JP4205505B2 - Corrosion-resistant and wear-resistant alloys and equipment using them - Google Patents

Corrosion-resistant and wear-resistant alloys and equipment using them Download PDF

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JP4205505B2
JP4205505B2 JP2003202165A JP2003202165A JP4205505B2 JP 4205505 B2 JP4205505 B2 JP 4205505B2 JP 2003202165 A JP2003202165 A JP 2003202165A JP 2003202165 A JP2003202165 A JP 2003202165A JP 4205505 B2 JP4205505 B2 JP 4205505B2
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resistant
corrosion
wear
valve
alloy
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JP2004131840A (en
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芳久 清時
良照 千葉
真 熊谷
裕広 小川
明 坂本
博之 篠原
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Hitachi GE Nuclear Energy Ltd
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    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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  • Heat Treatment Of Steel (AREA)
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Description

【0001】
【発明の属する技術分野】
本発明は、耐蝕・耐摩耗性合金を用いた流体機器,動的機器に関する。
【0002】
【従来の技術】
タービン発電設備等のプラント設備では、安全弁を始めとする弁類には、運転中の弁座のエロージョン損傷を防止するため、また、弁の作動中のかじり防止のために、耐蝕・耐摩耗性能に優れた硬度の高いコバルトをベースにCrおよび/またはWを添加した耐蝕・耐摩耗性合金を肉盛した弁座または摺動部が使用されている。
【0003】
しかし、近年、タービン発電設備等のプラント設備では、水質調整の目的から過酸化水素水等の注入が行われている。その結果、注入点下流の溶存酸素量が増加し、弁の弁座面や摺動部にエロージョン防止,かじり防止を目的に肉盛した前記コバルトをベースに、Crおよび/またはWを添加した耐蝕・耐摩耗性合金を構成する共晶炭化物と鋳造組織の基材部のうち、共晶炭化物に腐蝕損傷が起こる。
【0004】
また、流れ(例えば、水流)のある場合には、共晶炭化物の腐蝕損傷に続いて、鋳造組織の基材部が脱落し、エロージョンが発生するという報告がある。
【0005】
上記の関連報告としては、「火力原子力発電 Vol.30−5,火力発電所の水蒸気系統の酸素およびアンモニアによるボイラ水の処理法」,「機械の損害1982−第2号 VEW Gerstein発電所における組合わせ運転方法による運転経験について」、または、「材料と環境Vol.47,No.3,コバルト基合金溶接部の粒界腐蝕に及ぼす熱処理条件の影響」等がある。
【0006】
しかし、上記報告でも、エロージョンの発生を無くすための有効な手段は無いとされており、問題となっていた。
【0007】
その一方で、特開平8−334280号公報(対応米国特許第6164624号明細書)には、弁本体の材料よりも硬度の高い(ビッカース硬度150〜500)金属材料により作成したオリフィス部材をその弁本体に組み込み、オリフィスが装備された弁口のエロージョンの発生を防止できる膨張弁が開示されている。
【0008】
また、特開平5−208325号公報(対応米国特許第5183390号明細書)には、蒸気タービンの羽根の後縁部に、コバルト,ニッケル,タングステン,マンガン及びセレンを含む棒状の耐摩耗性材料を摩擦サーフエーシング法で装着してその羽根の耐摩耗性を向上することを開示している。その摩擦サーフエーシング法での耐摩耗性材料の羽根への装着に際しては、硬度の変化や縮み割れ防止の観点から棒状の耐摩耗性材料が溶融を生じないように注意する点を開示している。
【0009】
また、特開昭59−179283号公報には、Cr30〜45重量%,Ti3.0〜8.0重量%,Mo0〜10重量%、及び残部Niからなる弁座が弁体,弁箱に拡散接合された弁について開示されている。
【0010】
また、特開昭60−86239号公報には、Cr10〜45重量%,Al及びTiのうちの少なくともいずれか1種1.5 〜6重量%,Mo20重量%以下、及び残部Niからなる弁座が弁体及び/又は弁箱に拡散接合された弁について開示されている。
【0011】
また、特開平4−19476号公報には、弁箱の弁座部にアモルファス合金層を介して超硬材料又は耐熱材料から成る弁座をロウ付けしてある弁が開示されている。
【0012】
また、特開平7−16610号公報には、高炭素マルテンサイト系ステンレス鋼素材を熱間塑性加工により中間寸法の中間素材とし、その中間素材に冷間塑性加工を施し、再度850℃以上で熱間塑性加工を施すことによって、目的寸法の鋼材を作る技術が開示されている。その開示技術によれば、目的寸法の鋼材中の共晶化炭化物平均寸法が4.2μmに達したことが同公報に掲載されている。
【0013】
【発明が解決しようとする課題】
タービン発電プラントに使用する安全弁を始めとする弁類には、運転中の弁座部の流速が早く、エロージョン損傷を防止するために耐蝕・耐摩耗性能に優れた硬度の高いコバルトをベースに、Crおよび/またはWを添加した耐蝕・耐摩耗性合金を用いた弁座が使用されている。
【0014】
また、ケージ弁等にあっては、弁の作動中のかじり防止のために、弁体をガイドするガイド表面またはケージ内面に、上記の耐蝕・耐摩耗性合金を用いた弁箱が使用されている。
【0015】
しかし、溶存酸素の多い高温高圧の水・蒸気雰囲気下で上記の耐蝕・耐摩耗性合金製の弁座を使用すると、該合金中の鋳造組織の基材部層と、網目状に鋳造組織の基材部層を包み込んでいる共晶炭化物が、流体中の溶存酸素によって選択的に腐蝕される。これにより弁座の面荒れが著しくなると共に、腐蝕損傷部に高速ジェットが侵入して発生するトンネル作用(F.j.Heymann:Machine Dedign.42,118(1970))の効果も手伝って、共晶炭化物の腐蝕脱落により、網目状の共晶炭化物による保持を失った鋳造組織の基材部が、流れによって容易に脱落することで、耐蝕・耐摩耗性合金にエロージョンが発生する。
【0017】
発明は、耐摩耗性能,耐エロージョン性能が向上した耐蝕・耐摩耗性合金を機器の耐摩耗部,エロージョンシールド部に用いた機器を提供することにある。
【0018】
【課題を解決するための手段】
前記目的を達成する本発明の要旨は次のとおりである。
