JPH02239582A - Sealing material for spark plug - Google Patents
Sealing material for spark plugInfo
- Publication number
- JPH02239582A JPH02239582A JP5854189A JP5854189A JPH02239582A JP H02239582 A JPH02239582 A JP H02239582A JP 5854189 A JP5854189 A JP 5854189A JP 5854189 A JP5854189 A JP 5854189A JP H02239582 A JPH02239582 A JP H02239582A
- Authority
- JP
- Japan
- Prior art keywords
- sealing material
- weight
- glass
- spark plug
- insulator
- 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.)
- Pending
Links
- 239000003566 sealing material Substances 0.000 title claims abstract description 56
- 239000011521 glass Substances 0.000 claims abstract description 56
- 239000012212 insulator Substances 0.000 claims abstract description 28
- 239000000919 ceramic Substances 0.000 claims abstract description 23
- 239000000945 filler Substances 0.000 claims abstract description 18
- 239000011231 conductive filler Substances 0.000 claims abstract description 17
- 238000007789 sealing Methods 0.000 claims abstract description 9
- 229910052751 metal Inorganic materials 0.000 claims description 12
- 239000002184 metal Substances 0.000 claims description 12
- 239000002245 particle Substances 0.000 claims description 7
- 150000004767 nitrides Chemical class 0.000 claims description 3
- 238000002156 mixing Methods 0.000 abstract description 6
- 238000001816 cooling Methods 0.000 abstract description 4
- 238000000034 method Methods 0.000 abstract description 4
- 230000035939 shock Effects 0.000 abstract description 3
- 230000000704 physical effect Effects 0.000 abstract description 2
- 239000000463 material Substances 0.000 description 15
- 239000000843 powder Substances 0.000 description 9
- 239000005388 borosilicate glass Substances 0.000 description 8
- 239000000203 mixture Substances 0.000 description 6
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- 229910052581 Si3N4 Inorganic materials 0.000 description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 4
- 229910000990 Ni alloy Inorganic materials 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- 229910000975 Carbon steel Inorganic materials 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 239000010962 carbon steel Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- -1 oxygen nitride Chemical class 0.000 description 2
- 238000012856 packing Methods 0.000 description 2
- 229910010271 silicon carbide Inorganic materials 0.000 description 2
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 2
- MTPVUVINMAGMJL-UHFFFAOYSA-N trimethyl(1,1,2,2,2-pentafluoroethyl)silane Chemical compound C[Si](C)(C)C(F)(F)C(F)(F)F MTPVUVINMAGMJL-UHFFFAOYSA-N 0.000 description 2
- 229910000505 Al2TiO5 Inorganic materials 0.000 description 1
- 229910052580 B4C Inorganic materials 0.000 description 1
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 241000872198 Serjania polyphylla Species 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910000410 antimony oxide Inorganic materials 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- QDWJUBJKEHXSMT-UHFFFAOYSA-N boranylidynenickel Chemical compound [Ni]#B QDWJUBJKEHXSMT-UHFFFAOYSA-N 0.000 description 1
- INAHAJYZKVIDIZ-UHFFFAOYSA-N boron carbide Chemical compound B12B3B4C32B41 INAHAJYZKVIDIZ-UHFFFAOYSA-N 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000009863 impact test Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- AABBHSMFGKYLKE-SNAWJCMRSA-N propan-2-yl (e)-but-2-enoate Chemical compound C\C=C\C(=O)OC(C)C AABBHSMFGKYLKE-SNAWJCMRSA-N 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 239000000565 sealant Substances 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 229910002076 stabilized zirconia Inorganic materials 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明はスパークプラグの、端子電極と中心電極とを接
着するためのシール材に閏する．［従来の技術Ｊ
特公昭５７− １９８４２号公報には、アルミナ製絶縁
体を用いたスパークプラグの、端子電極と中心電極との
