実施例の試料の作製にあたって、Ｓ
ｒＴｉＯ３：９９．４ｍｏｌ％、ＮｂＯ５：０．２ｍｏ
ｌ％、ＳｉＯ２：０．１ｍｏｌ％、Ａｌ２Ｏ３：０．１
ｍｏｌ％となるように秤量、混合し、有機バインダとし
てポリビニルアルコールを５重量％加え、整粒を行い、
顆粒状粉末を得た。これを、１．５ｔｏｎ／ｃｍ２の成
型圧力で、直径１０ｍｍ、肉厚０．４５ｍｍの円板を成
形した。
これを、大気中、１１００℃で１時間脱バインダ焼成し
た後、表１に示す窒素に対する酸素の濃度（酸素のみの
場合を含む）の酸素含有雰囲気および焼成温度パターン
で１４５０℃で焼成して、本実施例試料１〜１０を得た
。First, in preparing the sample of the example, S
rTiO3: 99.4 mol%, NbO5: 0.2 mo
l%, SiO2: 0.1 mol%, Al2O3: 0.1
Weighed and mixed so that it was mol%, added 5% by weight of polyvinyl alcohol as an organic binder, sized the particles,
A granular powder was obtained. This was molded into a disk having a diameter of 10 mm and a wall thickness of 0.45 mm at a molding pressure of 1.5 ton/cm2. This was baked at 1100°C in the air to remove the binder for 1 hour, and then baked at 1450°C in an oxygen-containing atmosphere and firing temperature pattern with the concentration of oxygen to nitrogen (including the case of only oxygen) shown in Table 1. Samples 1 to 10 of this example were obtained.
【００１３】一方、比較例試料は、上記成形体を、上記
脱バインダ焼成後、９９％Ｎ２−１５Ｈ２の還元雰囲気
中にて、１４５０℃で２時間焼成し、半導体磁器を得、
次にこの半導体磁器を、空気中において、表２に示す各
条件で再酸化焼成を行い、比較例試料１〜５を得た。On the other hand, as a comparative example, the molded body was fired at 1450° C. for 2 hours in a reducing atmosphere of 99% N2-15H2 after the binder removal firing to obtain semiconductor porcelain.
Next, this semiconductor porcelain was reoxidized and fired in air under the conditions shown in Table 2 to obtain comparative samples 1 to 5.
【００１４】上記実施例試料および比較例試料の両主面
に銀ペーストを塗布し、７００℃で３０分焼き付け、電
極を形成し、これを用いて、各バリスタ電圧Ｅ１０（Ｖ
）、非直線係数α、静電容量（ｎＦ）、Ｖ１０バラツキ
（バリスタ電圧のバラツキ）σｎ／ｘ（％）を測定した
。その結果を、表１および表２にそれぞれ示した。Silver paste was applied to both main surfaces of the above example sample and comparative example sample, and baked at 700°C for 30 minutes to form electrodes. Using this, each varistor voltage E10 (V
), nonlinear coefficient α, capacitance (nF), and V10 variation (varistor voltage variation) σn/x (%) were measured. The results are shown in Tables 1 and 2, respectively.
【００１５】[0015]
【表１】[Table 1]
【００１６】[0016]
【表２】[Table 2]
【００１７】上記表１から分かるように、本製造方法に
よる場合は、実施例試料１〜６に示されているように、
酸化雰囲気中での焼成時の降温時間を一定にしておき、
上記雰囲気における酸素濃度を１〜１００％と変化させ
ることにより、バリスタ電圧を１０．２Ｖから６８．１
Ｖとコントロールすることができる。また、実施例試料
７〜１０に示されているように、上記雰囲気における酸
素濃度を一定にしておき、上記降温時間５０℃／時間〜
４００℃／時間と変化させることにより、バリスタ電圧
を４４．５Ｖから２１．４Ｖとコントロールすることが
できる。このように、本方法による場合、焼成における
酸素含有雰囲気中の酸素濃度および／または焼成時の降
温時間を適宜制御することにより、バリスタ電圧を容易
にコントロールすることができる。As can be seen from Table 1 above, in the case of this manufacturing method, as shown in Example Samples 1 to 6,
Keep the temperature drop time constant during firing in an oxidizing atmosphere,
By changing the oxygen concentration in the above atmosphere from 1 to 100%, the varistor voltage can be changed from 10.2V to 68.1V.
It can be controlled with V. Further, as shown in Example Samples 7 to 10, the oxygen concentration in the above atmosphere was kept constant, and the temperature drop time was 50°C/hour to 50°C/hour.
By changing the temperature at 400°C/hour, the varistor voltage can be controlled from 44.5V to 21.4V. As described above, in the case of the present method, the varistor voltage can be easily controlled by appropriately controlling the oxygen concentration in the oxygen-containing atmosphere during firing and/or the temperature drop time during firing.
