JPH07335368A - Surge absorbing element, and its manufacture - Google Patents
Surge absorbing element, and its manufactureInfo
- Publication number
- JPH07335368A JPH07335368A JP14555494A JP14555494A JPH07335368A JP H07335368 A JPH07335368 A JP H07335368A JP 14555494 A JP14555494 A JP 14555494A JP 14555494 A JP14555494 A JP 14555494A JP H07335368 A JPH07335368 A JP H07335368A
- Authority
- JP
- Japan
- Prior art keywords
- metal layer
- cap
- sealing material
- absorbing element
- envelope
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000004519 manufacturing process Methods 0.000 title claims description 8
- 229910052751 metal Inorganic materials 0.000 claims abstract description 64
- 239000002184 metal Substances 0.000 claims abstract description 64
- 239000003566 sealing material Substances 0.000 claims abstract description 49
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 31
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 31
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 8
- 239000011521 glass Substances 0.000 claims description 19
- 229910045601 alloy Inorganic materials 0.000 claims description 15
- 239000000956 alloy Substances 0.000 claims description 15
- 239000007789 gas Substances 0.000 claims description 10
- 229910000640 Fe alloy Inorganic materials 0.000 claims description 9
- 239000006096 absorbing agent Substances 0.000 claims description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 8
- 230000008018 melting Effects 0.000 claims description 8
- 238000002844 melting Methods 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 7
- 239000001257 hydrogen Substances 0.000 claims description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- 230000003647 oxidation Effects 0.000 claims description 7
- 238000010521 absorption reaction Methods 0.000 claims description 4
- 230000000903 blocking effect Effects 0.000 abstract 2
- 239000003795 chemical substances by application Substances 0.000 abstract 1
- 238000007789 sealing Methods 0.000 abstract 1
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 description 10
- 238000000034 method Methods 0.000 description 9
- 239000000463 material Substances 0.000 description 6
- 238000005498 polishing Methods 0.000 description 4
- 229910000679 solder Inorganic materials 0.000 description 4
- 229910000990 Ni alloy Inorganic materials 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 239000011651 chromium Substances 0.000 description 3
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 description 3
- 229910052839 forsterite Inorganic materials 0.000 description 3
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 238000010891 electric arc Methods 0.000 description 2
- 239000007769 metal material Substances 0.000 description 2
- 230000002159 abnormal effect Effects 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
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000007517 polishing process Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000004043 responsiveness Effects 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000001052 transient effect Effects 0.000 description 1
Landscapes
- Thermistors And Varistors (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】この発明はサージ吸収素子及びそ
の製造方法に係り、特に、外囲器の開口部とキャップを
封着材を介して気密に接合して気密容器を形成し、該気
密容器内に少なくとも放電ガスと放電間隙を封入した構
造を備えたサージ吸収素子及びその製造方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a surge absorber and a method of manufacturing the same, and more particularly, to an airtight container formed by hermetically joining an opening of an envelope and a cap via a sealing material. The present invention relates to a surge absorbing element having a structure in which at least a discharge gas and a discharge gap are sealed in a container and a method for manufacturing the surge absorbing element.
【０００２】[0002]
【従来の技術】従来、電子機器に侵入する過渡的な異常
電圧や誘導雷等のサージから電子回路素子を保護するた
め、気密容器内に封入した放電間隙における放電現象を
利用したサージ吸収素子が用いられている。図４はその
一例を示すものであり、このサージ吸収素子50は、気密
容器52内にＮｉ・Ｆｅ合金等より成る一対の放電電極54
を所定の距離を隔てて対向配置して、両放電電極54間に
放電間隙56を形成すると共に、両放電電極54間にＺｎＯ
等より成る電圧非直線抵抗体58を接続し、所定の放電ガ
スを封入して成る。2. Description of the Related Art Conventionally, in order to protect an electronic circuit element from a transient abnormal voltage intruding into an electronic device or a surge such as an induced lightning, a surge absorbing element utilizing a discharge phenomenon in a discharge gap enclosed in an airtight container has been used. It is used. FIG. 4 shows an example thereof. This surge absorbing element 50 includes a pair of discharge electrodes 54 made of Ni / Fe alloy or the like in an airtight container 52.
Are arranged to face each other with a predetermined distance, and a discharge gap 56 is formed between the both discharge electrodes 54, and ZnO is formed between the both discharge electrodes 54.
A voltage non-linear resistor 58 made of, for example, is connected and a predetermined discharge gas is sealed therein.
【０００３】上記気密容器52は、両端が開口した円筒状
の外囲器60と、該外囲器60の開口部62を閉塞する一対の
キャップ64と、上記外囲器60の開口部62とキャップ64の
内面との間に介在して両者間を気密に接合する封着材66
より形成される。この封着材66は、低融点ガラスによっ
て構成される。上記キャップ64の材質は、この封着材66
と熱膨張係数が略等しいものとして、４２・６合金が選
定される。上記放電電極54の基端部54ａは、このキャッ
プ64の内面に溶接されている。また、キャップ64の外面
には、ハンダ68を介してリード線70が接続される。ある
いは、キャップ64の外面に、リード線70を溶接してもよ
い。上記外囲器60も、上記封着材66と熱膨張係数が略等
しいフォルステライトにより形成される。The airtight container 52 has a cylindrical envelope 60 having both ends opened, a pair of caps 64 for closing the opening 62 of the envelope 60, and an opening 62 of the envelope 60. A sealing material 66 that is interposed between the inner surface of the cap 64 and the airtight connection between the two.
