JP3625262B2 - Spark plug electrode material with excellent high-temperature oxidation resistance and hot workability - Google Patents
Spark plug electrode material with excellent high-temperature oxidation resistance and hot workability Download PDFInfo
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Description
【０００１】
【発明の属する技術分野】
本発明は、内燃機関に用いられる点火プラグ用材料の中で、特に高温において耐酸化性に優れ、且つ熱間加工性が良好な点火プラグ用電極材料に関するものである。
【０００２】
【従来の技術】
従来、点火プラグ用電極材料には、熱伝導率の高い高Ｎｉ合金が多く使用されており、一部ではより高温での強度・耐酸化性に優れたＮｉ−１６Ｃｒ−８Ｆｅ（Ａｌｌｏｙ６００）合金が用いられてきた。さらにＡｌｌｏｙ６００を改良した合金についても種々の検討がなされており、Ａｌｌｏｙ６００の合金を耐食性改善（特開昭６３−１１８０４０号）、加工性改善（特開昭６２−２７０７４０号、特公平 ５−７１６５５ 号、特公平５−４０８０７）および耐酸化性改善（特開昭６３−１５３２３６号、特公平５−１４７８１号）したものが提案されている。
【０００３】
【発明が解決しようとする課題】
上述した特開昭６３−１１８０４０号および特開昭６２−２７０７４０号と特公平５−７１６５５号および特公平５−４０８０７に開示される合金は、それぞれ耐食性および加工性の点では改善されるものの、耐酸化性の点で改善効果はなかった。また、特開昭６３−１５３２３６号および特公平５−１４７８１号では耐酸化性の改善が行われているが、近年の内燃機関の燃焼室高温化の流れの中では耐酸化性は不十分である。また、従来のＡｌｌｏｙ６００およびその改良材では熱間加工性も不十分である。これらは点火プラグ用電極材を実用化する上で大きな問題となる。
本発明の目的は高温での耐酸化性を向上し、さらに熱間加工性を改善した点火プラグ用電極材料を提供することである。
【０００４】
【課題を解決するための手段】
本発明者は高温での耐酸化性の問題を検討したところ、従来のＡｌｌｏｙ６００または上述した特許で提案されている改良材では酸化被膜から材料内部に向かって粒界にそうようにＴｉ酸化物が生成し、それにより酸化被膜が剥離しやすくなり耐酸化性を低下させていることを知見した。Ａｌｌｏｙ６００は、前述の通りＮｉ−１６Ｃｒ−８Ｆｅを主成分とするが、例えば、特公平５−４０８０７号に示されるように０．２％程度のＴｉを含み、これが耐酸化性に影響を及ぼしていることが考えられる。
そこで本発明者はＴｉ酸化物生成に及ぼすＴｉ量の影響を検討した。その結果、Ｔｉ量を低く抑えることで、耐酸化性を改善できることを見出した。そして、さらに耐酸化性を向上させる方法を検討したところ、Ａｌ添加或いは更に希土類元素、Ｙ、Ｈｆ、Ｚｒの少量添加により耐酸化性を著しく向上させられることを見出した。
【０００５】
次に、本発明者は熱間加工性の問題について検討し、従来のＡｌｌｏｙ６００または特開昭６３−１１８０４号、特開昭６２−２７０７４０号、特公平５−７１６５５号、特開昭６３−１５３２３６号、特公平５−１４７８１号および特公平５−４０８０７号のようなＡｌｌｏｙ６００の改良材ではＮｉとＮｉ３Ｓ２の共晶が粒界に発生していることを知見した。そして、この共晶が熱間加工時に溶融し、割れを引き起こすことをつきとめた。そこでこれを改善するためにはＭｇ添加によりＭｇとＳの化合物を生成して、Ｓを除去または固定することが有効であることを見出し、本発明に到達した。
【０００６】
すなわち本発明は質量％でC:0.032 〜0.1％、Si:1.0％以下、Mn:2.0％以下、Cr:12〜20％、Fe:20％以下、Ti:0.03％以下(0を含む)、Mg:0.001〜0.04％、Al:0.2〜5％、不純物であるSは0.01％以下(但しMg/S≧1)を含み残部はNiおよび不可避不純物からなることを特徴とする高温耐酸化性および熱間加工性に優れた点火プラグ用電極材料である。
【０００７】
そして、本発明において好ましくは、質量％で希土類元素 0.2 ％以下、 Y:0.5 ％以下、 Hf:0.5 ％以下、 Zr:1 ％以下のうち１種または２種以上を含み且つそれらの合計が 1 ％以下含有することを特徴とする請求項１に記載の高温耐酸化性および熱間加工性に優れた点火プラグ用電極材料である。
【０００８】