接着用のシール材が開示されている．このシール材は、
ガラスと、導電性金属粉と、希土類元素の酸化物および
炭化物の１種以」〕とからなる．
［発明が解決しようとするｎ題］
しかるに、従来のシール材は、つぎような欠点がある．
窒化物や酸素窒素化物のセラミック焼結体で形成された
絶縁体に上記シール材を用いると、シール材の熱膨張係
数が前記絶縁体よりかなり大きく、かつシール材と絶縁
体の濡れ性が悪いため、冷却時にシール材と絶縁体との
間にＲ間が生じる．このため、スパークプラグがｖａ返
し機械的な衝撃を受けると、端子電極や中心電極との接
合が離れ、導通不良を誘発する．
本発明の目的は、端子電極と中心電極との接合時、冷却
過程で、低膨張セラミック焼結体で形成された絶縁体と
シール材との間に隙間が生じ難く、かつスパークプラグ
が衝撃を受けても接合が離れ難いシール材の提供にある
．
［課題を解決するための手段］
上記目的達成のため、本発明はつぎの構成を採用した．
■シール材はつぎの楕成上りなる．筒状主体金具と、該
主体金具に嵌め込まれ、窒化物および酸素窒素化物セラ
ミック焼結体などを主体として形成されるとともに、？
．７Ｘ１０−’／”Ｃ以下の熱膨脹係数を有する軸孔付
きの絶縁体と、前記軸孔の先端側に嵌め込まれる中心電
掻および後端側に嵌め込まれる端子電極とを有するスパ
ークプラグに用いられ、前記中心電極の後端と、端子電
極の先端とを電気的に接続するとともに前記軸孔内で加
熱封着するシール材において、２０重量％〜３５重量％
の範囲で、かつ、熱ｍ＊係数が７．７Ｘ１０−６／℃以
下である絶縁性セラミックフィラーと、１０重量％〜３
０重量％の導電性フィラーと、３５重量％〜７０重量％
のガラスとを調合してなる．■シール材は、前記■の構
成を有し、かつ、つぎの構成よりなる．スパークプラグ
に用いられ、シール材は、熱膨張係数を前記絶縁体に対
し８％〜７５％の範囲内とされる２０重量％〜３５重量
％の絶縁性セラミックフィラーと、１０重量％〜３０重
量％の導電性フ２イラーと、３５重量％〜７０重量％で
、かつ、平均粒径が３５０μ以下のガラスとを調合し、
加熱封着後、２０℃における電気抵抗値が２５ｋΩ以下
である．
［作用および発明の効果］
本発明はつぎの作用および効果を奏する．く請求項１に
ついて〉
シール材は、２０１１１１％〜３５重量％の範囲で、か
つ、熱ｍ張係数が７．７Ｘ１０−６／℃以下である絶縁
性セラミックフィラーと、１０重量％〜３０．Ｉｊ量％
の導電性フィラーと、３５重量％〜７０重産％のガラス
とを調合している．このため、シール材の熱膨張係数が
下がり、中心電極の後端と端子電極の先端とを軸孔内に
加熱封着する際、シール材の収縮が少なく、絶縁体とシ
ール材との間に隙間が生じ難くて密着性に優れる．また
、密着性に優れるので、スパークプラグが繰返し機械的
な衝撃を受でも、端子電極と中心電極との接合が離れた
りぜず、軸孔への封着が保たれ導通路は安定に確保され
る．
数値限定の理由はつぎのとおりである．絶縁性セラミッ
クフィラーが２０重量％未満であると少なすぎシール材
の熱ｉｌＩ５ｉ係数を下げることが困難であり、３５重
量％を越えると多すぎ端子電極の封着が困難になる．ま
た、熱膨張係数が７ ． ７ Ｘ １ ０−６／℃を越
えるものを用いると導電性ガラスシール材の熱膨張係数
を下げることが困難となる．
導電性フィラーが１０重量％未満であるとシール材の電
気抵抗値が高くなりすぎ、３０重量％を越えると、ホウ
クイ酸系のガラスの占める割合が少なくなり端子電極の
封着が困難になる．ガラスが３５重量％未満であると端
子電極の封着が困難になり、７０重量％を越えると導電
性フィラーおよび絶縁性セラミックフィラーの占める割
合が少なくなり必要量が得られない．く請求項２につい
て〉
使用する絶縁性セラミックフィラーの熱膨張係数を前記
絶縁体に対し８％〜７５％の範囲と限定している．この
ため、シール材は絶縁体の熱膨張係数に近似しやすくな
る．よって、各材料の調合割合の著しい精密さを必要と
せず上記記載の作用効果が得られる，
ガラスの平均粒径が３５０μ以下と限定し゛Ｃいるので
、加熱時、軸孔内への充填が良く、特に中心電極との封
着性を良好にできる．
シール材の電気抵抗値を、加熱封着後、２０℃で２５ｋ
Ωとしている．このため、火花エネルギーにより導電性
フィラーが焼け切れ難く、耐久性が向上する．
［実施ＰＡ］
本発明の楕成（請求項ｌ、２に対応）を第１図に示すス
パークプラグ１００に適用した各実施例を第１表〜第５
表とともに説明する．
第１図に示すごとく、導電性ガラスシール材１は、筒状
主体金具２と、該主体金具２に嵌め込まれる軸孔３ｌ付
きの絶縁体３と、前記軸孔３１の先端側に嵌め込まれる
中心電ｗｌ４および後端側に嵌め込まれる端子電極５と
を有するスパークプラグ１００の前記各電極４、５の後
端、先端に加熱封着されている．
導電性ガラスシール材１は、絶縁性セラミックフィラー
と、導電性フィラーと、ホウケイ酸系のガラスとを調合
してなる．絶縁性セラミックフイラーは、第１表のＦ１
〜Ｆ８、ＦＩＯ、Ｆｉｌに示すように、窒化珪素（Ｓｌ
ｊＮ４）．窒化アルミニウム（ＡＩ Ｎ） ．窒化硼素
（ＢＮ） 、珪酸（ＳｉＯ！）．燐酸ジルコニル［ （
ＺｒＯ）２ Ｐｉｏｔａ、チタン酸アルミニウム（ ’
Ｉ’ ｉ ０ ｘ ・Ａｊｚｏｓ）、窒化珪素トアル
ミナ、窒化硼素ト珪酸であり、これらは単体または混合
してその合計を２０重量％〜３５重量％とじている．ま
た、熱膨張率は、最大でも７．７Ｘ１０−’／”Ｃであ
り、好ましくは５、７×１０″゜６／℃以下である．導
電性フィラーは、粒径（以下略）１。５μのグラフデイ
ト、１μ以下のカーボンブラック、４５μの炭化硼素（
Ｂａ Ｃ） 、３０μの炭化珪素（ＳＬＣ）、１５μの
炭化チタン（ＴｉＣ）、３５μの銅粉、４０μの鉄粉、
２５μのアルミニウム粉、５５μの亜鉛粉４５μのフェ
ロボロン粉（ Ｆ ｅ −Ｂ ）、２５μのニッケルボ
ロン粉（Ｎｉ−Ｂ）、２．５μのチタニア（ＴＬＯｘ
）．５μのジルコニア（Ｚｒｏ２＞．５μの安定化ジル
コニア（５％Ｙ２０，）、３μの酸化アンチモン（Ｓｂ
ｚ Ｏ，）、１０μの酸化スズ（Ｓｎｏ２）であり、第
２表のｆ１・〜ｆｌ７に示す組成明細表のように単体ま
たは混合して１０重量％〜３０重量％としている．ホウ
ケイ酸系のガラスは、第３表に示す物性を有するガラス
Ａ（ホウゲイ酸ガラス）、ガラスＢ（ホウケイ酸バリウ
ムガラス）、ガラスＣ（ホウケイ酸ソーダガラス）、ガ
ラスＤ（ホウケイ酸リチウムガラス）、ガラスＥ（ホウ
ケイ酸鉛ガラス）を用い残部を槽成している．また、こ
れらのガラスの平均粒径は１４５μ〜２２５μである．
簡状主体金具２は、炭素鋼で作られ、先端のねじ部、後
端の後端部、中央の中胴部よりなる．ねじ部の外周には
機関への取付けねじ２１が形成され、先端面に，前記中
心電極４の先端を覆うように略Ｊ字状の外側電極２２（
ニッケル合金）が溶接されている．後端部の外周は六角
部２３が形成され、後端は内方にかしめられるとともに
線パッキン２４により絶縁体３を固定している．絶縁体
３は、窒化アルミニウム《第４表中では「窒ア』と略記
し以下のものも同様》、窒化珪素（窒珪）、アルミナ＋
３０％窒化アルミニウム（ア窒）、アルミナ＋３０％窒
化珪素＋２０％窒化アルミニウム（ア窒珪）で形成され
ている．この絶縁体３は、先端が径小の脚長部３２とな
り、中央はテーバ面を介し径大となり、後端は先端より
やや径大のコルゲーション部３３となっている．前記軸
孔３１は、脚長部３２（絶縁体３の先端》では径小に、
中央およびコルゲーション部３３（絶縁体３の後端）で
は段部３４を介し径大（直径４．５ｍｍ）に形成されて
いる．また、テーバ面３５は主体金具２の内壁に形成さ
れたテーバ面２６にパッキン２７を介して係止されてい
る．中心電極４は、丸棒状の脚部４１、該脚部４１の後
端部に設けられ前記段部３４に係止される鍔状部４２お
よびさらに該鍔状部４２の後に形成され、略矢羽状の頭
部４３からなる．また、中心電極４は、表皮が耐熱金属
であるニッケル合金４４（Ｎｉ９０％以上）であり、軸
芯には良熱伝導性金属である銅（Ｃｕ）４５が封入され
ている．この銅４５の封入状態は中心電極４の先端付近
ではニッケル合金４４の外表ｉＩｉＪ＝ｉでの距離を他
の部分より長くとり、頭部４３の中央付近で露出するよ
うに行われている．
端子電極５は、炭素鋼で形成されて、ニッケルメッキさ
れ、前記軸孔３１の後端側に嵌め込まれている．また、
後端は前記絶縁体３の後端より突出して配設されている
．
つぎに、スパークプラグ１００の導電性ガラスシール材
１の周辺部分の製造方法を説明する．■中心電極４を、
絶縁体３の径大の軸孔３１側から脚部４１を先にして差
し込む．
■第１表の絶縁性セラミックフィラー、第２表の組成の
導電性フィラー、および第３表のガラスを第４表の組成