【0019】
Crおよび/またはWを添加したコバルトベースである素材を、インゴットまたはスラブに鋳造した中間素材を、650℃以上、固相線温度以下で熱間塑性加工を施すことにより、該中間素材中の網目状共晶炭化物と、これに囲まれた基材部とからなる組織のうち、共晶炭化物を複数の粒状または複数の塊状に形成して非連続分布とし、摩擦係数が0.1〜0.5、時効効果処理を施さないビッカウス硬度が300〜600Hvであることを特徴とする耐蝕・耐摩耗性合金にある。
【0020】
そのCrおよび/またはWを添加したコバルトベース素材は、重量比で0.1〜3.5%C ,25%以下Ni,25〜35%Cr,5%以下Fe,20%以下W,1.5%以下Mn,1.5%以下Siと、残部Coおよび不可避不純物から成る。
【0021】
例えば、コバルトをベースにCrおよび/またはWを添加してインゴットまたはスラブに代表される中間素材に鋳造した鋳造組織の基材部と、共晶炭化物からなる鋳造素材のうち、網目状に連続して分布する高硬度で、延性が低く、脆い共晶炭化物を熱間塑性加工を施す。これにより上記中間素材を細かな粒状または塊状とする。これによって、共晶炭化物間に生じた隙間に基材部の組織が入り込み、その結果、硬度が低く,延性が高く,強靭な基材部を細かな粒状化または塊状化した共晶炭化物の周辺に分布させることで、共晶炭化物を非連続化する。
【0022】
これと共に、650℃以上の高温に保持することで、共晶炭化物中に多く存在するクロムの拡散を促し、共晶炭化物の周辺のクロム欠乏層を減少させ、共晶炭化物自体の耐蝕性能の向上も合わせて図った耐蝕・耐摩耗性合金が得られる。
【0023】
上記によれば、コバルトをベースにCrおよび/またはWを添加して溶解した鋳造組織の基材部と共晶炭化物のうち、網目状に連続して分布する共晶炭化物を複数の粒状または塊状に変化させることで非連続の共晶炭化物とし、腐蝕現象を不連続なごく浅い表面的な一部の事象とすることができる。
【0024】
その結果、腐蝕の進行が抑制され、腐蝕損傷部に高速のジェットが侵入して発生するトンネル作用(F.j.Heymann:Machine Dedign.42,118(1970))をも抑制でき、耐エロージョン性能も向上する。
【0025】
以上の効果により、耐エロージョン・コロージョン性能を向上することができる。
【0026】
また、650℃以上の高温に保持することで、共晶炭化物中に多く存在するCrの共晶炭化物周辺への拡散を促すことになり、Crを含有する共晶炭化物の周辺に存在するCr欠乏層が減少し、共晶炭化物自体の耐蝕性能の向上も併せて図ることができる。
【0028】
上記の耐蝕・耐摩耗性合金は、その全てまたは一部を溶融すると、溶融部分の共晶炭化物は耐蝕性の低い網目状の共晶炭化物を形成するため、該耐蝕・耐摩耗性合金を機械加工により任意の形状、または、耐蝕・耐摩耗性合金が装着される母材である台金に溶融せずに母材に接合して使用できる。
【0029】
網目状の共晶炭化物が存在せずに塊状または粒状の共晶炭化物となることで、それを用いたポンプ,弁,圧力機器,タービン等の流体機器を腐蝕雰囲気下で用いても、高い耐蝕性,耐エロージョン性を得ることができる。
【0030】
また、耐蝕・耐摩耗性合金を、金属組成を変えずにそのまま台金に接合し、摺動部、または、接触部に用いたポンプ,弁,タービン,エンジン等の動的機器を腐蝕雰囲気下で用いても、高い耐蝕性,耐エロージョン性を得ることができる。
【0031】
なお、摩擦係数は0.1〜0.3とダイヤモンド(無潤滑状態での摩擦係数0.1)やサファイヤ(無潤滑状態での摩擦係数0.2),ルビー並みのものが得られ場合があり、黄銅(無潤滑状態での摩擦係数0.35)や鋼(無潤滑状態での摩擦係数0.8)などの他の金属の摩擦係数0.35〜0.8に比べて摩擦抵抗を低くできる。
【0032】
このような耐蝕・耐摩耗性合金は、流体機器の耐摩耗部、または、エロージョンシールド部、及び動的機器の摺動部、または、接触部に用いられる。
【0033】
流体機器及び動的機器に本発明の耐蝕・耐摩耗性合金を装着するには、上述の耐摩耗部またはエロージョンシールド部または摺動部または接触部へその耐蝕・耐摩耗性合金の組成を極力変えずに装着する。その装着の手法としては、その耐蝕・耐摩耗性合金を溶融することがない接合方法を用いる。その接合方法の一例として液相拡散接合方法が利用できる。
【0034】
一層具体的には、本発明の耐蝕・耐摩耗性合金は、原子力発電プラント等の配管系統に設けられる弁の弁体と弁箱の接触面に装着される弁座として、又は、ポンプの回転軸の周囲に相対的に回転するシートとワッシャーとの接触面の少なくとも一方の接触面材として、又は、内燃機関のシリンダヘッドに備わるバルブシートと弁の接触面に装着される弁座として、又は、内燃機関のバルブリフターとカムの両者の接触面の少なくとも一方の面材に用いられる。
【0035】
【発明の実施の形態】
コバルトをベースにCrおよび/またはWを添加した耐蝕・耐摩耗性合金の表面の代表的なSEM写真を図1(但し、(a)はSEM写真、(b)はその模式図で、図2〜図5も同様)に、高倍率で撮影したSEM写真像を図2に、該耐蝕・耐摩耗性合金の表面の図2と同一位置のCr面分析SEM写真を図3に示す。
【0036】
さらに、鍛造,圧延等の塑性加工を熱間で行った該耐蝕・耐摩耗性合金の表面の金属組織のSEM像を図4に示す。また、該耐蝕・耐摩耗性合金の表面の図4と同一位置のCr面分析SEM写真を図5に示す。
【0037】
図1,図2,図3ではCrとCを主成分とする共晶炭化物1は、コバルトが主成分の鋳造組織の基材部2に網目状に連続して表面溶着合金の表面に分布している。
【0038】
一方、本発明の実施例である図4,図5では、基材部2に対して共晶炭化物1は粒状または塊状に、耐蝕・耐摩耗性合金の表面に一様に分布しているが不連続である。共晶炭化物1は、網目状から粒状または塊状に変化したことで、表面に占める共晶炭化物1の割合が減少している。
【0039】
図6は、コバルトをベースにCrおよび/またはWを添加した耐蝕・耐摩耗性合金の溶存酸素による繰り返し損傷の進行状況を示す模式図である。
【0040】
耐蝕・耐摩耗性合金の腐蝕・エロージョンは、溶存酸素により共晶炭化物1が腐蝕することで、鋳造組織の基材部2層が脱落し易くなり、進行する。
【0041】
図3のSEA写真に示すように、通常のコバルトをベースにCrおよび/またはWを添加した耐蝕・耐摩耗性合金は、網目状に連続した共晶炭化物1が存在する。そのため、溶存酸素による共晶炭化物1の腐蝕と、鋳造組織の基材部2層の脱落が連続的に発生する結果、溶存酸素雰囲気下の腐蝕・エロージョンが進行する。
【0042】
これに対し、熱間塑性加工を行ったコバルトベースにCrおよび/またはWを添加した耐蝕・耐摩耗性合金では、共晶炭化物1が粒状または塊状に不連続に存在し、溶存酸素による共晶炭化物1の腐蝕損傷は、溶存酸素に接する面の共晶炭化物1に限られる。
【0043】
従って、表面の共晶炭化物1が腐蝕脱落後はそれ以上の腐蝕損傷は進行することはない。これを図7の溶存酸素による損傷抑止状況を示す模式図により説明する。
【0044】
上記の効果を確認するために、JIS G 0575“ステンレス鋼の硫酸・硫酸銅腐蝕試験”(ストラウス試験)を適用した。共晶炭化物が網目状に連続した分布を有するコバルトベースの耐蝕・耐摩耗性合金に、同様な試験を行った高久,本田らの試験(材料と環境Vol.47:コバルト基合金溶接部の粒界腐蝕に及ぼす熱処理条件の影響)では、コバルト基合金の耐蝕・耐摩耗性合金の表面溶着合金は腐蝕の進行が認められることを報告している。
【0045】