Formed by. The sealing material 66 is made of low melting point glass. The cap 64 is made of this sealing material 66.
42.6 alloy is selected as a material whose thermal expansion coefficient is substantially equal to. The base end portion 54 a of the discharge electrode 54 is welded to the inner surface of the cap 64. A lead wire 70 is connected to the outer surface of the cap 64 via a solder 68. Alternatively, the lead wire 70 may be welded to the outer surface of the cap 64. The envelope 60 is also made of forsterite having a thermal expansion coefficient substantially equal to that of the sealing material 66.
【０００４】しかして、上記リード線70を介して定格以
上のサージが印加されると、まず上記電圧非直線抵抗体
58が通電してサージの吸収が直ちに開始され、このサー
ジ電流値と電圧非直線抵抗体58の抵抗値との積に相当す
る電圧降下が生じることとなる。そして、サージ電流量
の増加に伴って上記電圧降下も増大し、これが上記放電
間隙56の放電開始電圧以上となった時点で、即座に放電
間隙56にグロー放電を経てアーク放電が生成され、この
アーク放電の大電流を通じてサージの本格的な吸収が実
現される。このように、このサージ吸収素子50は、放電
間隙56と電圧非直線抵抗体58との並列接続構造を備えて
いるため、バリスタの速応性と、アレスタの大電流耐量
性を兼ね備えた、優れたサージ吸収特性を発揮し得るも
のである。However, when a surge exceeding the rated value is applied through the lead wire 70, first, the voltage non-linear resistor is applied.
When 58 is energized, absorption of surge is immediately started, and a voltage drop corresponding to the product of this surge current value and the resistance value of the voltage non-linear resistor 58 occurs. Then, as the surge current amount increases, the voltage drop also increases, and when this becomes equal to or higher than the discharge start voltage of the discharge gap 56, arc discharge is immediately generated in the discharge gap 56 through glow discharge, Full-scale absorption of surge is realized through the large current of arc discharge. As described above, since the surge absorbing element 50 has the parallel connection structure of the discharge gap 56 and the voltage non-linear resistor 58, it has excellent responsiveness of the varistor and large current withstanding capability of the arrester. It is possible to exhibit surge absorption characteristics.
【０００５】[0005]
【発明が解決しようとする課題】上記のように、キャッ
プ64は封着材66の熱膨張係数に適合させる関係で４２・
６合金によって形成されているが、この４２・６合金は
そのままの状態では封着材66との馴染みが悪く、外囲器
60を気密に封止することができないため、その表面に金
属酸化膜を形成し、両者間の馴染みを良好にすることが
行われている。すなわち、キャップ64の内面に予め放電
電極54を溶接した状態で、全体に湿潤水素処理を施し、
キャップ64の表面に緻密な凹凸を備えた深緑色の酸化ク
ロム膜を強固に形成することにより、封着材66との接合
力を高めている。As described above, the cap 64 has a relationship of matching the coefficient of thermal expansion of the sealing material 66.
It is made of 6 alloy, but this 42.6 alloy is not as familiar with the sealing material 66 as it is, and the envelope is
Since 60 cannot be hermetically sealed, a metal oxide film is formed on the surface thereof to improve the familiarity between the two. That is, in a state in which the discharge electrode 54 is previously welded to the inner surface of the cap 64, wet hydrogen treatment is applied to the whole,
By strongly forming a deep green chromium oxide film having dense irregularities on the surface of the cap 64, the bonding force with the sealing material 66 is enhanced.
【０００６】しかしながら、この金属酸化膜の形成に際
しては、キャップ64の内面のみならず、外面にまでも絶
縁性の金属酸化膜が形成されてしまうため、リード線70
等との電気的接続を実現するためには、後でキャップ64
外面の金属酸化膜を研磨して除去する工程が不可欠とな
り、製造の煩雑化及び製造コストの上昇を招いていた。
また、この金属酸化膜は、キャップ64表面を極めて強固
に覆っているため、これを除去する過程で熱的・機械的
な衝撃によってキャップ64やサージ吸収素子50本体を破
損したり、有害な粉塵が発生するといった問題が生じ
る。もちろん、キャップ64の外面を予めマスクで覆って
おき、金属酸化膜形成後にそのマスクを剥がすようにす
れば、キャップ64の外面に金属酸化膜が形成されること
を回避できるが、今度はそのマスクの被覆・剥離工程自
体が大きな負担となるため、問題の本質的な解決とはな
り得ない。However, when the metal oxide film is formed, the insulating metal oxide film is formed not only on the inner surface of the cap 64 but also on the outer surface thereof.
In order to realize the electrical connection with
A step of polishing and removing the metal oxide film on the outer surface is indispensable, which causes complication of manufacturing and increase in manufacturing cost.
In addition, since the metal oxide film covers the surface of the cap 64 extremely strongly, the cap 64 and the surge absorbing element 50 main body may be damaged or harmful dust may be caused by thermal / mechanical shock in the process of removing the metal oxide film. Occurs. Of course, if the outer surface of the cap 64 is covered with a mask in advance and the mask is peeled off after the metal oxide film is formed, the formation of the metal oxide film on the outer surface of the cap 64 can be avoided. Since the coating / peeling process itself of (1) becomes a heavy burden, it cannot be an essential solution to the problem.