となるように混合し、濃度５％のＰＶＡ水溶液、もしく
は同濃度のＣＭＣ溶液を適量加え、よく混合した後１０
０℃の恒温乾燥器中で乾燥させ導電性ガラスシール材】
，の素地粉末とする．
■つぎに、この素地粉末を径大〈内径４。５ ｍ ＋ｎ
）の軸孔３１から０、５ｇ〜０．６ｇ入れ、押棒（図
示せず）により約２００ｋｇの荷重をかけ、粉末の充填
プレスを行う．
■８５０℃〜９５０℃で約１０分同加熱し、素地粉末を
溶融させ端子電極５を圧入する．その後室温《２０℃》
まで冷却させる．
つぎに、第５表について説明する．第５表は、第４表の
各実施例のもののガラスシールの封着状態と、冷却後の
抵抗値を測定して記載している５また、ＪＩＳＢ−８０
３１ ３．３の衝撃試験器による耐衝撃性（抵抗値の
変化の有無），ＪＩＳＤ−５１０２ ３．１１による
負荷寿命試＠（抵抗値の変化率）結果もあわせて記載し
ている．「接合状態』の欄において、ガラスシール接合
が良好なものを「○』、不良なものを「×」、端子圧入
不可のものを［不可』としている．『耐衝撃性」は、各
実施例船のスパークプラグｌ００に前記衝撃試験器で楕
撃を加え、試験終了後に抵抗値を測定し、２０℃の抵抗
値と比較して抵抗値に変化が認められないものを「０」
、変化を億か起こすものを「Δ』、変化を起こすものを
１゛×Ｊとしている．
『負荷寿命試験」は、各実施例社のスパークプラグ１０
０を繰り返しスパークさせ導電性ガラスシール材１の導
電経路の耐久性を調べ、抵抗値の変化率がＪＩＳ規格内
のものを１０」、外れたものを［×１としている．
つぎに、導電性ガラスシール材１を用いたスパークプラ
グ１００の作用および効果を述べる．（あ）第５表にお
いて、つぎのちのは、電極４、５の後端と先端とが軸孔
３１内で加熱封着できないか困難である．
実施例Ｎ１１７、２０、２６、２９、３２、４４、５０
、６２、７１．また、実施例随１、５、８、１２．１５
− １８、２１、２４、２７、３０、３３、３６、３
９、４５、４８、５１、５５、５９、６３、６４、６５
、６６、７０、７１のものは、絶縁性セラミックフィラ
ーがＯ重量％〜２０重量％未満であり、更に実施例Ｎ［
１４、７、１１、１４、１７、２０、２６、２９、３２
、４４、５０、５４、６２のものは絶縁性セラミックフ
ィラーが４０重量％以上であり除外される．本発明品の
導電性ガラスシール材１は、２０重量％〜３５重厘％の
範囲で、かつ、熱ｍ張係数が７。７ Ｘ １ ０ −’
／℃以下である第１表記載の絶縁性セラミックフィラー
（Ｐｉ〜Ｆ８、ＦＩＯ、Ｆ１１）と、１０重量％〜３０
重量％の範囲で、第２表記載の導電性フィラー（ｆｌ〜
ｆ１７）と、３５重量％〜７０重量％の範囲で、第３表
記載のガラス《ガラスＡ〜Ｅ）とを調合している．この
ため導電性ガラスシール材１の熱ｍ張係数が下がり、中
心電極４の後端と端子電極５の先端とを軸孔３１内に加
熱封着する際、導電性ガラスシール材１の収縮が少なく
絶縁体３とシール材１との間に隙間が生じ難くて密着性
が良い．また、密着性が良いので、スパークブラグ１０
０にＪＩＳＢ−８０３１による耐衝撃試験を行った場合
、大部分は良好な耐久性を示す．しかし、つぎのらのは
耐衝撃試験で抵抗値の変化を温か起こし、ＪＩＳＤ−５
１０２による負１命試験でＪＩＳ規格を外れる．これは
、導電性ガラスシール材１を楕成する絶縁性セラミック
フィラー、導電性フィラー、およびガラスに用いる各材
料の種類によってそれらの最適値の範囲が異なるためで
ある．実施例Ｎｔ１ｉ、４、８、１１、１２、１４、１
５、１７、２１、２４、２７、３０、３３、３６、３９
、４５、４８、５９、６０．くい》使用する絶縁性セラ
ミックフィラーの熱膨張係数を絶縁体３に対し８％〜７
５％の範囲と限定している．このため、導電性ガラスシ
ール材１は絶縁体の熱膨張係数に近似しやすくなる．よ
って、各材料の調合割合の著しい精密さを必要とせず中
心ｔ極４との良好な封着性が得られる．また、ガラスの
平均粒径を３５０μ以下と限定している．このため、鍔
状部４２や頭部４３と、軸孔３１との隙問に導電性ガラ
スシール材１が良好に充填される．上記理由により、．
ＪＩＳＢ−８０３１による耐衝撃性は大部分は良好であ
る。[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a sealing material for bonding a terminal electrode and a center electrode of a spark plug. [Prior Art J Japanese Patent Publication No. 19842/1984 discloses a sealing material for bonding a terminal electrode and a center electrode of a spark plug using an alumina insulator. This sealing material is
It consists of glass, conductive metal powder, and one or more rare earth element oxides and carbides. [Problems to be solved by the invention] However, conventional sealing materials have the following drawbacks. When the above sealing material is used for an insulator formed of a ceramic sintered body of nitride or oxygen nitride, the coefficient of thermal expansion of the sealing material is considerably larger than that of the above-mentioned insulator, and the wettability between the sealing material and the insulator is poor. Therefore, an R gap is created between the seal material and the insulator during cooling. For this reason, when the spark plug is subjected to a mechanical shock due to va-return, the connection with the terminal electrode and center electrode separates, causing poor conduction. An object of the present invention is to prevent a gap from forming between an insulator made of a low expansion ceramic sintered body and a sealing material during the cooling process when joining a terminal electrode and a center electrode, and to prevent the spark plug from being subjected to impact. The objective is to provide a sealing material that does not easily come apart even when exposed to heat. [Means for Solving the Problems] To achieve the above object, the present invention employs the following configuration. ■The sealing material has the following oval shape. A cylindrical metal shell, fitted into the metal shell, and formed mainly of nitride and oxygen nitride ceramic sintered bodies, and ?