しかし、鍛造,圧延等の塑性加工を行ったコバルトをベースにCrおよび/またはWを添加した耐蝕・耐摩耗性合金に同様の試験を行ったところ、表面に殆どエッチングも認められず、深さ方向への腐蝕の進展もなく、良好な耐腐蝕性が確認できた。その試験結果を図8、並びに、表1に示す。また、摺動回数の増減に応じた摩擦係数の測定結果を図9に示す。
【0046】
【表1】

Figure 0004205505
【0047】
上記の結果から、腐蝕環境下で共晶炭化物1が粒状または塊状に不連続に存在するコバルトをベースにCrおよび/またはWを添加した耐蝕・耐摩耗性合金の場合には、腐蝕深さは従来に比べ、約1/30程度に抑制でき、さらに、予熱温度を上げると、Crがさらに拡散することで腐蝕深さを低減できる。
【0048】
この結果、共晶炭化物1が粒状または塊状に不連続に存在する該耐蝕・耐摩耗性合金は溶存酸素による腐蝕を抑制でき、結果として、エロージョンも抑止できる。
【0049】
さらに、コバルトをベースにCrおよび/またはWを添加した耐蝕・耐摩耗性合金の予熱温度を、約600℃とした場合と約700℃とした場合を比較すると、Crがより多く拡散する予熱温度約700℃の場合が、粒状または塊状の共晶炭化物1自体の耐蝕性が高く、接合の際に予熱温度を高くして母材と接合すると、より耐蝕・耐摩耗性に優れた耐蝕・耐摩耗性合金とすることができる。
【0050】
なお、ニッケルベースのFeおよび/またはCr添加の耐蝕・耐摩耗性合金,鉄ベースのCrおよび/またはNiを添加した耐蝕・耐摩耗性合金についても、固相線温度以下に加熱した状態で熱間塑性加工を行うことで、前記のコバルトベースのCrおよび/またはWを添加した耐蝕・耐摩耗性合金と同様に、耐蝕・耐摩耗性を向上させることができ、併せて、低摩擦な摺動面を提供することができる。
【0051】
又、鉄をベースにCrおよび/またはNiを添加した耐蝕・耐摩耗性合金についても、固相線温度以下に加熱した状態で熱間塑性加工を行うことで、前記のコバルトベースのCrおよび/またはWを添加した耐蝕・耐摩耗性合金と同様に、耐蝕・耐摩耗性を向上させることができ、併せて、低摩擦な摺動面を提供することができる。
【0052】
以上に述べたコバルトをベースにCrおよび/またはWを添加した耐蝕・耐摩耗性合金の素材成分は、重量比で0.1〜3.5%C,25%以下Ni,25〜35%Cr,5%以下Fe,20%以下W,1.5%以下Mo,1.5%以下Siと、残部Coおよび不可避不純物から成る。
【0053】
又、ニッケルをベースにFeおよび/またはCrを添加した耐蝕・耐摩耗性合金の素材成分は、重量比で0.1〜2.5%C,3〜9%Si,7〜25%Cr,0.5〜5%B ,2〜6%Fe,1〜5%W,17%以下Moと、残部Niおよび不可避不純物から成る。
【0054】
又、鉄をベースにCrおよび/またはNiを添加した耐蝕・耐摩耗性合金の素材成分は、重量比で0.1〜1.5%C ,0.3〜4%Si,4〜9%Ni,3%以下Mo,6〜10%Mn,15〜25%Crと、残部Feおよび不可避不純物から成る。
【0055】
このような耐蝕・耐摩耗性合金の素材に上述のように熱間塑性加工を施すと、耐蝕・耐摩耗性を向上させることができ、併せて、低摩擦な耐蝕・耐摩耗性合金の面が得られる。
【0056】
その耐蝕・耐摩耗性合金の面の摩擦測定によって摩擦係数を求めると、室温大気中で無潤滑の条件で平均0.16 となり、温度288℃の飽和水蒸気雰囲気で平均0.19 となった。摩擦測定に供した耐蝕・耐摩耗性合金の金属成分は以下の表2の金属成分を有し、その耐蝕・耐摩耗性合金中の共晶炭化物の形態は、複数の粒状または複数の塊状になった非連続分布の形態を有していた。
【0057】
【表2】
Figure 0004205505
【0058】
本発明の耐蝕・耐摩耗性合金は、以下のように各種の機器に用いられる。即ち、 図10には原子力発電プラントの配管系統が図示されている。その配管系統の中で、給水系10には給水管11に仕切弁及び逆止弁が非常に多く装着されている。給水管11に装着された仕切弁及び逆止弁は給水管11の途中に装着された給水ポンプ12,各給水加熱器13,14等の他の機器に比べて小さく且つ非常に多く存在しているので、図10では仕切弁及び逆止弁の図示は省略されている。
【0059】
原子力発電プラントでは、原子炉圧力容器16内で得られた高温高圧蒸気が主蒸気管15を通って高圧タービン18に導入される。次いで、高圧タービン18から排出された蒸気は低圧タービン19に導入され、これらのタービンの回転力で発電機20を駆動する。高圧タービン18と低圧タービン19を通った蒸気は高圧タービン18及び低圧タービン19から排出されて主腹水器22やグランド蒸気復水器21で凝縮されて水にされ、その水は仕切弁及び逆止弁を有する給水系10により給水ポンプ12,各給水加熱器13,14を経て給水管11を通って原子炉圧力容器16に戻される。
【0060】
その給水系46の配管に採用された弁の内、仕切弁に本発明を適用した例について以下に説明する。
【0061】
図11は、給水系10の給水管11に装備される仕切弁の縦断面を示している。図12のようにその仕切弁の弁体30側の弁座としてコバルト基合金のリング状の板31が装着されている。同じく弁箱32側の弁座33の摺動面にもコバルト基合金のリング状の板31が装着されている。
【0062】
そのコバルト基合金はコバルトをベースに1.0重量%C−30.0重量%Cr−3.9重量%W を含んでいて、そのコバルト基合金は熱間鍛造と熱間圧延によってコバルト基合金中の共晶炭化物を30μm以下の複数の粒状又は塊状としてある。そのリング状のコバルト基合金の板31を液相拡散接合によって、図12に示すように弁箱32側の弁座33及び弁体30の弁座部位に接合した。
【0063】
仕切弁の弁体30は図12に示す様に、上部が厚くて下部が薄い円盤状の形状を有し、弁棒の上下方向の動きに連動して上下に駆動されて図中左右に弁箱32内を流入する水や水蒸気の流れを開閉するものである。
【0064】
リング状のコバルト基合金の板31を弁体30に装着する具体例を以下に説明する。即ち、仕切弁の弁体30の左右の表面に段差を設けて左右に突き出た突起34を設けた後に、段差を設けることで生じた凹んでいる部位に接合用インサート材を置いた。次いで該接合用インサート材の表面上に厚さ約7mmのリング状の板31を突起34に嵌めるようにして置いた。その後に接合用インサート材のみを溶融して弁体30にリング状の板31を液相拡散接合によって装着した。
【0065】
液相拡散接合に用いたインサート材は4.5 重量%Si,3重量%Bを含むNi基合金で、約1040℃以上で完全に溶融するものである。液相拡散接合条件は、接合温度:1100℃,保持時間:1h,真空度:1〜2×10-4Torr,加圧力:15g/cm2 とした。接合後の冷却は1100℃から650℃までを約150℃/h,650℃から425℃までを約100℃/h,425℃以下を室内で空冷により自然に除熱するものとした。
【0066】
弁座33にも環状の突起35を加工する。その突起の周囲の凹んでる部位に接合用インサート材を置いた。突起35に厚さ約7mmのリング状の板31を嵌めて接合用インサート材表面に置いた。その後に接合用インサート材のみを溶融して弁座7にリング状の板31を液相拡散接合によって装着した。リング状の板31や接合用インサート材の材質や液相拡散接合条件や接合後の冷却条件は弁体30への板31の接合の場合と同じである。
【0067】