【０００７】この発明は、上記従来の問題に鑑みてなさ
れたものであり、その目的とするところは、外囲器の開
口部を閉塞するキャップ内面に、封着材との馴染みを良
好にするための金属酸化膜を形成する際に、同時にキャ
ップ外面に絶縁性の酸化膜が強固に形成されてしまうこ
とのないサージ吸収素子を実現することにある。また、
このようなサージ吸収素子の製造方法を実現することに
ある。The present invention has been made in view of the above-mentioned conventional problems, and an object of the present invention is to make the inner surface of the cap that closes the opening of the envelope fit well with the sealing material. It is to realize a surge absorbing element in which an insulating oxide film is not firmly formed on the outer surface of the cap at the same time when the metal oxide film for forming is formed. Also,
It is to realize a method of manufacturing such a surge absorber.
【０００８】[0008]
【課題を解決するための手段】上記の目的を達成するた
め、この発明に係るサージ吸収素子は、開口部を備えた
外囲器と、該外囲器の開口部を閉塞するキャップと、上
記外囲器の開口部とキャップとを接合させる封着材とか
ら成る気密容器内に、少なくとも放電ガスと、複数の放
電電極間に形成された放電間隙とを封入して成るサージ
吸収素子において、上記キャップを、上記封着材と接す
る第１の金属層と、該第１の金属層よりも耐酸化性の強
い第２の金属層との積層構造と成し、上記第１の金属層
の表面の中、少なくとも上記封着材と接する部分に金属
酸化膜が形成されていることを特徴とする。この第１の
金属層表面の金属酸化膜は、例えば、湿潤水素中で上記
キャップ全体に加熱処理を施すことによって形成され
る。To achieve the above object, a surge absorbing element according to the present invention has an envelope having an opening, a cap for closing the opening of the envelope, and In a surge absorbing element formed by enclosing at least a discharge gas and a discharge gap formed between a plurality of discharge electrodes in an airtight container formed of a sealing material that joins the opening of the envelope and the cap, The cap has a laminated structure of a first metal layer in contact with the sealing material and a second metal layer having stronger oxidation resistance than the first metal layer. A metal oxide film is formed on at least a portion of the surface that is in contact with the sealing material. The metal oxide film on the surface of the first metal layer is formed, for example, by subjecting the entire cap to heat treatment in wet hydrogen.
【０００９】上記封着材は、例えば低融点ガラスによっ
て構成される。上記第１の金属層は、上記封着材と熱膨
張係数が略等しい金属によって形成されることが望まし
く、その一例として４２・６合金が該当する。この４２
・６合金は、Ｎｉを４２％、Ｃｒを６％を含有し、残り
の成分をＦｅで構成した合金である。上記第２の金属層
は、上記第１の金属層と熱膨張係数が略等しい金属によ
って形成されることが望ましく、例えば５０Ｎｉ・Ｆｅ
合金が該当する。この５０Ｎｉ・Ｆｅ合金は、ＮｉとＦ
ｅを１：１の比率で含有するものである。この発明は、
上記放電電極間に、電圧非直線抵抗体を接続したタイプ
のサージ吸収素子にも応用できる。The sealing material is made of, for example, low melting glass. The first metal layer is preferably formed of a metal having a thermal expansion coefficient substantially equal to that of the sealing material, and an example thereof is a 42.6 alloy. This 42
The 6 alloy is an alloy containing 42% of Ni and 6% of Cr, and the remaining components being Fe. It is desirable that the second metal layer be formed of a metal having a thermal expansion coefficient substantially equal to that of the first metal layer. For example, 50Ni.Fe.
Alloys are applicable. This 50Ni ・ Fe alloy is made of Ni and F
e is contained in a ratio of 1: 1. This invention
It can also be applied to a surge absorbing element of a type in which a voltage non-linear resistor is connected between the discharge electrodes.
【００１０】[0010]
【作用】キャップを構成する第２の金属層は、第１の金
属層よりも耐酸化性に優れるため、キャップ全体に酸化
処理を施しても、第２の金属層の表面に絶縁性の金属酸
化膜が強固に形成されることがなく、したがってリード
線等の接続に際し、キャップ外面を研磨して金属酸化膜
を除去する必要がほとんどない。これに対し、第１の金
属層の表面には金属酸化膜が強固に形成されるため、封
着材との馴染みが良好となり、キャップによって外囲器
の開口部を気密に閉塞できる。Since the second metal layer forming the cap is more excellent in oxidation resistance than the first metal layer, even if the entire cap is oxidized, an insulating metal layer is formed on the surface of the second metal layer. Since the oxide film is not strongly formed, it is almost unnecessary to remove the metal oxide film by polishing the outer surface of the cap when connecting the lead wire or the like. On the other hand, since the metal oxide film is firmly formed on the surface of the first metal layer, the compatibility with the sealing material becomes good, and the opening of the envelope can be airtightly closed by the cap.
【００１１】[0011]
【実施例】以下、添付図面に基づき、本発明の実施例を
説明する。図１は、本発明に係る第１のサージ吸収素子
10を示す断面図である。この第１のサージ吸収素子10
は、両端が開口した円筒状の外囲器12と、該外囲器12の
両端開口部14を閉塞する一対のキャップ16と、該キャッ
プ16の内面と外囲器12の開口部14とを気密に接合させる
封着材18とから成る気密容器20内に、一対の放電電極22
を所定の距離を隔てて配置し、両放電電極22間に放電間
隙24を形成すると共に、両放電電極22間に電圧非直線抵
抗体26を接続し、以て放電間隙24と電圧非直線抵抗体26
との並列接続構造を実現している。この気密容器20内に
は、Ｎｅ，Ｈｅ，Ａｒ，Ｘｅ等の希ガスを主体とした放
電ガスが充填されている。また、上記キャップ16の外面
には、ハンダ28を介してリード線30が接続されている。
あるいは、このキャップ16の外面に、リード線30を溶接
してもよい。Embodiments of the present invention will be described below with reference to the accompanying drawings. FIG. 1 shows a first surge absorbing element according to the present invention.