【発明の実施の形態】
上述したように本発明の重要な特徴は高温での十分な耐酸化性および良好な熱間加工性を併せもった最適組成にある。
以下に各元素の作用について説明する。
CはCr等と結びついて炭化物を形成し、結晶粒粗大化を防止する作用があり、少量添加が必要である。しかし、過度の添加は多量の炭化物形成による冷間加工性の低下およびマトリックス中のCrの欠乏を招くため 0.032 〜0.1％に限定する。
【０００９】
Ｓｉは溶湯に対して強力な脱酸作用を発揮するほか、鋳造性を向上させる作用がある。また、ＳｉＯ２は酸化被膜と母材の中間に形成され、酸化被膜の剥離を阻止する。これらの理由でＳｉを添加するが、過度の添加は耐酸化性の低下を招くためＳｉの上限は１．０％である。
ＭｎはＳｉと同じく脱酸作用を発揮するほか、鋳造性を向上させる作用があるが、過度の添加は耐酸化性の低下を招くためＭｎの上限は２．０％である。
【００１０】
Crはマトリックス中に存在することにより高温において材料表面にCr2O3被膜を形成し耐酸化性を向上させる。高温での十分な耐酸化性を付与させるためには、下限を12％以上とすることが必要である。しかし、過度の添加は加工性を低下させ、かつCr2O3被膜の剥離を引き起こす。従って、Crの添加量は 12〜20％である。
【００１１】
Ｆｅは高温強度を低下させる元素であり、添加しないと熱間加工性が著しく悪くなる。従って、製造上必要な元素である。しかし、過度の添加は逆にプラグ材を使用する高温での強度を低下させ、また耐酸化性もやや低下させる。従って、Ｆｅの添加量は２０％以下である。望ましくは１０％以下である。
【００１２】
Ｔｉ添加により酸化被膜から材料内部に向かって粒界にそうようにＴｉ酸化物が生成する。これにより酸化被膜が剥離しやすくなり、耐酸化性が悪くなる。また、点火プラグの電極は溶接により点火プラグ本体に取り付けられるが、Ｔｉはその際の溶接性を低下させる元素である。そのためＴｉの含有量は０．０３％以下である。望ましくは０を含んで０．０２％以下である。
【００１３】
ＳはＮｉ中の固溶限が非常に小さいため微量含有するだけで結晶粒界にＮｉ３Ｓ２が偏析し、ＮｉとＮｉ３Ｓ２の共晶が発生する。この共晶の融点は非常に低く、熱間加工の温度範囲において非常に脆弱になる。それゆえＳは熱間加工時に粒界を脆弱にし、割れなどをひきおこし、熱間加工性を低下させる元素である。従って、Ｓの含有量は０．０１％以下である。
【００１４】
ＭｇはＳと結びついて化合物を形成し、Ｓを除去または固定するために必須の元素である。しかしながら、ＭｇはＮｉ中の固溶限が小さいため過度に添加すると粒界にＮｉ２Ｍｇを形成する。このためＮｉとＮｉ２Ｍｇの共晶が粒界において発生し、熱間加工時には粒界が脆弱になり、熱間加工性が低下する。従って、Ｍｇの添加は０．００１〜０．０４％である。
また、Ｓを確実に除去または固定するためにＭｇ／Ｓの比率を１以上とすることが必要である。
【００１５】
Alは材料表面に酸化被膜を生成するため主に耐酸化性向上に有効であり、また、脱酸剤としての効果もある。しかし、過度の添加は加工性を低下させるためAlの添加量は5％以下とし、その下限を 0.2 ％とする。
【００１６】
希土類元素、Ｙ、ＨｆおよびＺｒは微量添加することにより耐酸化性が著しく向上する。本発明で添加する好ましい希土類元素はＬａ、Ｃｅである。これは主に酸化膜の密着性を向上させることによると考えられる。しかしながら、過度の添加は熱間加工性を低下させる。したがって、添加量は希土類元素０．２％以下、Ｙ０．５％以下、Ｈｆ０．５％以下、Ｚｒ１％以下のうち１種または２種以上を含み且つそれらの合計が１％以下が良い。
【００１７】
希土類、Ｙ、ＨｆおよびＺｒのなかでも特にＬａとＺｒは膜の密着性を向上させ、耐酸化性を向上させる効果が大きい。従って、希土類、Ｙ、ＨｆおよびＺｒのうちで特に望ましい添加元素および添加量はＬａおよびＺｒのうち１種または２種を含み且つそれらの合計が０．３％以下が良い。
【００１８】
以下の元素は下記の範囲内で本発明鋼に含まれても良い。
Ｍｏ≦１、Ｗ≦１、Ｎｂ≦０．５、Ｐ≦０．０４、Ｃｕ≦０．３０、Ｖ≦０．５、Ｔａ≦０．５、Ｃａ≦０．０２、Ｃｏ≦２
【００１９】
【実施例】
以下に実施例として本発明を詳しく説明する。
真空溶解により、表１に示す組成の点火プラグ用電極材料の１０ｋｇインゴットを溶製し、このインゴットを３０ｍｍ角の棒材に鍛伸した。この棒材に９５０℃×１ｈ空冷なる溶体化処理を施した。
表１でＮｏ．１〜Ｎｏ．１４が本発明材であり、Ｎｏ．１５〜Ｎｏ．２１は比較材である。ただし、Ｎｏ．１９〜２１については鍛伸できなかった。
なお、特開昭６２−２７０７４０号で示されるＴｉを０．２０％含有するＡｌｌｏｙ６００の改良合金をＮｏ．１８として示す。