弁体30や板31や弁座33は接合温度1100℃では溶融しない。板31が装着される弁体30側の部位や弁座33の材質は機械構造用炭素鋼S25Cである。機械構造用炭素鋼S25Cの熱膨張係数はCo基合金に比較して小さい。弁体30と弁座33の互いに向かい合う表面には図12に示したように、接合されるリング状の板6に内接して高さが2mmのリング状の突起34,35(段差)を設けた。これによって、接合時の板31と弁体30や弁座33の位置合わせを容易に行えると同時に、仕切弁の作動時に摺動部や接合部に負荷されるせん断力に対する抵抗力を高めることができる。
【0068】
図12の弁体30側の弁座となる板31は紙面に対して各々左右から見て、いずれも円形であり、更にリング状の板31は、弁体30の左右両側に凸型円形の突起34の外周に接して接合されている。
【0069】
弁箱32側の弁座33は円筒体であり、弁座33は弁箱32に組み込まれている。その弁座33の弁体30側の端面は摺動面であり、その端面の構成は、紙面に対して左側から見て、リング状の板31がリング状の突起35の外周に接して液相拡散接合されている。いずれの突起34,35もその高さは、リング状の板31の厚さ7mmよりも小さい2mmとしてある。
【0070】
このような方法で作製した仕切弁では、弁体と弁箱との間の相互接触面が板31で構成される。その板31の材質であるCo基合金においては、液相拡散接合の後も、その合金中の共晶炭化物が複数の粒状または塊状になって非連続分布で分散しているから、溶存酸素等の腐蝕環境を生む雰囲気によって共晶炭化物が連続的に腐蝕されるという事象が抑制される。そのため。そのCo基合金における鋳造組織の基地の脱落が抑制されるために、弁座の腐蝕・エロージョンの進行が抑止され、仕切弁における耐漏洩性能の低下が防止される。
【0071】
なお、本実施例ではいずれもリング状の耐蝕・耐摩耗性合金としてCo基合金の板31を用いたが、既述のように、ニッケルをベースにFeおよび/またはCrを添加した耐蝕・耐摩耗性合金や、鉄をベースにCrおよび/またはNiを添加した耐蝕・耐摩耗性合金や既述の表2の成分を有する合金に熱間鍛造や熱間圧延を施して合金中の共晶炭化物を非連続分布としたNi基合金やFe基合金なども同様に用いることができる。
【0072】
なお、本実施例ではインサート材として低融点のNi基合金を用いたが、Fe基又はCo基の低融点インサート材を用いることもできる。また、本発明の実施例と同様なことを仕切弁のみならず、逆止弁,安全弁,玉型弁等の弁座部等の摺動部や接触部に適用することで、それらの各弁の耐漏洩性能の低下,制御性・作動性能の低下を抑制する効果がある。
【0073】
このような実施例では、原子力発電プラントに用いられた弁の正常な機能を長く維持できる効果があり、その効果によって原子力発電プラントの信頼性を向上できる。
【0074】
この実施例による弁を配管に組み込んだ配管系を有するプラントにおいて、水質調整の目的からの過酸化水素水を配管に注入しても、溶存酸素の影響による弁の弁座等の摺動部の腐蝕・エロージョンを抑制でき、プラントの安全性向上に効果がある。
【0075】
特に、この実施例の弁を原子力発電プラントの給水系統の配管に装備して用いた場合には、弁座に採用したCo基合金の共晶炭化物の腐蝕脱落とそれに伴う、コバルトの給水系統内への流出・拡散を抑制できる。そのために、給水系統から各系統へと流出拡散するコバルトとそのコバルトの放射化が抑制できて原子力発電プラントでの作業者の放射線被曝の低減を顕著に図ることができる。
【0076】
本発明の耐蝕・耐摩耗性合金は内燃機関にも次のようにして用いることができる。即ち、ガソリンを燃料とする内燃機関は、図13,図14,図15のようにガソリンが燃焼するためのシリンダ40を備えている。そのシリンダ40は上部がシリンダヘッド41でふさがれている。そのシリンダヘッド41には、吸気口と排気口を備え、各吸気口と排気口とがバルブ42で開閉できるようになっている。
【0077】
バルブ42はシリンダヘッド41に設けられた動弁機構によって開閉駆動される。動弁機構は、バルブ42の駆動軸廻りに設けられたばね43と、その駆動軸の上端に連結されたバルブリフター44と、そのバルブリフター44の上部に設けられたアジャステングシム45と、そのアジャステングシム45の上面に接触しているカム46と、そのカム46をエンジン出力を用いて回転駆動する動力伝達手段とからなる。
【0078】
その動弁機構にあっては、エンジンの出力の一部を用いてカム46を回転させる。そのカム46の動きでバルブリフター44をばね43に抗してアジャステングシム45を介して押し下げる。その押し下げによって、バルブ42は各吸気口と排気口のバルブシート47から下方へ離れてそのルブ42が装着されている吸気口あるいは排気口が開く。
【0079】
カム46の回転がさらに進むと逆にバルブ42はバルブシート47に接触してバルブ42が閉じる。そのバルブシート47とバルブ42との接触部分がシール部分として機能してシリンダ40内のガスが漏れないように成っている。
【0080】
このような動きが有る動弁機構にあっては、アジャステングシム45とカム46との間で摺動運動による摩擦が生じる。バルブ42とバルブシート47間にも摩擦が生じる。これらの摩擦に抗して動弁機構を駆動するからエンジンの出力は損失を受け、エンジン効率が低下する。
【0081】
そこで、エンジンのバルブ42とバルブシート47との接触部に、図14,図15のように、耐蝕・耐摩耗合金としてCo基合金48を液相拡散接合49によって接合する。その接合の方法は前述の液相拡散接合と同じように行い、接合後の冷却条件も先述のとおりである。そのCo基合金48は少なくとも接合前に熱間鍛造されてコバルトの基材部に複数の粒状又は塊状に組成されている共晶炭化物を有する金属組織とされている。
【0082】
同様に、バルブリフター45の上端にも基材部に複数の粒状又は球状に組成されている共晶炭化物を有するCo基合金を液相拡散接合してアジャステングシム4とした。
【0083】
Co基合金48や液相拡散接合に用いたインサート材の成分は表3に示すような成分を持っている。
【0084】
【表3】
Figure 0004205505
【0085】
液相拡散接合では、インサート材は溶融するもののCo基合金48や弁42やバルブシート47は溶融しない。そのため、接合後のCo基合金48は複数の粒状又は塊状の共晶炭化物が基材中に非連続分布で分散した金属組織を保つことができる。
【0086】
このように接合後にあってもCo基合金48内部や表面に共晶炭化物が粒状又は球状のまま存在できる。このように、Co基合金48に共晶炭化物が粒状又は塊状のまま存在し、その共晶炭化物の露出が限定的となり、その結果、損傷が抑制される。
【0087】
即ち、共晶炭化物が粒状又は塊状のまま非連続分布で分散して存在しているCo基合金48が硫黄分による腐蝕環境にさらされると、腐蝕環境に接触した粒状又は塊状の共晶炭化物は腐蝕や摺動作用を受けて表面から脱落して腐蝕環境に接触する表面には共晶炭化物が存在しない基材部のみの表面となる。従って、腐蝕と脱落が交互且つ繰り返し連続して起こる現象が防止されて損傷が抑制される。
【0088】
粒状又は塊状に組成されている共晶炭化物を有するCo基合金48の摩擦係数を常温、高面圧(約2000kg/cm2 )負荷した条件で測定して開発材と表示してグラフにしたところ、図9に示すように、従来の網目状の共晶炭化物を有するCo基合金の摩擦係数の約1/2〜2/3と低いことが確認されている。
【0089】
エンジンのバルブ42は高温下(最大約500〜600℃),高摺動回数下での使用が想定されるが、この試験条件における高面圧下での試験結果により低摩擦係数が確認されていること、また、摩擦係数は剪断強さ/硬度の比に支配されるが、本材料は剪断強さ/硬度の比の温度依存性がほとんどなく材料の組成が同じであれば変化がないと考えられるため、高温下,高摺動回数下でも低摩擦の効果が得られると考えられる。