FIG. 11 is a sectional view showing 10. This first surge absorber 10
Is a cylindrical envelope 12 having both ends opened, a pair of caps 16 for closing both end openings 14 of the envelope 12, an inner surface of the cap 16 and the opening 14 of the envelope 12. A pair of discharge electrodes 22 are provided in an airtight container 20 composed of a sealing material 18 that is airtightly joined.
Are arranged at a predetermined distance, a discharge gap 24 is formed between both discharge electrodes 22, and a voltage nonlinear resistor 26 is connected between both discharge electrodes 22. Body 26
It realizes a parallel connection structure with. The airtight container 20 is filled with a discharge gas mainly composed of a rare gas such as Ne, He, Ar or Xe. A lead wire 30 is connected to the outer surface of the cap 16 via a solder 28.
Alternatively, the lead wire 30 may be welded to the outer surface of the cap 16.
【００１２】上記封着材18は、フリットガラス等の低融
点結晶化ガラスより成る。また、上記外囲器12は、この
封着材18と熱膨張係数が略等しいフォルステライトによ
って形成されている。あるいは、アルミナ等、他のセラ
ミックやガラス等の絶縁材によって形成してもよい。上
記放電電極22は、ＦｅやＮｉ、あるいはＮｉ・Ｆｅ合金
など放電特性の良好な金属材よりなり、各放電電極22の
基端部22ａは上記キャップ16内面の略中央部に溶接され
ている。また、上記電圧非直線抵抗体26は、ＺｎＯを円
柱状に加工したものであり、その両端面が導電性接着剤
を介して各放電電極22の先端凹部22ｂに接続されてい
る。The sealing material 18 is made of low melting point crystallized glass such as frit glass. The envelope 12 is made of forsterite having a thermal expansion coefficient substantially equal to that of the sealing material 18. Alternatively, it may be formed of another ceramic such as alumina or an insulating material such as glass. The discharge electrodes 22 are made of a metal material having good discharge characteristics such as Fe, Ni, or a Ni / Fe alloy, and the base end portions 22a of the discharge electrodes 22 are welded to the substantially central portion of the inner surface of the cap 16. The voltage non-linear resistor 26 is formed by processing ZnO into a columnar shape, and both end faces thereof are connected to the tip recesses 22b of the discharge electrodes 22 via a conductive adhesive.
【００１３】上記キャップ16は、第１の金属層16ａと第
２の金属層16ｂとを積層させた、厚さ０．２〜０．４mm
のクラッド材より成り、内面側に位置する第１の金属層
16ａは、上記封着材18と熱膨張係数の略等しい４２・６
合金より構成されると共に、外面側に位置する第２の金
属層16ｂは、４２・６合金よりも耐酸化性が強いＮｉや
Ｎｉ・Ｆｅ合金より構成される。特に、ＮｉとＦｅの含
有率が約１：１の５０Ｎｉ・Ｆｅ合金を用いれば、第１
の金属層16ａと第２の金属層16ｂの熱膨張係数を略等し
くすることができる。なお、第１の金属層16ａと第２の
金属層16ｂの層厚比は１：１に設定されているが、これ
は必要に応じて調節することが可能である。図２に示し
たように、第１の金属層16ａの表面には、酸化クロム
（Ｃｒ2Ｏ3）より成る深緑色の金属酸化膜32が形成され
ている。The cap 16 has a thickness of 0.2 to 0.4 mm in which a first metal layer 16a and a second metal layer 16b are laminated.
First metal layer which is made of the clad material and is located on the inner surface side
16a has a coefficient of thermal expansion approximately equal to that of the sealing material 42.6.
The second metal layer 16b, which is made of an alloy and is located on the outer surface side, is made of Ni or a Ni.Fe alloy having stronger oxidation resistance than the 42.6 alloy. In particular, if a 50Ni.Fe alloy with a Ni and Fe content of about 1: 1 is used,
The thermal expansion coefficients of the metal layer 16a and the second metal layer 16b can be made substantially equal. Although the layer thickness ratio of the first metal layer 16a and the second metal layer 16b is set to 1: 1, this can be adjusted as necessary. As shown in FIG. 2, a deep green metal oxide film 32 made of chromium oxide (Cr 2 O 3 ) is formed on the surface of the first metal layer 16a.
【００１４】この第１のサージ吸収素子10は、以下の手
順によって製造される。まず、円板状と成されたクラッ
ド材にプレス加工を施し、その周縁を第１の金属層16ａ
側に立ち上げてフランジ16ｃを形成してキャップ16と成
し、その第１の金属層16ａの略中央部に予め放電電極22
を溶接しておく。つぎに、このキャップ16に、放電電極
22を接続したままの状態で湿潤水素処理を施して、第１
の金属層16ａ表面における、上記放電電極22が接続され
ていない部分に金属酸化膜32を形成する。この湿潤水素
処理とは、水中を通過させて水蒸気を含ませた水素ガス
雰囲気中にキャップ16を保持し、１０００〜１３００゜
Ｃの温度で数十分間の加熱を行うものであり、この過程
において、４２・６合金に含まれたＣｒが水分中のＯと
結合してＣｒ2Ｏ3となる。なお、この湿潤水素処理にお
いて酸化されるのは、４２・６合金より成る第１の金属
層16ａの露出部分だけであり、Ｎｉ・Ｆｅ合金より成る
第２の金属層16ｂ及び放電電極22の表面はほとんど変化
しない。このため、第１の金属層16ａに金属酸化膜32を
形成した後に、放電電極22の表面及びキャップ16の外面
を研磨する必要はほとんどなく、研磨するとしても極僅
かの作業で足りる。The first surge absorbing element 10 is manufactured by the following procedure. First, a disk-shaped clad material is press-worked, and the periphery of the clad material is pressed against the first metal layer 16a.