【００２０】
【表１】
表１に示す材料から試料を切り出し、耐酸化試験および溶接性試験を行った。
耐酸化試験はφ10mm×20mmの試験片を1000℃×100hおよび1050℃×100h加熱後、酸化増量を求めた。ただし、No.16およびNo.19〜21については鍛伸できなかったのでインゴットを切り出して耐酸化試験片を作製した。
溶接性試験はTi量の影響を確認するためにNo.2、6および18合金について行った。試験片には1×3×60mmの点火プラグ用電極材料試験片と2×10×50mmの軟鋼製相手材を用いた。
これら試験片の1×3mmの断面と2×10mmの断面を突合わせて抵抗溶接を行い、この溶接された試験片の曲げ試験後の破断面を観察し、1×3mmの断面のうち接合している面積率を求めた。本溶接性試験では接合面積率40％以上であれば溶接性が良好であると判断した。
表２に本発明材、参考材および比較材について1000℃×100hおよび1050℃×100hの耐酸化試験による酸化増量および溶接性試験の接合面積率を示す。
【００２２】
【表２】
本発明材は1000℃×100hおよび1050℃×100hの耐酸化試験において酸化増量が少なくかつ酸化膜剥離がない非常に良好な耐酸化性を示した。本発明材はいずれもAlloy600改良材相当のNo.18より良好な耐酸化性を示した。
Ti の影響を調べた参考例No.2および6の溶接性は良好で40％以上の接合面積率を有していた。No.6合金の溶接性は特に良好である。
また、本発明材は、熱間加工性も良好であるため鍛伸割れなどの問題は起こらなかった。
【００２４】
一方、比較材はＣｒが１２％より少なくなると（Ｎｏ．１５）耐酸化性が不足するため耐酸化試験後の酸化増量が多くなっている。Ｃｒが３２％より多くなると（Ｎｏ．１６）Ｃｒ２Ｏ３の剥離が発生するため酸化増量が多くなっている。
Ｆｅが多くなると（Ｎｏ．１７）やや耐酸化性が低下する。Ｔｉが０．０３％を超えて含まれているＡｌｌｏｙ６００相当材（Ｎｏ．１８）も酸化被膜の剥離が発生し酸化増量が多くなっており、また、接合面積率が低く溶接性も悪くなっている。
Ｍｇが０．００１％未満でＭｇ／Ｓ＜１の材料（Ｎｏ．１９）、Ｍｇが０．０４％を超える材料（Ｎｏ．２０）およびＳが０．０１を超えＭｇ／Ｓ＜１の材料（Ｎｏ．２１）はそれぞれ共晶が発生するため鍛伸中に割れが起きた。
このように各々の元素が本発明の範囲内に含まれて初めて、高温での使用に耐えられ、鍛伸可能であり、かつ溶接性が良好な点火プラグ用電極材料ができることがわかる。
【００２５】
【発明の効果】
本発明によれば、高温で優れた耐酸化性を有し、かつ熱間加工性にも優れた材料を作製することができ、例えば自動車エンジン用の点火プラグ用電極材料として用いたときその性能を向上させることができる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to an electrode material for a spark plug that is excellent in oxidation resistance at high temperatures and has good hot workability among spark plug materials used in internal combustion engines.
[0002]
[Prior art]
Conventionally, high Ni alloys with high thermal conductivity have been used as spark plug electrode materials, and some of them are Ni-16Cr-8Fe (Alloy 600) alloys that are superior in strength and oxidation resistance at higher temperatures. Has been used. Further, various studies have been made on alloys improved from Alloy 600. Alloys made of Alloy 600 are improved in corrosion resistance (JP-A-63-118040), workability is improved (JP-A-62-270740 , JP-B-5-71655) . JP-B-5-40807) and oxidation resistance improvement (Japanese Patent Laid-Open No. 63-153236, JP-B-5-14781) have been proposed.