【0090】
また、耐蝕性能の比較のため、ストラウス試験,希硫酸中エロージョン試験を行った。結果として、粒状又は球状に組成されている共晶炭化物を有するCo基合金48(開発材)は、ストラウス試験では、表1に示すように網目状に組成されている共晶炭化物を有するCo基合金にくらべ、30倍以上の耐蝕性を示し、希硫酸中のエロージョン試験では、図15に示す開発材の特性曲線のように従来の網目状の共晶炭化物を有するCo基合金に比べて20〜30倍の耐久性能を示した。
【0091】
これにより、本実施例では、高耐蝕化,低摩耗性の向上及び低摩擦化を実現することで動弁系の耐久性向上,動力損失低減が図れ、エンジン全体の効率向上,出力向上と共に耐久力向上を図ることが出来る。
【0092】
本実施例で採用されるCo基合金は、表2の成分を有するCo基合金であっても良く、表3に示すような成分を持つNi基合金やFe基合金を熱間鍛造して塊状または粒状の共晶炭化物を有するNi基合金やFe基合金を作ってCo基合金48に置き換えて採用しても、エンジン全体の効率向上,出力向上と共に耐久力向上を図ることが出来る。
【0093】
この場合も、バルブ42やバルブシート47にCo基合金やNi基合金やFe基合金を接合するに際して、接合後もCo基合金やNi基合金やFe基合金に共晶炭化物が球状又は粒状に存在出来るように接合手段や接合条件を選択する。選択すべき接合手段は、液相拡散接合が好ましい。
【0094】
本実施例では、エンジンのバルブ42とバルブシート47のシール機能を有する部位に塊状又は粒状の共晶炭化物を有するCo基合金またはNi基合金又はFe基合金を液相拡散接合することで、高い硬度を維持しながら、強靭かつ耐摩耗性及び耐蝕性に富み、且つ低摩擦のシール面を提供できる。
【0095】
そのため、エンジンの燃料であるガソリン中に含まれる硫黄分等に起因する腐蝕と腐蝕部を起点とする割れの進行,エロージョンによるシール性能の劣化を防止することで、内燃機関のエンジンの耐久性を向上させ、エンジン効率の低下を防止できるばかりか、さらに、低摩擦のシール面を提供することで摩擦によるエンジン効率低下を防止でき、エンジンの出力向上に寄与することが出来る。
【0096】
エンジンの動弁機構を構成するバルブリフター44の外周面に塊状又は粒状の共晶炭化物を有する表2や表3のCo基合金又はNi基合金又はFe基合金を液相拡散接合して装着すると、一層のこと、エンジンの耐久性を向上させると共に、エンジン効率の低下を防止できる。
【0097】
網目状に共晶炭化物を有するCo基合金を従来例とし、共晶炭化物を粒状または塊状にして基材中に非連続分布で分散した表2に示した成分を有するCo基合金を本実施例とし、両合金を比較すると、以下の表4のように性能に差が出る。
【0098】
【表4】
Figure 0004205505
【0099】
このように従来例と本実施例では合金の性能に差があるので、バルブリフターに本実施例の合金を液相拡散接合によって接合して用いれば、動弁機構の摩擦によるエンジン出力ロスを軽減できる。また、バルブやシートに本実施例の合金を液相拡散接合によって接合して用いれば、SOx雰囲気下での腐蝕感受性がなく、且つ衝撃値が高いため、バルブやシートの健全性を長く維持できる。
【0100】
本発明の耐蝕・耐摩耗性合金はポンプ設備にも次のようにして用いることができる。即ち、図16に示したポンプ設備は、電動モータなどによりシャフト50を回転すると、そのシャフト50に固定されているインペラ51はポンプケーシング52内で回転する。そのインペラ51の回転によって、ポンプケーシング52内に流入してきた流体Xが高圧になってポンプケーシング52の外へ吐出される。
【0101】
その液体Xと気体Yとの境界に液体Xが気体Y側へ漏れないようにメカニカルシールが採用されている。そのメカニカルシールは図17に図示した。図17のメカニカルシールは、以下の構成を備えている。
【0102】
即ち、ポンプケーシング52と一体のシールボックス53の内側でシャフト50の周囲に配置されたトメガネ55は、ノック54によってシャフト50に固定されている。そのトメガネ55の内側において、シャフト50の周囲にばね56と押しがね57とパッキング58とワッシャ59とが配備されている。
【0103】
その一方、シールボックス53の端部にはシャフト50の周囲に配備したシールカバー60が取り付けられる。そのシールカバー60にはシャフト50の周囲に配備したシート61が取り付けられている。
【0104】
押しがね57とパッキング58とワッシャ59はばね56で右側に押されているので、ワッシャ59はシート61と密封端面Sで押し当てられている。このようにして、ワッシャ59をシート61にばね56で押し当てることによって液体Xが気体Y側へ漏れないようにシールしている。
【0105】
トメガネ55とばね56と押しがね57とパッキング58とワッシャ59とはシャフト50といっしょに回転するが、シート61は回転しないので、密封端面Sでは摩擦熱が発生し、密封端面Sの焼き付きや摩耗や腐蝕を促進させる。そのために密封端面に低摩擦で耐蝕性の高い材料を使用したメカニカルシールが必要となる。
【0106】
その必要性を満たすために、本実施例では、ワッシャ59のシート61と接触する部位に図17に示すように耐蝕・耐摩耗性合金の板62を装着する。その耐蝕・耐摩耗性合金としては、既述のいずれの合金を用いても良く、その合金の基材中には共晶炭化物が粒状または塊状で非連続分布で分散している。そして、その合金のワッシャ59への装着は液相拡散接合による接合によって達成する。その液相拡散接合の接合方法や接合条件は既述のとおりの内容とする。同様にしてシート61のワッシャ59に接触する部位に同様な耐蝕・耐摩耗性合金を装着しても良いし、同様にしてワッシャ59とシート61との両方に対して、相互に接触し合う個所に同様な耐蝕・耐摩耗性合金を装着して耐蝕・耐摩耗性合金同士を密封端面Sで接触させるようにしても良い。
【0107】
このような実施例によれば、ワッシャ59またはシート61の少なくとも一方に接合された耐蝕・耐摩耗性合金は共晶炭化物が粒状または塊状で非連続分布で分散していて腐蝕しにくい状態に維持されている上、摩擦係数が図9の耐蝕・耐摩耗性合金の摩擦係数のように低く維持できる。
【0108】
そのため、密封端面Sにおける硫黄分や溶存酸素といった腐蝕環境下での耐蝕性の向上と低摩擦化を達成できる。そのため、本実施例によれば、メカニカルシールの性能が長く維持でき、信頼性の高いメカニカルシールが提供できる。メカニカルシールの性能が長く維持できるので、そのメカニカルシールを採用したポンプや、そのポンプを採用したプラントの信頼性も向上する。
【0109】
従来、ワッシャ59はワッシャ59の密封端面SにCo基合金を肉盛して用い、シート61は焼成フェノール含浸カーボンやフェノール成型カーボンやホワイト含浸カーボンで製作されていた。このような従来例に対して、ワッシャ59またはシート61若しくはワッシャ59とシート61の両方に共晶炭化物が粒状または塊状になって基材中に非連続分布で分散して存在している耐蝕・耐摩耗性合金(Co基合金)を液相拡散接合で装着した本実施例のそのCo基合金の性能を比較すると、表5のとおりである。表5での本実施例のCo基合金は表2に示した成分を有し、合金中の共晶炭化物が粒状または塊状で合金中に非連続分布で分散している。
【0110】
【表5】
Figure 0004205505