．． Used in a spark plug having an insulator with a shaft hole having a coefficient of thermal expansion of 7X10-'/''C or less, a center electrode fitted into the front end side of the shaft hole, and a terminal electrode fitted into the rear end side, 20% by weight to 35% by weight of the sealing material that electrically connects the rear end of the center electrode and the tip of the terminal electrode and seals them by heat in the shaft hole.
and an insulating ceramic filler with a thermal m* coefficient of 7.7X10-6/°C or less, and 10% by weight to 3% by weight.
0% by weight conductive filler and 35% to 70% by weight
It is made by mixing with glass. (2) The sealing material has the structure (2) above, and also has the following structure. The sealing material used in the spark plug includes 20% to 35% by weight of an insulating ceramic filler whose thermal expansion coefficient is within the range of 8% to 75% relative to the insulator, and 10% to 30% by weight. % conductive filler and 35% to 70% by weight glass with an average particle size of 350μ or less,
After heat sealing, the electrical resistance value at 20°C is 25 kΩ or less. [Actions and Effects of the Invention] The present invention has the following actions and effects. Regarding Claim 1> The sealing material contains an insulating ceramic filler in a range of 201111% to 35% by weight and having a thermal tensile coefficient of 7.7X10-6/°C or less, and 10% to 30% by weight. Ij amount%
The conductive filler is mixed with 35% to 70% glass by weight. For this reason, the coefficient of thermal expansion of the sealing material decreases, and when the rear end of the center electrode and the tip of the terminal electrode are heat-sealed into the shaft hole, there is less shrinkage of the sealing material, and there is a gap between the insulator and the sealing material. Excellent adhesion with no gaps. In addition, it has excellent adhesion, so even if the spark plug is subjected to repeated mechanical shocks, the connection between the terminal electrode and center electrode will not separate, and the seal to the shaft hole will be maintained, ensuring a stable conduction path. Ru. The reason for the numerical limitation is as follows. If the amount of insulating ceramic filler is less than 20% by weight, it is too small and it is difficult to lower the heat ilI5i coefficient of the sealing material, and if it exceeds 35% by weight, it is too large and it becomes difficult to seal the terminal electrodes. Also, the coefficient of thermal expansion is 7. If a material with a coefficient exceeding 7 x 10-6/°C is used, it will be difficult to lower the thermal expansion coefficient of the conductive glass sealing material. If the content of the conductive filler is less than 10% by weight, the electrical resistance value of the sealing material will be too high, and if it exceeds 30% by weight, the proportion of the borosilicate glass will decrease, making it difficult to seal the terminal electrodes. If the glass content is less than 35% by weight, it will be difficult to seal the terminal electrode, and if it exceeds 70% by weight, the proportion of the conductive filler and the insulating ceramic filler will be too small to obtain the required amount. Regarding Claim 2> The coefficient of thermal expansion of the insulating ceramic filler used is limited to a range of 8% to 75% with respect to the insulator. Therefore, the thermal expansion coefficient of the sealing material can be easily approximated to that of the insulator. Therefore, the above-mentioned effects can be obtained without requiring extreme precision in the mixing ratio of each material.Since the average particle size of the glass is limited to 350μ or less, it can be easily filled into the shaft hole during heating. In particular, the sealing properties with the center electrode can be improved. The electrical resistance value of the sealing material is 25k at 20℃ after heat sealing.