[0003]
[Problems to be solved by the invention]
Although the alloys disclosed in JP-A-63-118040, JP-A-62-270740, JP-B-5-71655 and JP-B-5-40807 are improved in terms of corrosion resistance and workability, There was no improvement effect in terms of oxidation resistance. Further, although Japanese Patent Application Laid-Open No. 63-153236 and Japanese Patent Publication No. 5-14781 have improved the oxidation resistance, the oxidation resistance is insufficient in the recent trend of increasing the combustion chamber temperature of internal combustion engines. is there. Further, the conventional Alloy 600 and its improved material have insufficient hot workability. These become a big problem when putting the electrode material for spark plugs into practical use.
An object of the present invention is to provide an electrode material for a spark plug that has improved oxidation resistance at high temperatures and further improved hot workability.
[0004]
[Means for Solving the Problems]
The present inventor examined the problem of oxidation resistance at high temperature. In the improved alloy proposed in the conventional Alloy 600 or the above-mentioned patent, the Ti oxide is formed so as to enter the grain boundary from the oxide film toward the inside of the material. It was found that the oxide film was easily peeled off, thereby reducing the oxidation resistance. Alloy 600 has Ni-16Cr-8Fe as the main component as described above, but contains, for example, about 0.2% Ti as shown in Japanese Patent Publication No. 5-40807, which affects the oxidation resistance. It is possible that
Therefore, the present inventor examined the influence of Ti amount on Ti oxide formation. As a result, it was found that the oxidation resistance can be improved by keeping the amount of Ti low. Then, when a method for further improving the oxidation resistance was examined, it was found that the oxidation resistance could be remarkably improved by adding Al or further adding a small amount of rare earth elements, Y, Hf, and Zr.