【0111】
このような性能差によって、本実施例によるメカニカルシールでは、密封端面Sでの焼き付きや摩耗や腐蝕が抑制できる。その上、本実施例では従来になく高い圧縮応力や衝撃値にも耐えるメカニカルシールが提供できる。また、本実施例では耐蝕・耐摩耗性合金の板62をワッシャ59などに接合した後でも耐蝕・耐摩耗性合金の基材中に共晶炭化物が球状または塊状で非連続分布で分散して存在できるので、耐蝕性も高く密封端面Sでの漏れが確実に抑制でき、その漏れによる密封端面Sにおけるエロージョンの発生も抑制できる。このように、本実施例によれば、性能の高いメカニカルシールが提供できる。
【0112】
図16に示したポンプ設備の運転時において、ワッシャ59は回転軸50とともに回転しており、ワッシャ59に装着された板62はポンプケーシング52に取り付けられて動かないシート61と接触しながら回転する。板62とシート61との接触により、回転側の部材である回転軸50と固定側の部材であるポンプケーシング52との間のシールが行われ、液体の漏洩を防止している。ワッシャ59,板62及びシート61はポンプ設備におけるメカニカルシール装置を構成している。ワッシャ59(本体部)及び板62(耐蝕・耐摩耗性合金部)は第1シール部を構成し、シート61は第2シール部を構成する。第1シール部をポンプケーシング52に設置し、第2シール部を回転軸50側に設置してもよい。更には、ポンプケーシング52に設置される第2シール部を第1シール部と同じ構成にしてもよい。
【0113】
板62はシール性能を確保するためにばね56の作用により常にシート61に接触しながら高速回転している。このため、シール面を形成する板62の摩耗,焼付,腐蝕が懸念されるが、板62は共晶炭化物が前述のように粒状または塊状になって耐摩耗性,摺動性に優れているためほとんど摩耗しない。また、板62は耐蝕性にも優れているため液体との接触による腐蝕も防止できる。このため、メカニカルシール装置の保守の頻度が減少し、メカニカルシール装置の寿命も延びる。これは、ポンプ設備の保守作業を軽減することにつながる。また、前述の粒状または塊状の共晶炭化物を有する耐蝕・耐摩耗性合金より構成される板62は摩擦係数が約0.16と小さいため、回転軸50の回転動力が板62とシート61との接触部で熱エネルギーに変わる割合が著しく小さくなる。すなわち、回転軸50の回転動力の損失が小さくなる。
【0114】
本実施例における板62のような粒状または塊状の共晶炭化物を有する耐蝕・耐摩耗性合金を含むメカニカルシール装置は、流体昇圧装置である本実施例のようなポンプ設備以外に、回転軸とケーシングとのシールを行う必要のある、ガスを昇圧するコンプレッサまたは送風機に適用することが可能である。コンプレッサ及び送風機は流体昇圧装置の一種である。更には、蒸気が流れるタービンに適用することも可能である。すなわち、タービンの回転軸とケーシングの間のシールを行うメカニカルシール装置として、ポンプ設備に用いた、粒状または塊状の共晶炭化物を有する耐蝕・耐摩耗性合金を接触部に有するメカニカルシール装置を適用する。ポンプ設備,上記のコンプレッサ,送風機及びタービンは、内部に流体が流れる回転装置である。
【0115】
図16に示すポンプ設備,上記のコンプレッサ,送風機及びタービンを包含する好ましい発明の概念は、以下に示すようにも把握できる。
【0116】
部に流体が流れるケーシングと、前記ケーシング内に挿入された回転軸と、前記回転軸と前記ケーシングとの間のシールを行うメカニカルシール装置とを備えた回転装置であって、
前記メカニカルシール装置は、前記回転軸と一緒に回転する第1シール部と、前記ケーシングに取付けられて前記第1シール部に接触する第2シール部とを備え、
前記第1シール部及び前記第2シール部の少なくとも一方は、金属ミクロ組織の基地部に粒状または塊状をした共晶炭化物が分散する耐蝕・耐摩耗性合金部であって他方のシール部に接触される耐蝕・耐摩耗性合金部、及び本体部を有し、前記耐蝕・耐摩耗性合金部が前記本体部に拡散接合されている回転装置。
【0117】
上記の回転装置は、回転軸とケーシングとの間のシールを行うメカニカルシール装置が、前記回転軸と一緒に回転する第1シール部と、前記ケーシングに取付けられて前記第1シール部に接触する第2シール部とを備え、前記第1シール部及び前記第2シール部の少なくとも一方が、金属ミクロ組織の基地部に粒状または塊状をした共晶炭化物が分散する耐蝕・耐摩耗性合金部であって他方のシール部に接触される耐蝕・耐摩耗性合金部、及び本体部を有し、前記耐蝕・耐摩耗性合金が前記本体部に拡散接合されている、という特徴を有する。シール部には本体部に拡散接合された耐蝕・耐摩耗性合金部が存在するので、拡散接合された耐蝕・耐摩耗性合金部は前述のように粒状または塊状の共晶炭化物が存在し、網目状共晶炭化物が存在しない。このため、第1シール部と第2シール部の接触部で発生する摩擦熱によってシール部の温度上昇が生じることによるシール端面の焼付き,摩耗,シール材料の腐蝕促進を抑制でき、結果、シール部の耐蝕・耐摩耗性が向上し、第1シール部及び第2シール部を有するメカニカルシール装置の保守の頻度が減少し、メカニカルシール装置の寿命も延びる。これは、回転装置の保守作業を軽減することにつながる。また、上記の耐蝕・耐摩耗性合金部は摩擦係数が小さいため、第1シール部と第2シール部との接触部で発生する熱エネルギーを少なくできる。これは、回転装置の回転軸を回転させる動力の損失を低減させることにつながる。
【0125】
【発明の効果】
本発明によれば、耐蝕・耐摩耗性合金をポンプ設備及び弁の摺動部や接触部に用いることにより、腐蝕環境下による共晶炭化物の腐蝕損傷に伴うの摺動部や接触部の荒れが少なく、その摺動部や接触部の摩擦抵抗を良好に維持することができる。その結果低摩擦な摺動面や接触面を有するポンプ設備及び弁を提供することができる。
【図面の簡単な説明】
【図1】コバルトをベースにCrおよび/またはWを添加した耐蝕・耐摩耗性合金の表面の金属組織を示すSEM写真(a)とその模式図(b)である。
【図2】図1の耐蝕・耐摩耗性合金の金属組織を一部拡大して示した(a)とその模式図(b)である。
【図3】コバルトをベースにCrおよび/またはWを添加した耐蝕・耐摩耗性合金の表面の面分析にて表された金属組織を示す(a)とその模式図(b)である。
【図4】熱間塑性加工を行ったコバルトをベースにCrおよび/またはWを添加した耐蝕・耐摩耗性合金の表面の金属組織を示す(a)とその模式図(b)である。
【図5】熱間塑性加工を行ったコバルトをベースにCrおよび/またはWを添加した耐蝕・耐摩耗性合金の表面の面分析にて表された金属組織を示す(a)とその模式図(b)である。
【図6】コバルトをベースにCrおよび/またはWを添加した耐蝕・耐摩耗性合金の溶存酸素による損傷の繰り返し進行状況を表した模式図である。
【図7】熱間塑性加工を行ったコバルトをベースにCrおよび/またはWを添加した耐蝕・耐摩耗性合金の溶存酸素による損傷抑止状況を表した模式図である。
【図8】熱間塑性加工を行ったコバルトをベースにCrおよび/またはWを添加した耐蝕・耐摩耗性合金のストラウス試験結果で得られた金属組織を示すSEM写真である。
【図9】熱間塑性加工を行ったコバルトをベースにCrおよび/またはWを添加した耐蝕・耐摩耗性合金の摺動試験による摩擦係数を示すグラフである。
【図10】原子力発電プラントの配管系統図である。
【図11】原子力発電プラントの配管系統に採用された仕切弁の縦断面図である。
【図12】図11の仕切弁における弁体と弁箱との各弁座の接触状態を示した断面図である。
【図13】内燃機関の一部断面表示による全体図である。