It is set to Ω. Therefore, the conductive filler is difficult to burn out due to spark energy, improving durability. [Implementation PA] Examples in which the elliptical structure of the present invention (corresponding to claims 1 and 2) is applied to the spark plug 100 shown in FIG. 1 are shown in Tables 1 to 5.
This will be explained along with the table. As shown in FIG. 1, the conductive glass sealing material 1 includes a cylindrical metal shell 2, an insulator 3 with a shaft hole 3l fitted into the metal shell 2, and a center fitted into the tip side of the shaft hole 31. The rear end and tip of each of the electrodes 4 and 5 of the spark plug 100 has an electric terminal 4 and a terminal electrode 5 that is fitted into the rear end side. The conductive glass sealing material 1 is made by blending an insulating ceramic filler, a conductive filler, and a borosilicate glass. The insulating ceramic filler is F1 in Table 1.
~ As shown in F8, FIO, Fil, silicon nitride (Sl
jN4). Aluminum nitride (AIN). Boron nitride (BN), silicic acid (SiO!). Zirconyl phosphate [ (
ZrO)2 Piota, aluminum titanate ('
I' i0 The coefficient of thermal expansion is at most 7.7 x 10-'/"C, preferably 5.7 x 10"/"C or less. The conductive fillers include Graphdate with a particle size (hereinafter omitted) of 1.5μ, carbon black with a particle size of 1μ or less, and boron carbide (45μ).
Ba C), 30μ silicon carbide (SLC), 15μ titanium carbide (TiC), 35μ copper powder, 40μ iron powder,
25μ aluminum powder, 55μ zinc powder, 45μ ferroboron powder (F e -B), 25μ nickel boron powder (Ni-B), 2.5μ titania (TLOx)
). 5μ zirconia (Zro2>.5μ stabilized zirconia (5% Y20,), 3μ antimony oxide (Sb
zO,), 10μ tin oxide (Sno2), and as shown in the composition table shown in Table 2, f1 to fl7, it is used singly or in combination to give 10% to 30% by weight. Borosilicate-based glasses include glass A (borosilicate glass), glass B (barium borosilicate glass), glass C (sodium borosilicate glass), glass D (lithium borosilicate glass), and glass D (lithium borosilicate glass), which have the physical properties shown in Table 3. The rest of the tank is made of glass E (lead borosilicate glass). Moreover, the average particle diameter of these glasses is 145μ to 225μ.
The simple metal shell 2 is made of carbon steel and consists of a threaded portion at the tip, a rear end portion at the rear end, and a middle body portion at the center. A mounting screw 21 to the engine is formed on the outer periphery of the threaded portion, and a substantially J-shaped outer electrode 22 (
Nickel alloy) is welded. A hexagonal part 23 is formed on the outer periphery of the rear end, and the rear end is caulked inward and the insulator 3 is fixed with a wire packing 24. The insulator 3 is made of aluminum nitride (abbreviated as "nitria" in Table 4 and the same applies to the following), silicon nitride (silicon nitride), alumina +
It is made of 30% aluminum nitride (anitride), alumina + 30% silicon nitride + 20% aluminum nitride (silicon anitride). This insulator 3 has a long leg portion 32 having a small diameter at the tip, a large diameter portion at the center through a tapered surface, and a corrugation portion 33 having a slightly larger diameter at the rear end. The shaft hole 31 has a smaller diameter at the long leg portion 32 (the tip of the insulator 3).
The central and corrugated portions 33 (rear end of the insulator 3) are formed with a large diameter (4.5 mm in diameter) via a stepped portion 34. Further, the tapered surface 35 is locked to a tapered surface 26 formed on the inner wall of the metal shell 2 via a packing 27. The center electrode 4 includes a round bar-shaped leg 41, a flange 42 provided at the rear end of the leg 41 and locked to the step 34, and further formed behind the flange 42. It consists of a feather-like head 43. The outer surface of the center electrode 4 is made of a nickel alloy 44 (90% or more Ni), which is a heat-resistant metal, and the axial core is filled with copper (Cu) 45, which is a metal with good thermal conductivity. The copper 45 is encapsulated in such a way that near the tip of the center electrode 4, the distance from the outer surface iIiJ=i of the nickel alloy 44 is longer than in other parts, and the copper 45 is exposed near the center of the head 43. The terminal electrode 5 is made of carbon steel, plated with nickel, and fitted into the rear end of the shaft hole 31. Also,
The rear end is arranged to protrude from the rear end of the insulator 3. Next, a method for manufacturing the peripheral portion of the conductive glass sealing material 1 of the spark plug 100 will be explained. ■Center electrode 4,
Insert the insulator 3 from the large diameter shaft hole 31 side with the leg 41 first. ■ Mix the insulating ceramic filler in Table 1, the conductive filler with the composition in Table 2, and the glass in Table 3 to have the composition in Table 4, and use a PVA aqueous solution with a concentration of 5% or a PVA aqueous solution with the same concentration. After adding an appropriate amount of CMC solution and mixing well,
Conductive glass sealing material dried in a constant temperature dryer at 0℃]
, as a base powder. ■Next, this base powder is made into a large diameter (inner diameter 4.5 m + n
), 0.5 to 0.6 g is put into the shaft hole 31 of the powder, and a load of about 200 kg is applied using a push rod (not shown) to perform a powder filling press. ■Heat at 850°C to 950°C for about 10 minutes to melt the base powder and press-fit the terminal electrode 5. Then room temperature (20℃)
Cool until cooled. Next, Table 5 will be explained. Table 5 shows the sealed state of the glass seal and the resistance value after cooling of each example in Table 4.