[0005]
Next, the present inventor examined the problem of hot workability, and used the conventional Alloy 600 or JP-A-63-18044, JP-A-62-270740, JP-B-5-71655, JP-A-63-153236. It was found that eutectics of Ni and Ni 3 S 2 were generated at the grain boundaries in the improved materials of Alloy 600 such as No. 5, JP-B-5-14781 and JP-B-5-40807. It was found that this eutectic melts during hot working and causes cracking. Therefore, in order to improve this, it has been found that it is effective to produce a compound of Mg and S by adding Mg and to remove or fix S, and the present invention has been achieved.
[0006]
That C in the present invention is mass%: 0.032 ~ 0.1%, Si : 1.0% or less, Mn: 2.0% or less, Cr: 12~20%, Fe: 20% or less, Ti: (including 0) 0.03% or less, Mg: 0.001 to 0.04%, Al: 0.2 to 5%, S, which is an impurity, contains 0.01% or less (provided that Mg / S ≧ 1), and the balance consists of Ni and inevitable impurities. It is an electrode material for a spark plug excellent in hot workability.
[0007]
In the present invention, the rare earth element is preferably 0.2 % or less by mass% , Y: 0.5 % or less, Hf: 0.5 % or less, and Zr: 1 % or less, and the total thereof is 1 The spark plug electrode material excellent in high-temperature oxidation resistance and hot workability according to claim 1, characterized in that it is contained in an amount of at most%.
[0008]
DETAILED DESCRIPTION OF THE INVENTION
As described above, an important feature of the present invention resides in an optimum composition that combines sufficient oxidation resistance at high temperatures and good hot workability.
The operation of each element will be described below.
C combines with Cr and the like to form carbides and has the effect of preventing coarsening of crystal grains, and needs to be added in a small amount. However, excessive addition is limited in order from .032 to 0.1%, which leads to lack of Cr of cold workability decreases and matrix due to a large amount of carbide forming.
[0009]
Si exhibits a strong deoxidizing action on the molten metal and has an effect of improving castability. In addition, SiO 2 is formed between the oxide film and the base material, and prevents the oxide film from peeling off. For these reasons, Si is added, but excessive addition causes a decrease in oxidation resistance, so the upper limit of Si is 1.0%.
Mn exerts a deoxidizing effect as well as Si and has an effect of improving castability. However, excessive addition causes reduction in oxidation resistance, so the upper limit of Mn is 2.0%.
[0010]
When Cr is present in the matrix, it forms a Cr 2 O 3 film on the surface of the material at high temperature and improves oxidation resistance. In order to provide sufficient oxidation resistance at high temperatures, the lower limit needs to be 12% or more. However, excessive addition reduces workability and causes peeling of the Cr 2 O 3 coating. Therefore, the addition amount of Cr is 12 to 20%.
[0011]
Fe is an element that lowers the high temperature strength, and if not added, the hot workability is remarkably deteriorated. Therefore, it is an element necessary for production. However, excessive addition, on the contrary, decreases the strength at a high temperature at which the plug material is used, and also slightly decreases the oxidation resistance. Therefore, the addition amount of Fe is 20% or less. Desirably, it is 10% or less.
[0012]
By adding Ti, Ti oxide is generated so as to reach the grain boundary from the oxide film toward the inside of the material. As a result, the oxide film is easily peeled off and the oxidation resistance is deteriorated. Further, the electrode of the spark plug is attached to the spark plug body by welding, and Ti is an element that lowers the weldability at that time. Therefore, the Ti content is 0.03% or less. Desirably, it is 0.02% or less including 0.