【図14】図13に示したバルブ近傍の拡大断面図である。
【図15】図14のバルブとシートとの接触部の拡大断面図である。
【図16】ポンプの断面図である。
【図17】図16のポンプのメカニカルシール近傍の断面図である。
【符号の説明】
1…共晶炭化物、2…鋳造組織の基材部、10…給水系、30…弁体、31,62…板、32…弁箱、33…弁座、41…シリンダヘッド、42…バルブ、50…シャフト、51…インペラ、52…ポンプケーシング、53…シールボックス、59…ワッシャ、61…シート。[0001]
BACKGROUND OF THE INVENTION
  The present invention provides a combination of corrosion resistance and wear resistance.MoneyIt relates to the fluid equipment and dynamic equipment used.
[0002]
[Prior art]
In plant equipment such as turbine power generation equipment, for valves such as safety valves, anti-corrosion and anti-wear performance is required to prevent erosion damage to the valve seat during operation and to prevent galling during valve operation. In addition, a valve seat or a sliding portion is used in which a corrosion-resistant and wear-resistant alloy in which Cr and / or W is added based on cobalt having a high hardness and excellent in hardness is used.
[0003]
However, in recent years, in plant facilities such as turbine power generation facilities, hydrogen peroxide water or the like has been injected for the purpose of water quality adjustment. As a result, the amount of dissolved oxygen in the downstream of the injection point increases, and the corrosion resistance of the valve seat surface and sliding parts with the addition of Cr and / or W based on the cobalt that has been built up to prevent erosion and galling. -Corrosion damage occurs in the eutectic carbide among the eutectic carbide constituting the wear resistant alloy and the base portion of the cast structure.
[0004]
In addition, when there is a flow (for example, a water flow), there is a report that the base material portion of the cast structure falls off and erosion occurs following the corrosion damage of the eutectic carbide.
[0005]
The above-mentioned related reports include “Thermal Nuclear Power Generation Vol.30-5, Treatment Method of Boiler Water with Oxygen and Ammonia in Steam System of Thermal Power Plant”, “Machine Damage 1982-2 No. 2 at VEW Gerstein Power Plant For example, “Experience of operation by combined operation method” or “Effect of heat treatment conditions on intergranular corrosion of welded zone of materials and environment Vol.47, No.3, cobalt base alloy”.
[0006]
However, even in the above report, there is no effective means for eliminating the occurrence of erosion, which is a problem.
[0007]
On the other hand, JP-A-8-334280 (corresponding US Pat. No. 6,164,624) discloses an orifice member made of a metal material having a hardness higher than that of the valve body (Vickers hardness 150 to 500). An expansion valve is disclosed that can be incorporated into a main body and prevent erosion of a valve port equipped with an orifice.
[0008]
Japanese Patent Laid-Open No. 5-208325 (corresponding US Pat. No. 5,183,390) discloses a rod-shaped wear-resistant material containing cobalt, nickel, tungsten, manganese and selenium at the rear edge of a steam turbine blade. It is disclosed that the frictional surfing method is used to improve the wear resistance of the blades. When attaching the wear-resistant material to the blades by the friction surfing method, disclose that the rod-shaped wear-resistant material should not be melted from the viewpoint of change in hardness and prevention of shrinkage cracking. Yes.