31 The results of impact resistance (presence or absence of change in resistance value) using the impact tester in 3.3 and load life test @ (rate of change in resistance value) according to JISD-5102 3.11 are also listed. In the ``Joining condition'' column, items with good glass seal bonding are marked as ``○'', those with poor bonding are marked as ``x'', and items that cannot be press-fitted with terminals are marked as ``impossible''. "Impact resistance" is determined by applying an elliptical impact to the spark plug 100 of each example ship using the impact tester, measuring the resistance value after the test, and comparing it with the resistance value at 20 degrees Celsius. "0" for things that cannot be done
, the one that causes a change is "Δ", and the one that causes a change is 1゛×J.
The durability of the conductive path of the conductive glass sealing material 1 was examined by repeatedly sparking 0, and the rate of change in resistance value was rated as 10'' if it was within the JIS standard, and 1 if it was outside the JIS standard. Next, the functions and effects of the spark plug 100 using the conductive glass sealing material 1 will be described. (A) In Table 5, in the following case, it is difficult to heat seal the rear ends and tips of the electrodes 4 and 5 within the shaft hole 31. Examples N117, 20, 26, 29, 32, 44, 50
, 62, 71. Also, Examples 1, 5, 8, 12.15
- 18, 21, 24, 27, 30, 33, 36, 3
9, 45, 48, 51, 55, 59, 63, 64, 65
, 66, 70, and 71, the insulating ceramic filler is O weight % to less than 20 weight %, and Example N[
14, 7, 11, 14, 17, 20, 26, 29, 32
, 44, 50, 54, and 62 have an insulating ceramic filler content of 40% by weight or more and are excluded. The conductive glass sealing material 1 of the present invention has a content in the range of 20% by weight to 35% by weight, and a thermal tensile coefficient of 7.7 x 10 -'
/°C or less and the insulating ceramic fillers listed in Table 1 (Pi to F8, FIO, F11) and 10% by weight to 30% by weight.
The conductive fillers listed in Table 2 (fl~
f17) and the glasses listed in Table 3 (Glass A to E) in the range of 35% to 70% by weight. Therefore, the thermal tensile coefficient of the conductive glass sealing material 1 decreases, and when the rear end of the center electrode 4 and the tip of the terminal electrode 5 are heat-sealed in the shaft hole 31, the contraction of the conductive glass sealing material 1 is reduced. There are few gaps between the insulator 3 and the sealing material 1, resulting in good adhesion. In addition, since it has good adhesion, Spark Blag 10
When the impact resistance test according to JISB-8031 was conducted on 0.0, most of them showed good durability. However, the next one caused a change in resistance value in the impact test, and was JISD-5.
The negative 1 life test by 102 deviates from the JIS standard. This is because the range of their optimum values differs depending on the type of insulating ceramic filler forming the conductive glass sealing material 1, the conductive filler, and each material used for the glass. Examples Nt1i, 4, 8, 11, 12, 14, 1
5, 17, 21, 24, 27, 30, 33, 36, 39
, 45, 48, 59, 60. 》The coefficient of thermal expansion of the insulating ceramic filler used is 8% to 7 relative to the insulator 3.
The range is limited to 5%. Therefore, the conductive glass sealing material 1 easily approximates the coefficient of thermal expansion of the insulator. Therefore, good sealing performance with the center t-pole 4 can be obtained without requiring extreme precision in the mixing ratio of each material. Additionally, the average particle size of the glass is limited to 350μ or less. Therefore, the conductive glass sealing material 1 is well filled into the gap between the flange portion 42, the head portion 43, and the shaft hole 31. Due to the above reasons.
Impact resistance according to JISB-8031 is mostly good.
導電性ガラスシール材の電気抵抗値を、加熱封着後、２
０℃で２５ｋΩとしている．このため、火花エネルギー
により導電性フィラーが焼け切れ難く、大部分、ＪＩＳ
Ｄ−５１０２による負荷寿命試験に優れた耐久性を奏す
る。The electrical resistance value of the conductive glass sealing material is 2 after heat sealing.
It is set to 25kΩ at 0℃. For this reason, the conductive filler is difficult to burn out due to spark energy, and most of the conductive filler is
It shows excellent durability in the load life test using D-5102.