And a flange 16c is formed on the side of the first metal layer 16a to form a flange 16c.
Weld in advance. Next, the discharge electrode is attached to the cap 16.
Wet hydrogen treatment with 22 connected,
A metal oxide film 32 is formed on the surface of the metal layer 16a where the discharge electrode 22 is not connected. In this wet hydrogen treatment, the cap 16 is held in a hydrogen gas atmosphere containing water vapor by passing through water, and heating is performed at a temperature of 1000 to 1300 ° C. for several tens of minutes. In, the Cr contained in the 42.6 alloy is combined with O in the water to form Cr 2 O 3 . In this wet hydrogen treatment, only the exposed portion of the first metal layer 16a made of the 42.6 alloy is oxidized, and the surfaces of the second metal layer 16b made of the Ni.Fe alloy and the discharge electrode 22 are oxidized. Hardly changes. Therefore, there is almost no need to polish the surface of the discharge electrode 22 and the outer surface of the cap 16 after forming the metal oxide film 32 on the first metal layer 16a.
【００１５】つぎに、何れか一方のキャップ16に接続さ
れた放電電極22の先端凹部22ｂに、導電性接着剤を介し
て電圧非直線抵抗体26の一端を接続すると共に、上記外
囲器12の一方の開口部14の端面付近に低融点結晶化ガラ
スの粉末を含むペーストを塗布し、これを上記キャップ
16内面の金属酸化膜32に当接させ、上記ペースト中のガ
ラス以外の成分（バインダや溶剤、結着剤等）を分解・
蒸発させ得る温度（２００〜３００゜Ｃ）で一旦加熱し
て、これら不要成分を除去する。その後、上記ガラスの
結晶化温度である４５０゜Ｃで再加熱し、ペースト中の
ガラス成分を結晶化させて封着材18を形成し、該封着材
18を介して外囲器12の開口部14とキャップ16とを気密に
接合させる。Next, one end of the voltage non-linear resistor 26 is connected to the tip recess 22b of the discharge electrode 22 connected to one of the caps 16 via a conductive adhesive, and the envelope 12 described above is connected. A paste containing a powder of low melting point crystallized glass is applied to the vicinity of the end face of the opening 14 on one side, and the paste is applied to the cap.
16 Contact the metal oxide film 32 on the inner surface to decompose components (binder, solvent, binder, etc.) other than glass in the paste.
These unnecessary components are removed by heating once at a temperature (200 to 300 ° C) at which evaporation is possible. Then, it is reheated at 450 ° C. which is the crystallization temperature of the above glass to crystallize the glass component in the paste to form the sealing material 18, and the sealing material 18 is formed.
The opening (14) of the envelope (12) and the cap (16) are airtightly joined via (18).
【００１６】続いて、他方のキャップ16に接続された放
電電極22の先端凹部22ｂに導電性接着剤を塗布すると共
に、該キャップ16内面の金属酸化膜32付近に上記と同様
のペーストを塗布し、これを２００〜３００゜Ｃで一旦
加熱して、ペースト中のガラス以外の成分を除去した
後、該ガラスの溶融温度以上で、かつ結晶化温度よりも
若干低い温度（４００゜Ｃ程度）で加熱して半硬化状態
としておく。つぎに、該キャップ16を外囲器12の他方の
開口部14に係合して半硬化状態のガラスを該開口部14の
端面に当接させ、これらをチャンバ内に配置して真空排
気を施した後、所定の放電ガスを内部に充填させる。そ
の後、４５０゜Ｃで再加熱し、上記半硬化状態のガラス
を結晶化させて封着材18を形成し、該封着材18を介して
外囲器12の開口部14とキャップ16とを気密に接合させ
る。なお、半硬化状態のガラスの表面には微細な凹凸が
あるため、これを上記のように開口部14の端面に当接さ
せると両者間に隙間が生じ、該隙間を介して上記の真空
排気及び放電ガスの充填が実現されるのである。これに
対し、４５０゜Ｃで再加熱を施すと、半硬化状態のガラ
スが一旦溶融した後、結晶化して完全な硬化状態となる
ため、気密性を備えた封着材18が得られるものである。Subsequently, a conductive adhesive is applied to the tip recess 22b of the discharge electrode 22 connected to the other cap 16, and a paste similar to the above is applied near the metal oxide film 32 on the inner surface of the cap 16. After heating this at 200 to 300 ° C once to remove components other than glass in the paste, the temperature is higher than the melting temperature of the glass and slightly lower than the crystallization temperature (about 400 ° C). Heat to leave a semi-cured state. Next, the cap 16 is engaged with the other opening 14 of the envelope 12 to bring the semi-cured glass into contact with the end surface of the opening 14, and these are placed in the chamber for vacuum evacuation. After that, a predetermined discharge gas is filled inside. Then, it is reheated at 450 ° C. to crystallize the semi-cured glass to form the sealing material 18, and the opening 14 of the envelope 12 and the cap 16 are connected via the sealing material 18. Bond airtightly. Since the surface of the glass in the semi-cured state has fine irregularities, when it is brought into contact with the end face of the opening 14 as described above, a gap is created between the two, and the vacuum exhaust is performed through the gap. And the filling of the discharge gas is realized. On the other hand, when the glass is reheated at 450 ° C., the semi-cured glass is once melted and then crystallized into a completely cured state, so that the sealing material 18 having airtightness can be obtained. is there.