[0013]
Since S has a very small solid solubility limit in Ni, Ni 3 S 2 is segregated at the grain boundaries just by containing a trace amount, and a eutectic of Ni and Ni 3 S 2 is generated. The eutectic has a very low melting point and becomes very brittle in the temperature range of hot working. Therefore, S is an element that weakens the grain boundary during hot working, causes cracking, and reduces hot workability. Therefore, the S content is 0.01% or less.
[0014]
Mg combines with S to form a compound, and is an essential element for removing or fixing S. However, since Mg has a small solid solubility limit in Ni, Ni 2 Mg is formed at the grain boundary when excessively added. For this reason, a eutectic of Ni and Ni 2 Mg is generated at the grain boundary, the grain boundary becomes brittle during hot working, and the hot workability is lowered. Therefore, the addition of Mg is 0.001 to 0.04%.
Moreover, in order to remove or fix S reliably, the Mg / S ratio needs to be 1 or more.
[0015]
Al produces an oxide film on the surface of the material, so that it is mainly effective for improving the oxidation resistance and also has an effect as a deoxidizer. However, excessive addition reduces workability, so the amount of Al is 5% or less , and the lower limit is 0.2 % .
[0016]
Oxidation resistance is remarkably improved by adding trace amounts of rare earth elements, Y, Hf and Zr. Preferred rare earth elements added in the present invention are La and Ce. This is considered to be mainly due to improving the adhesion of the oxide film. However, excessive addition reduces hot workability. Therefore, the addition amount includes one or more of rare earth elements of 0.2% or less, Y of 0.5% or less, Hf of 0.5% or less, and Zr of 1% or less, and the total thereof is preferably 1% or less.
[0017]
Among rare earths, Y, Hf, and Zr, La and Zr are particularly effective in improving film adhesion and improving oxidation resistance. Therefore, among the rare earth elements, Y, Hf, and Zr, particularly desirable additive elements and addition amounts include one or two of La and Zr, and the total thereof is preferably 0.3% or less.
[0018]
The following elements may be included in the steel of the present invention within the following range.
Mo ≦ 1, W ≦ 1, Nb ≦ 0.5, P ≦ 0.04, Cu ≦ 0.30, V ≦ 0.5, Ta ≦ 0.5, Ca ≦ 0.02, Co ≦ 2
[0019]
【Example】
Hereinafter, the present invention will be described in detail as examples.
A 10 kg ingot of a spark plug electrode material having the composition shown in Table 1 was melted by vacuum melting, and the ingot was forged into a 30 mm square bar. The bar was subjected to a solution treatment of air cooling at 950 ° C. × 1 h.
In Table 1, No. 1-No. 14 is the material of the present invention. 15-No. 21 is a comparative material. However, no. It was not possible to forge about 19-21.
An improved alloy of Alloy 600 containing 0.20% of Ti shown in JP-A-62-270740 is No. It is shown as 18.
[0020]
[Table 1]
Samples were cut out from the materials shown in Table 1 and subjected to an oxidation resistance test and a weldability test.
In the oxidation resistance test, a test piece of φ10 mm × 20 mm was heated at 1000 ° C. × 100 h and 1050 ° C. × 100 h, and then the oxidation increase was determined. However, since No.16 and No.19-21 could not be forged, the ingot was cut out and the oxidation-resistant test piece was produced.
Weldability tests were conducted on Nos. 2, 6 and 18 alloys to confirm the effect of Ti content. For the test piece, a 1 × 3 × 60 mm spark plug electrode material test piece and a 2 × 10 × 50 mm mild steel counterpart were used.
Resistance welding was performed with the 1 × 3 mm cross section and 2 × 10 mm cross section of these specimens butted, and the fractured surface of the welded specimen after bending test was observed. The area ratio is calculated. In this weldability test, it was judged that the weldability was good when the joint area ratio was 40% or more.
Table 2 shows the increase in oxidation by the oxidation resistance test at 1000 ° C. × 100 h and 1050 ° C. × 100 h for the inventive material , the reference material and the comparative material, and the joint area ratio in the weldability test.