【００１８】また、本方法によって得られた試料におい
ては、Ｖ１０バラツキにおいて、最高で３．６％だった
のに対して、比較例の試料においては、最低で５．１％
と高く、本方法により、バリスタを安定して製造するこ
とができる。更に、本方法によって得られた試料におい
ては、非直線係数αにおいて、７．２〜９．１と高かっ
たのに対して、比較例の試料においては、３．９〜４．
４と低く、本方法により、高い非直線係数αのバリスタ
を製造することができる。In addition, in the sample obtained by this method, the maximum variation in V10 was 3.6%, whereas in the sample of the comparative example, the minimum variation was 5.1%.
This method allows stable production of varistors. Furthermore, in the samples obtained by this method, the nonlinear coefficient α was as high as 7.2 to 9.1, whereas in the sample of the comparative example, it was 3.9 to 4.
By this method, a varistor with a high nonlinear coefficient α can be manufactured.
【００１９】[0019]
【発明の効果】以上説明したように、本発明によるバリ
スタの製造方法によれば、ＡＢＯ３（Ａ：Ｓｒ，Ｂａ，
Ｃａ，Ｍｇ，Ｂ：Ｔｉ，Ｚｒ）である主成分に、原子価
制御剤を添加した組成物を酸素含有雰囲気中で焼成する
ことにより、焼成体にバリスタ特性を与えることができ
、従来の還元焼成を省略することができ、簡略化された
工程でバリスタを製造することができる。Effects of the Invention As explained above, according to the method for manufacturing a varistor according to the present invention, ABO3 (A: Sr, Ba,
By firing a composition in which a valence control agent is added to the main components (Ca, Mg, B: Ti, Zr) in an oxygen-containing atmosphere, it is possible to impart varistor properties to the fired body, and it is possible to Firing can be omitted, and the varistor can be manufactured through a simplified process.
【００２０】また、本発明によれば、焼成における酸素
含有雰囲気中の酸素濃度および／または焼成時の降温時
間を適宜制御することにより、バリスタ電圧を容易にコ
ントロールすることができるので、バリスタの製造設計
が容易となる。Furthermore, according to the present invention, the varistor voltage can be easily controlled by suitably controlling the oxygen concentration in the oxygen-containing atmosphere during firing and/or the temperature drop time during firing. Design becomes easier.
【００２１】更に、本発明によれば、製造されたバリス
タのバリスタ電圧のバラツキが小さくなり、量産におけ
る歩留まりを向上させることができるとともに、非直線
係数α等の特性も向上させることができる。Furthermore, according to the present invention, variations in the varistor voltage of manufactured varistors are reduced, making it possible to improve the yield in mass production, and also to improve characteristics such as the nonlinear coefficient α.
Claims (1)
ｇ，Ｂ：Ｔｉ，Ｚｒ）を主成分とするバリスタの製造方
法において、前記ＡＢＯ３を主成分とする原材料に原子
価制御剤を添加し、これにバインダを加えて成形して形
成した成形体を脱バインダ焼成し、この後、酸素含有雰
囲気中にて焼成して焼結体を得ることを特徴とするバリ
スタの製造方法。[Claim 1] ABO3 (A: Sr, Ba, Ca, M
g, B: Ti, Zr), a molded body is formed by adding a valence control agent to the raw material containing ABO3 as the main component, adding a binder to the raw material, and molding the mixture. A method for manufacturing a varistor, which comprises removing the binder and firing it, and then firing it in an oxygen-containing atmosphere to obtain a sintered body.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3064402A JPH04299804A (en) | 1991-03-28 | 1991-03-28 | Manufacture of varistor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3064402A JPH04299804A (en) | 1991-03-28 | 1991-03-28 | Manufacture of varistor |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH04299804A true JPH04299804A (en) | 1992-10-23 |
Family
ID=13257288
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3064402A Withdrawn JPH04299804A (en) | 1991-03-28 | 1991-03-28 | Manufacture of varistor |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH04299804A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8100954B2 (en) | 2005-01-28 | 2012-01-24 | Orthohelix Surgical Designs, Inc. | Orthopedic plate for use in small bone repair |
| US20190283507A1 (en) * | 2018-03-13 | 2019-09-19 | Hankook Tire Co., Ltd. | Tire with main kerfs and sub-kerfs |
-
1991
- 1991-03-28 JP JP3064402A patent/JPH04299804A/en not_active Withdrawn
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8100954B2 (en) | 2005-01-28 | 2012-01-24 | Orthohelix Surgical Designs, Inc. | Orthopedic plate for use in small bone repair |
| US20190283507A1 (en) * | 2018-03-13 | 2019-09-19 | Hankook Tire Co., Ltd. | Tire with main kerfs and sub-kerfs |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A300 | Application deemed to be withdrawn because no request for examination was validly filed |
Free format text: JAPANESE INTERMEDIATE CODE: A300 Effective date: 19980514 |