【００１７】図２に示すように、封着材18は外囲器12の
端面とキャップ16内面間のみならず、外囲器12の外面先
端部とキャップ16のフランジ16ｃ内面との間、及び外囲
器12の内面先端部とキャップ16内面間にも配されてお
り、しかも、キャップ16内面の金属酸化膜32には緻密な
凹凸が多数形成されているため、キャップ16内面と封着
材18との馴染みが極めて良好となり、金属酸化膜32と封
着材18とのイオン結合により、両者は強固に接合され
る。最後に、上記キャップ16外面に、ハンダ28を介して
リード線30を接続することにより、第１のサージ吸収素
子10が完成する。As shown in FIG. 2, the sealing material 18 is provided not only between the end face of the envelope 12 and the inner face of the cap 16, but also between the tip of the outer face of the envelope 12 and the inner face of the flange 16c of the cap 16, and It is also arranged between the tip of the inner surface of the envelope 12 and the inner surface of the cap 16, and moreover, since the metal oxide film 32 on the inner surface of the cap 16 has many fine irregularities, the inner surface of the cap 16 and the sealing material. Familiarity with 18 becomes extremely good, and the metal oxide film 32 and the sealing material 18 are bonded firmly by ionic bonding. Finally, the first surge absorbing element 10 is completed by connecting the lead wire 30 to the outer surface of the cap 16 via the solder 28.
【００１８】なお、外囲器12、封着材18、第１の金属層
16ａ及び第２の金属層16ｂを構成する材料として、それ
ぞれの熱膨張係数が略共通となるものを選定しているた
め、封着材18の上記加熱・焼成工程において、接合部分
に亀裂や歪みが生じるおそれがなく、高い気密性を維持
できる。また、上記電圧非直線抵抗体26は比較的熱に弱
いが、封着材18として低融点結晶化ガラスを選定したた
め、その加熱・焼成工程においても僅か４５０゜Ｃにし
かならず、電圧非直線抵抗体26が熱劣化を起こすことは
ない。The envelope 12, the sealing material 18, the first metal layer
As the materials forming the 16a and the second metal layer 16b are selected so that their thermal expansion coefficients are substantially common, cracks or strains may occur at the joints in the heating / baking process of the sealing material 18. It is possible to maintain high airtightness without the risk of Further, although the voltage nonlinear resistor 26 is relatively weak to heat, since low melting point crystallized glass is selected as the sealing material 18, only 450 ° C. is reached even in the heating / firing process. 26 does not undergo thermal degradation.
【００１９】図３は、この発明に係る第２のサージ吸収
素子40を示すものである。この第２のサージ吸収素子40
は、両端が開口した円筒状の外囲器12と、該外囲器12の
両端開口部14を閉塞する一対のキャップ16と、該キャッ
プ16の内面と外囲器12の開口部14とを気密に接合させる
封着材18から成る気密容器20内に、一対の放電電極22を
所定の距離を隔てて配置し、両放電電極22間に放電間隙
24を形成すると共に、所定の放電ガスを充填して成る。
また、上記キャップ16の外面には、ハンダ28を介してリ
ード線30が接続されている。FIG. 3 shows a second surge absorbing element 40 according to the present invention. This second surge absorber 40
Is a cylindrical envelope 12 having both ends opened, a pair of caps 16 for closing both end openings 14 of the envelope 12, an inner surface of the cap 16 and the opening 14 of the envelope 12. A pair of discharge electrodes 22 are arranged at a predetermined distance in an airtight container 20 made of a sealing material 18 that is airtightly joined, and a discharge gap is formed between the discharge electrodes 22.
24 is formed and is filled with a predetermined discharge gas.
A lead wire 30 is connected to the outer surface of the cap 16 via a solder 28.
【００２０】上記封着材18は低融点結晶化ガラスより成
り、上記外囲器12は該封着材18と熱膨張係数が略等しい
フォルステライトによって形成されている。上記放電電
極22は、Ｎｉ・Ｆｅ合金など放電特性の良好な金属材よ
り成り、各放電電極22の基端部22ａは上記キャップ16内
面の略中央部に溶接されている。上記キャップ16は、第
１の金属層16ａと第２の金属層16ｂを積層させた、厚さ
０．２〜０．４mmのクラッド材より成り、内面側に位置
する第１の金属層16ａは、上記封着材18と熱膨張係数の
略等しい４２・６合金より構成されると共に、外面側に
位置する第２の金属層16ｂは、４２・６合金よりも耐酸
化性が強く、しかも４２・６合金と略等しい熱膨張係数
を備えた５０Ｎｉ・Ｆｅ合金より構成されている。ま
た、図示は省略したが、第１の金属層16ａの表面には、
酸化クロム（Ｃｒ2Ｏ3）より成る金属酸化膜が形成され
ている。The sealing material 18 is made of low melting point crystallized glass, and the envelope 12 is made of forsterite having a thermal expansion coefficient substantially equal to that of the sealing material 18. The discharge electrode 22 is made of a metal material having a good discharge characteristic such as a Ni / Fe alloy, and the base end portion 22a of each discharge electrode 22 is welded to the substantially central portion of the inner surface of the cap 16. The cap 16 is made of a clad material having a thickness of 0.2 to 0.4 mm in which a first metal layer 16a and a second metal layer 16b are laminated, and the first metal layer 16a located on the inner surface side is The second metal layer 16b, which is composed of a 42.6 alloy having a thermal expansion coefficient substantially equal to that of the sealing material 18 and is located on the outer surface side, has a stronger oxidation resistance than the 42.6 alloy, and It is composed of a 50Ni.Fe alloy having a coefficient of thermal expansion approximately equal to that of the 6 alloy. Although not shown, the surface of the first metal layer 16a has
A metal oxide film made of chromium oxide (Cr 2 O 3 ) is formed.