[0022]
[Table 2]
The material of the present invention showed very good oxidation resistance with little increase in oxidation and no oxide film peeling in the oxidation resistance test at 1000 ° C. × 100 h and 1050 ° C. × 100 h. All of the inventive materials showed better oxidation resistance than No. 18 equivalent to Alloy 600 improved material.
The weldability of Reference Examples No. 2 and 6 in which the influence of Ti was examined was good and had a joint area ratio of 40% or more. The weldability of No.6 alloy is particularly good.
Further, since the material of the present invention has good hot workability, problems such as forge-cracking did not occur.
[0024]
On the other hand, when the Cr content is less than 12% (No. 15), the oxidation resistance is insufficient, so that the oxidation increase after the oxidation resistance test increases. When Cr is more than 32% (No. 16), Cr 2 O 3 is peeled off, and the amount of increase in oxidation is increased.
When the amount of Fe increases (No. 17), the oxidation resistance slightly decreases. Alloy 600 equivalent material (No. 18) containing more than 0.03% of Ti is also peeled off by an oxide film, increasing the amount of oxidation, and having a low joint area ratio and poor weldability. Yes.
Material with Mg less than 0.001% and Mg / S <1 (No. 19), material with Mg exceeding 0.04% (No. 20) and material with S exceeding 0.01 and Mg / S <1 In (No. 21), eutectic was generated, and cracking occurred during forging.
Thus, it can be seen that only when each element is included in the scope of the present invention, an electrode material for a spark plug that can withstand use at high temperatures, can be forged, and has good weldability can be obtained.
[0025]
【The invention's effect】
According to the present invention, a material having excellent oxidation resistance at high temperatures and excellent in hot workability can be produced. For example, when used as an electrode material for a spark plug for an automobile engine, its performance Can be improved.
Claims (2)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP28197399A JP3625262B2 (en) | 1999-03-19 | 1999-10-01 | Spark plug electrode material with excellent high-temperature oxidation resistance and hot workability |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11-74662 | 1999-03-19 | ||
| JP7466299 | 1999-03-19 | ||
| JP28197399A JP3625262B2 (en) | 1999-03-19 | 1999-10-01 | Spark plug electrode material with excellent high-temperature oxidation resistance and hot workability |
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| JP2000336446A JP2000336446A (en) | 2000-12-05 |
| JP3625262B2 true JP3625262B2 (en) | 2005-03-02 |
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Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4073636B2 (en) | 2001-02-28 | 2008-04-09 | 日本特殊陶業株式会社 | Spark plug and manufacturing method thereof |
| JP4171206B2 (en) | 2001-03-16 | 2008-10-22 | 株式会社デンソー | Spark plug and manufacturing method thereof |
| DE60206464T2 (en) * | 2001-12-21 | 2006-07-13 | Hitachi Metals, Ltd. | Ni alloy with improved oxidation resistance, hot strength and hot workability |
| JP4769070B2 (en) * | 2005-01-31 | 2011-09-07 | 日本特殊陶業株式会社 | Spark plug for internal combustion engine |
| DE102006053917B4 (en) | 2005-11-16 | 2019-08-14 | Ngk Spark Plug Co., Ltd. | Spark plug used for internal combustion engines |
| US7823556B2 (en) * | 2006-06-19 | 2010-11-02 | Federal-Mogul World Wide, Inc. | Electrode for an ignition device |
| DE102007040722A1 (en) | 2007-08-29 | 2009-03-05 | Robert Bosch Gmbh | Spark plug electrode made of improved electrode material |
| KR101625349B1 (en) | 2013-01-08 | 2016-05-27 | 니뽄 도쿠슈 도교 가부시키가이샤 | Electrode material and spark plug |
| CN104451267A (en) * | 2014-11-22 | 2015-03-25 | 湘潭高耐合金制造有限公司 | Nickel-yttrium alloy spark plug electrode material and preparation method thereof |
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