つぎに、本発明の楕成（謂求項１、２に対応）を第２図
に示すスパークプラグ２００に適応した各実施例を第６
表とともに説明する．
第２図に示すごとく、下側導電性ガラスシール材６およ
び上側導電性ガラスシール材７は、抵抗体８を挟んで、
中心電極４の後端側と端子電極５の先端側に配され、ス
パークプラグ２００の軸孔３１内で加熱封着されている
．
各ガラスシール材６、７は第５表の組成割合で調合され
、抵抗体８は、ガラスＤ８０重量％、ジルコニア１５重
量％、カーボンブラック５重量％の組成割合で調合され
ている．それぞれの粉末重量はガラスシール材６が０．
２ｇ，ガラスシール材７が０．２ｇ〜０，６ｇ、抵抗体
８の抵抗材が０．６ｇである．また、加熱封着温度は９
５０℃、シール寸法１は全て１０ｍｒｎである．各実施
例より、下側導電性ガラスシール材６および上側導電性
ガラスシール材７は、つぎの作用効果を奏する．
実施例Ｎａ７７ （従来晶）に示す、アルミナ絶縁体く
第６表中では１′アル」と略記）では良好な耐久性を示
すガラスシール材料も、絶縁体が窒化物や酸素窒素化物
セラミック焼結体で形成された低ｉ張係数のものである
と、実施例ＮＱ７６（比較晶）に示すようにＪ ＩＳＢ
−８０３１の耐衝撃試験に対し、耐久性に劣る．
実施例ＮＱ７２、７３（発明晶）に示すように、下側導
電性ガラスシール材６および上側導電性ガラスシール材
７に本発明の構成を用いたスパークプラグ２００はＪＩ
ＳＢ−８０３１の耐衝撃試験に対し、優れた耐久性を示
す．しかし、実施例随７４、７５（比較晶》に示すよう
に、どちらかのガラスシール材に従来の材料を使用する
と耐久性に劣り、実用に供し得なくなる．
（以下余白）
第１表（Ａ）
第２表
次頁に続く
第１表ＣＢ）
第３表（Ａ）
第４表
第３表（Ｂ）
熱膨張係数
条件：
ｒ．
ｔ．
〜４００℃（×１０
６／℃）
第５表
第６表Next, we will discuss each embodiment in which the elliptical structure (corresponding to so-called claims 1 and 2) of the present invention is applied to the spark plug 200 shown in FIG.
This will be explained along with the table. As shown in FIG. 2, the lower conductive glass seal material 6 and the upper conductive glass seal material 7 sandwich the resistor 8.
They are arranged on the rear end side of the center electrode 4 and on the front end side of the terminal electrode 5, and are heat-sealed within the shaft hole 31 of the spark plug 200. Each of the glass sealing materials 6 and 7 was prepared with the composition ratios shown in Table 5, and the resistor 8 was prepared with a composition ratio of 80% by weight of glass D, 15% by weight of zirconia, and 5% by weight of carbon black. The powder weight of each glass seal material 6 is 0.
2g, the glass sealing material 7 weighs 0.2g to 0.6g, and the resistance material of the resistor 8 weighs 0.6g. In addition, the heat sealing temperature is 9
50℃, seal dimension 1 is all 10 mrn. From each example, the lower conductive glass seal material 6 and the upper conductive glass seal material 7 have the following effects. Example Na77 (conventional crystal) The alumina insulator (abbreviated as 1'Al in Table 6) shows good durability. As shown in Example NQ76 (comparative crystal), J ISB
- Poor durability in impact resistance test of 8031. As shown in Examples NQ72 and 73 (invention crystals), the spark plug 200 using the structure of the present invention for the lower conductive glass sealing material 6 and the upper conductive glass sealing material 7 is JI
Shows excellent durability in the impact resistance test of SB-8031. However, as shown in Examples 74 and 75 (comparative crystals), if conventional materials are used for either glass sealing material, the durability will be poor and it will not be practical. ) Table 2 Table 1 CB continued on next page) Table 3 (A) Table 4 Table 3 (B) Thermal expansion coefficient conditions: r. t. ~400℃ (×106/℃) Table 5 Table 6
第１図は実施例Ｎｌｌｌ〜ｌＩＱ７１に用いた、導電性
ガラスシール材が封着されたスパークプラグの部分断面
図である．
第２図は実施例Ｎ１１？２〜ｋ７７に用いた、上側導電
性ガラスシール材、下側導電性ガラスシール材が封着さ
れた、抵抗体を有するスパークプラグの部分断面図であ
る．
図中 １・・・導電性ガラスシール材（シール材）２・
・・主体金具 ３・・・絶縁体 ４・・・中心電極 ５
・・・端子電極 ６・・・下部導電性ガラスシール材（
シール材） ７・・・上部導電性ガラスシール材（シー
ル材） ８・・・抵抗体 ３１・・・軸孔 １００、２
００・・・スパークプラグFIG. 1 is a partial sectional view of a spark plug sealed with a conductive glass sealant, which was used in Examples Nllll to IIQ71. FIG. 2 is a partial sectional view of a spark plug having a resistor and having an upper conductive glass sealing material and a lower conductive glass sealing material sealed together, which was used in Examples N11?2 to K77. In the diagram 1... Conductive glass sealing material (sealing material) 2.
...Metal shell 3...Insulator 4...Center electrode 5
... Terminal electrode 6 ... Lower conductive glass sealing material (
Seal material) 7... Upper conductive glass seal material (seal material) 8... Resistor 31... Shaft hole 100, 2
00...Spark plug
Claims (1)
ラミック焼結体などを主体として形成されるとともに、
７．７×１０＾−＾６／℃以下の熱膨脹係数を有する軸
孔付きの絶縁体と、 前記軸孔の先端側に嵌め込まれる中心電極および後端側
に嵌め込まれる端子電極とを有するスパークプラグに用
いられ、 前記中心電極の後端と、端子電極の先端とを電気的に接
続するとともに前記軸孔内で加熱封着するシール材にお
いて、 ２０重量％〜３５重量％の範囲で、かつ、熱膨張係数が
７．７×１０＾−＾６／℃以下である絶縁性セラミック
フィラーと、 １０重量％〜３０重量％の導電性フィラーと、３５重量
％〜７０重量％のガラスと を調合してなることを特徴とするスパークプラグのシー
ル材。 ２）前記スパークプラグに用いられ、 前記シール材は、 熱膨張係数を前記絶縁体に対し８％〜７５％の範囲内と
される２０重量％〜３５重量％の絶縁性セラミックフィ
ラーと、 １０重量％〜３０重量％の導電性フィラーと、３５重量
％〜７０重量％で、かつ、平均粒径が３５０μ以下のガ
ラスと を調合し、加熱封着後、２０℃における電気抵抗値が２
５ｋΩ以下であることを特徴とするスパープラグのシー
ル材。[Scope of Claims] 1) A cylindrical metal shell, which is fitted into the metal shell and is formed mainly of nitride and oxygen-nitride ceramic sintered bodies, and
A spark plug having an insulator with a shaft hole having a coefficient of thermal expansion of 7.7×10^-^6/°C or less, a center electrode fitted into the front end side of the shaft hole, and a terminal electrode fitted into the rear end side of the shaft hole. in the sealing material used for electrically connecting the rear end of the center electrode and the tip of the terminal electrode and heat-sealing them in the shaft hole, in a range of 20% to 35% by weight, and An insulating ceramic filler with a thermal expansion coefficient of 7.7 x 10^-^6/℃ or less, 10% to 30% by weight of a conductive filler, and 35% to 70% by weight of glass are blended. A spark plug sealing material that has the characteristic of: 2) Used in the spark plug, the sealing material includes: 20% to 35% by weight of an insulating ceramic filler whose thermal expansion coefficient is within the range of 8% to 75% relative to the insulator; % to 30% by weight of conductive filler and 35% to 70% by weight of glass with an average particle size of 350μ or less are mixed, and after heat sealing, the electrical resistance value at 20°C is 2.