【００２１】すなわち、この第２のサージ吸収素子40
は、上記第１のサージ吸収素子10から電圧非直線抵抗体
26を取り除いた点に特徴があり、他の構成は第１のサー
ジ吸収素子10と実質的に同じである。したがって、キャ
ップ16に湿潤水素処理を施す際に、封着材18と接するキ
ャップ16内面（第１の金属層16ａ）にのみ金属酸化膜32
が形成され、リード線30等と接続されるキャップ16外面
（第２の金属層16ｂ）には、電気的接続を阻害する金属
酸化膜がほとんど形成されないという効果も、同様に享
受することができる。That is, this second surge absorbing element 40
Is a voltage nonlinear resistor from the first surge absorbing element 10
It is characterized in that 26 is removed, and the other configuration is substantially the same as that of the first surge absorbing element 10. Therefore, when the cap 16 is subjected to wet hydrogen treatment, the metal oxide film 32 is formed only on the inner surface (first metal layer 16a) of the cap 16 that is in contact with the sealing material 18.
The same effect can be obtained in that a metal oxide film that hinders electrical connection is hardly formed on the outer surface (second metal layer 16b) of the cap 16 that is formed and is connected to the lead wire 30 and the like. .
【００２２】[0022]
【発明の効果】本発明に係るサージ吸収素子にあって
は、上記のように外囲器の開口部を閉塞するキャップ
を、封着材と接する第１の金属層と、該第１の金属層よ
りも耐酸化性の強い第２の金属層との積層構造と成した
ため、キャップ内面に封着材との馴染みを良好にするた
めの金属酸化膜を形成する際に、同時にキャップ外面に
金属酸化膜が強固に形成されてしまうことを防止でき
る。したがって、キャップ外面にリード線等を接続する
際に、金属酸化膜を除去するための研磨作業が全く不要
となるか、必要としても極簡単な研磨作業で済むため、
その分、製造の効率化及びコストの低廉化が図れる。ま
た、研磨工程を通じてサージ吸収素子が劣化したり、有
害な粉塵が発生するといった問題は当然に生じない。In the surge absorbing element according to the present invention, the cap for closing the opening of the envelope as described above is provided with the first metal layer in contact with the sealing material, and the first metal. Since it has a laminated structure with a second metal layer that has stronger oxidation resistance than the metal layer, when forming a metal oxide film on the inner surface of the cap for better compatibility with the sealing material, the metal is formed on the outer surface of the cap at the same time. It is possible to prevent the oxide film from being strongly formed. Therefore, when connecting a lead wire or the like to the outer surface of the cap, the polishing work for removing the metal oxide film is completely unnecessary, or even if necessary, a very simple polishing work can be performed.
To that extent, manufacturing efficiency and cost reduction can be achieved. Further, there is naturally no problem that the surge absorbing element is deteriorated or harmful dust is generated through the polishing process.
【図１】本発明に係るサージ吸収素子の一例を示す断面
図である。FIG. 1 is a sectional view showing an example of a surge absorber according to the present invention.
【図２】上記サージ吸収素子のキャップと封着材、及び
外囲器との接合部分を示す拡大断面図である。FIG. 2 is an enlarged cross-sectional view showing a joint portion between the cap of the surge absorbing element, a sealing material, and an envelope.
【図３】本発明に係るサージ吸収素子の他の例を示す断
面図である。FIG. 3 is a cross-sectional view showing another example of the surge absorber according to the present invention.
【図４】従来のサージ吸収素子の一例を示す断面図であ
る。FIG. 4 is a sectional view showing an example of a conventional surge absorbing element.
10 第１のサージ吸収素子 12 外囲器 14 開口部 16 キャップ 16ａ 第１の金属層 16ｂ 第２の金属層 18 封着材 20 気密容器 22 放電電極 24 放電間隙 26 電圧非直線抵抗体 32 金属酸化膜 40 第２のサージ吸収素子 10 First surge absorbing element 12 Enclosure 14 Opening 16 Cap 16a First metal layer 16b Second metal layer 18 Sealing material 20 Airtight container 22 Discharge electrode 24 Discharge gap 26 Voltage nonlinear resistor 32 Metal oxide Membrane 40 Second surge absorber
─────────────────────────────────────────────────────
─────────────────────────────────────────────────── ───
【手続補正書】[Procedure amendment]
【提出日】平成６年８月２２日[Submission date] August 22, 1994
【手続補正１】[Procedure Amendment 1]
【補正対象書類名】図面[Document name to be corrected] Drawing
【補正対象項目名】全図[Correction target item name] All drawings
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【図１】 [Figure 1]
【図２】 [Fig. 2]
【図３】 [Figure 3]
【図４】 [Figure 4]
Claims (8)
口部を閉塞するキャップと、上記外囲器の開口部とキャ
ップとを接合させる封着材とから成る気密容器内に、少
なくとも放電ガスと、複数の放電電極間に形成された放
電間隙とを封入して成るサージ吸収素子において、上記
キャップを、上記封着材と接する第１の金属層と、該第
１の金属層よりも耐酸化性の強い第２の金属層との積層
構造と成し、上記第１の金属層の表面の中、少なくとも
上記封着材と接する部分に金属酸化膜が形成されている
ことを特徴とするサージ吸収素子。1. An airtight container comprising an envelope having an opening, a cap that closes the opening of the envelope, and a sealing material that joins the opening of the envelope and the cap. In a surge absorbing element formed by enclosing at least a discharge gas and a discharge gap formed between a plurality of discharge electrodes, the cap includes a first metal layer in contact with the sealing material, and the first metal layer. It has a laminated structure with a second metal layer having stronger oxidation resistance than the metal layer, and a metal oxide film is formed on at least a portion of the surface of the first metal layer that is in contact with the sealing material. A surge absorbing element characterized by the above.
を特徴とする請求項１に記載のサージ吸収素子。2. The surge absorbing element according to claim 1, wherein the sealing material is a low melting point glass.
張係数が略等しい金属によって形成されていることを特
徴とする請求項１または２に記載のサージ吸収素子。3. The surge absorbing element according to claim 1, wherein the first metal layer is formed of a metal having a thermal expansion coefficient substantially equal to that of the sealing material.
って形成されていることを特徴とする請求項１乃至３の
何れかに記載のサージ吸収素子。4. The surge absorber according to claim 1, wherein the first metal layer is made of a 42.6 alloy.
と熱膨張係数が略等しい金属によって形成されているこ
とを特徴とする請求項１乃至４の何れかに記載のサージ
吸収素子。5. The surge absorber according to claim 1, wherein the second metal layer is formed of a metal having a thermal expansion coefficient substantially equal to that of the first metal layer. element.
金によって形成されていることを特徴とする請求項１乃
至５の何れかに記載のサージ吸収素子。6. The surge absorption element according to claim 1, wherein the second metal layer is formed of a 50Ni.Fe alloy.
接続されていることを特徴とする請求項１乃至６の何れ
かに記載のサージ吸収素子。7. The surge absorbing element according to claim 1, further comprising a voltage non-linear resistor connected between the discharge electrodes.
口部を閉塞するキャップと、上記外囲器の開口部とキャ
ップとを接合させる封着材とから成る気密容器内に、少
なくとも放電ガスと、複数の放電電極間に形成された放
電間隙とを封入して成り、上記キャップを、上記封着材
と接する第１の金属層と、該第１の金属層よりも耐酸化
性の強い第２の金属層との積層構造と成し、上記第１の
金属層の表面の中、少なくとも上記封着材と接する部分
に金属酸化膜を形成して成るサージ吸収素子の製造方法
であって、上記金属酸化膜を、上記キャップ全体を湿潤
水素中に保持し、これに加熱処理を施すことによって形
成することを特徴とするサージ吸収素子の製造方法。8. An airtight container comprising an envelope having an opening, a cap for closing the opening of the envelope, and a sealing material for joining the opening of the envelope and the cap. A first metal layer in which at least a discharge gas and a discharge gap formed between a plurality of discharge electrodes are sealed, and the cap is in contact with the sealing material; A surge absorbing element having a laminated structure with a second metal layer having strong oxidation resistance, wherein a metal oxide film is formed on at least a portion of the surface of the first metal layer in contact with the sealing material. A method of manufacturing a surge absorbing element, characterized in that the metal oxide film is formed by holding the entire cap in wet hydrogen and subjecting it to heat treatment.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6145554A JP2853010B2 (en) | 1994-06-02 | 1994-06-02 | Surge absorbing element and method of manufacturing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6145554A JP2853010B2 (en) | 1994-06-02 | 1994-06-02 | Surge absorbing element and method of manufacturing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH07335368A true JPH07335368A (en) | 1995-12-22 |
| JP2853010B2 JP2853010B2 (en) | 1999-02-03 |
Family
ID=15387858
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP6145554A Expired - Lifetime JP2853010B2 (en) | 1994-06-02 | 1994-06-02 | Surge absorbing element and method of manufacturing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2853010B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005008853A1 (en) * | 2003-07-17 | 2005-01-27 | Mitsubishi Materials Corporation | Surge absorber |
| US7733622B2 (en) | 2003-02-28 | 2010-06-08 | Mitsubishi Materials Corporation | Surge absorber and production method therefor |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5129861A (en) * | 1974-09-06 | 1976-03-13 | Torio Kk | Ad henkanki |
| JPH0668950A (en) * | 1992-08-21 | 1994-03-11 | Mitsubishi Materials Corp | Sealing electrode and surge absorber using the same |
-
1994
- 1994-06-02 JP JP6145554A patent/JP2853010B2/en not_active Expired - Lifetime
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5129861A (en) * | 1974-09-06 | 1976-03-13 | Torio Kk | Ad henkanki |
| JPH0668950A (en) * | 1992-08-21 | 1994-03-11 | Mitsubishi Materials Corp | Sealing electrode and surge absorber using the same |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7733622B2 (en) | 2003-02-28 | 2010-06-08 | Mitsubishi Materials Corporation | Surge absorber and production method therefor |
| WO2005008853A1 (en) * | 2003-07-17 | 2005-01-27 | Mitsubishi Materials Corporation | Surge absorber |
| US7660095B2 (en) | 2003-07-17 | 2010-02-09 | Mitsubishi Materials Corporation | Surge protector |
| US7937825B2 (en) | 2003-07-17 | 2011-05-10 | Mitsubishi Materials Corporation | Method of forming a surge protector |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2853010B2 (en) | 1999-02-03 |
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