A spar plug sealing material characterized by a resistance of 5kΩ or less.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5854189A JPH02239582A (en) | 1989-03-10 | 1989-03-10 | Sealing material for spark plug |
| BR9001203A BR9001203A (en) | 1989-03-10 | 1990-03-09 | IGNITION SEAL SEALING MATERIAL FOR THE INTERNAL COMBUSTION ENGINE |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5854189A JPH02239582A (en) | 1989-03-10 | 1989-03-10 | Sealing material for spark plug |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH02239582A true JPH02239582A (en) | 1990-09-21 |
Family
ID=13087303
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5854189A Pending JPH02239582A (en) | 1989-03-10 | 1989-03-10 | Sealing material for spark plug |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JPH02239582A (en) |
| BR (1) | BR9001203A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003022886A (en) * | 2001-07-06 | 2003-01-24 | Ngk Spark Plug Co Ltd | Spark plug |
| JP2011084463A (en) * | 2009-09-15 | 2011-04-28 | Ngk Spark Plug Co Ltd | Spark plug |
| WO2020120121A1 (en) | 2018-12-13 | 2020-06-18 | Robert Bosch Gmbh | Spark plug resistance element and spark plug |
-
1989
- 1989-03-10 JP JP5854189A patent/JPH02239582A/en active Pending
-
1990
- 1990-03-09 BR BR9001203A patent/BR9001203A/en unknown
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003022886A (en) * | 2001-07-06 | 2003-01-24 | Ngk Spark Plug Co Ltd | Spark plug |
| US6744189B2 (en) | 2001-07-06 | 2004-06-01 | Ngk Spark Plug Co., Ltd. | Spark plug |
| CN100346545C (en) * | 2001-07-06 | 2007-10-31 | 日本特殊陶业株式会社 | Sparking plug |
| KR100859068B1 (en) * | 2001-07-06 | 2008-09-17 | 니혼도꾸슈도교 가부시키가이샤 | Spark plug |
| JP4578025B2 (en) * | 2001-07-06 | 2010-11-10 | 日本特殊陶業株式会社 | Spark plug |
| JP2011084463A (en) * | 2009-09-15 | 2011-04-28 | Ngk Spark Plug Co Ltd | Spark plug |
| WO2020120121A1 (en) | 2018-12-13 | 2020-06-18 | Robert Bosch Gmbh | Spark plug resistance element and spark plug |
| JP2022511462A (en) * | 2018-12-13 | 2022-01-31 | ロベルト・ボッシュ・ゲゼルシャフト・ミト・ベシュレンクテル・ハフツング | Spark plug resistor element and spark plug |
Also Published As
| Publication number | Publication date |
|---|---|
| BR9001203A (en) | 1991-03-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP3813708B2 (en) | Manufacturing method of spark plug | |
| JP4249161B2 (en) | Spark plug with resistor | |
| US4939409A (en) | Spark plug with a surface discharge section | |
| EP0303353B1 (en) | Metallized glass seal resistor composition | |
| WO2011036871A1 (en) | Spark plug | |
| US6699807B2 (en) | Glass ceramic material, method for producing the same and spark plug containing such a glass ceramic material | |
| US6580202B1 (en) | Electrically conductive sealing mass for spark plugs | |
| US4144474A (en) | Low noise resistance containing spark plug | |
| JPH02239582A (en) | Sealing material for spark plug | |
| US6693053B2 (en) | Glass and glass powder mixture and use thereof for the production of a glass ceramic | |
| JP2004039634A (en) | Spark plug, spark plug insulator, and method of manufacturing spark plug | |
| JP3734293B2 (en) | Resistor plug | |
| JPS6134877A (en) | Ignition plug | |
| JP4834264B2 (en) | Spark plug | |
| JPH04167385A (en) | Spark plug for internal combustion engine | |
| JP2003342655A (en) | Alloy, electrode containing the alloy and ignition device | |
| US3360676A (en) | Spark plug with a sealing glass mixture with graphite and iron, nickel or cobalt | |
| JPH02220384A (en) | Resistor for spark plug | |
| JP5238003B2 (en) | Spark plug | |
| KR100287231B1 (en) | Spark plug and manufacturing method | |
| JPH09329334A (en) | Spark plug accommodating resistor | |
| JPH03226982A (en) | Spark plug for internal combustion engine | |
| JPH1022042A (en) | Electronic part sealing body | |
| JPH0751752Y2 (en) | Ceramic heater | |
| JPH02155184A (en) | Spark plug having nitride series ceramic insulator |