[0009]
Japanese Patent Laid-Open No. 59-179283 discloses that a valve seat made of 30 to 45% by weight of Cr, 3.0 to 8.0% by weight of Ti, 0 to 10% by weight of Mo, and the balance Ni diffuses in the valve body and the valve box. A bonded valve is disclosed.
[0010]
Japanese Laid-Open Patent Publication No. 60-86239 discloses a valve seat comprising 10 to 45% by weight of Cr, 1.5 to 6% by weight of at least one of Al and Ti, 20% by weight or less of Mo, and the balance Ni. Discloses a valve diffusion-bonded to a valve body and / or a valve box.
[0011]
Japanese Laid-Open Patent Publication No. 4-19476 discloses a valve in which a valve seat made of a super hard material or a heat-resistant material is brazed to the valve seat portion of the valve box via an amorphous alloy layer.
[0012]
Japanese Patent Laid-Open No. 7-16610 discloses that a high carbon martensitic stainless steel material is made into an intermediate material having an intermediate size by hot plastic working, and the intermediate material is subjected to cold plastic working and again heated at 850 ° C. or higher. A technique for producing a steel material having a target size by performing an interplastic working is disclosed. According to the disclosed technique, it is described in the publication that the average eutectic carbide size in the steel material having the target size has reached 4.2 μm.
[0013]
[Problems to be solved by the invention]
Valves such as safety valves used in turbine power plants are based on cobalt, which has a high hardness and excellent corrosion resistance and wear resistance to prevent erosion damage due to the high flow rate of the valve seat during operation. A valve seat using a corrosion-resistant and wear-resistant alloy to which Cr and / or W is added is used.
[0014]
Also, in cage valves, etc., the valve box using the above corrosion-resistant and wear-resistant alloy is used on the guide surface that guides the valve element or the inner surface of the cage to prevent galling during the operation of the valve. Yes.
[0015]
However, if the valve seat made of the above corrosion-resistant and wear-resistant alloy is used in a high-temperature and high-pressure water / steam atmosphere with a lot of dissolved oxygen, the base material layer layer of the cast structure in the alloy and the cast structure in a mesh form are used. The eutectic carbide enclosing the base material layer is selectively corroded by dissolved oxygen in the fluid. As a result, the surface roughness of the valve seat becomes remarkable, and the tunneling action (Fj Heymann: Machine Dedign. 42, 118 (1970)) that occurs when a high-speed jet penetrates into the damaged part of the corrosion is also helped. Due to the corrosion removal of the crystalline carbide, the base material portion of the cast structure that has lost its retention by the network-like eutectic carbide is easily removed by the flow, and erosion occurs in the corrosion-resistant and wear-resistant alloy.
[0017]
  BookIt is an object of the present invention to provide a device using a corrosion-resistant and wear-resistant alloy with improved wear resistance and erosion performance in a wear-resistant portion and erosion shield portion of the device.
[0018]
[Means for Solving the Problems]
The gist of the present invention for achieving the above object is as follows.
[0019]
  Cobalt base added with Cr and / or WIsAn intermediate material cast into an ingot or slab is subjected to hot plastic working at a temperature of 650 ° C. or higher and a solidus temperature or lower, thereby forming a reticulated eutectic carbide in the intermediate material and a base surrounded by the same. Of the structure composed of the material part, the eutectic carbide is formed into a plurality of grains or a plurality of aggregates to form a discontinuous distribution, the friction coefficient is 0.1 to 0.5, and the Bicaus hardness is 300 which is not subjected to the aging effect treatment. It is a corrosion-resistant and wear-resistant alloy characterized by being -600 Hv.
[0020]
  The cobalt base material to which Cr and / or W is added is 0.1 to 3.5% C, 25% or less Ni, 25 to 35% Cr, 5% or less Fe, 20% or less W, 1. 5% or less Mn, 1.5% or less Si, balance Co and inevitable impurities.The
[0021]
For example, a base material portion of a cast structure formed by adding cobalt and Cr and / or W to an intermediate material represented by an ingot or slab, and a cast material made of eutectic carbide, continuously in a mesh shape. The hard eutectic carbide, which has a low hardness and a low ductility, is subjected to hot plastic working. Thereby, the said intermediate material is made into a fine granular form or lump shape. As a result, the structure of the base material part enters into the gaps formed between the eutectic carbides, and as a result, the periphery of the eutectic carbides that have a low hardness, high ductility, and tough base material parts that are granulated or agglomerated The eutectic carbide is discontinuous by being distributed to.
[0022]
At the same time, by maintaining at a high temperature of 650 ° C or higher, the diffusion of chromium present in the eutectic carbide is promoted, the chromium deficient layer around the eutectic carbide is reduced, and the corrosion resistance of the eutectic carbide itself is improved. In addition, a corrosion-resistant and wear-resistant alloy can be obtained.
[0023]
According to the above, among the base material portion of the cast structure and the eutectic carbide melted by adding Cr and / or W to the base of cobalt, the eutectic carbide continuously distributed in a network shape is in the form of a plurality of particles or lumps. By changing to, discontinuous eutectic carbides can be obtained, and the corrosion phenomenon can be discontinuous and partly shallow and superficial.
[0024]
As a result, the progress of corrosion is suppressed, and the tunneling action (Fj Heymann: Machine Dedign. 42, 118 (1970)) that occurs when a high-speed jet invades the corrosion damaged part can also be suppressed, and the erosion resistance performance. Will also improve.
[0025]
Due to the above effects, erosion / corrosion resistance can be improved.
[0026]
Moreover, by maintaining at a high temperature of 650 ° C. or higher, the diffusion of Cr present in the eutectic carbide around the eutectic carbide is promoted, and the Cr deficiency existing around the eutectic carbide containing Cr The number of layers is reduced, and the corrosion resistance of the eutectic carbide itself can be improved.
[0028]
When all or part of the above corrosion-resistant and wear-resistant alloy is melted, the eutectic carbide in the molten part forms a network-like eutectic carbide with low corrosion resistance. It can be used by being joined to the base material without melting into a base metal that is a base material to which a corrosion-resistant / abrasion-resistant alloy is attached by processing.
[0029]
By forming a massive or granular eutectic carbide without the presence of a network of eutectic carbide, high corrosion resistance can be achieved even when fluid equipment such as pumps, valves, pressure equipment, and turbines are used in a corrosive atmosphere. And erosion resistance can be obtained.
[0030]
In addition, corrosion-resistant and wear-resistant alloys are directly joined to the base metal without changing the metal composition, and dynamic equipment such as pumps, valves, turbines, engines, etc. used for sliding parts or contact parts are corrosive. High corrosion resistance and erosion resistance can be obtained even if used in the above.
[0031]
The friction coefficient is 0.1 to 0.3, and diamonds (friction coefficient 0.1 in the unlubricated state), sapphire (friction coefficient 0.2 in the unlubricated state), and ruby-like ones may be obtained. Friction resistance can be lowered compared to the friction coefficient 0.35 to 0.8 of other metals such as brass (friction coefficient 0.35 in the unlubricated state) and steel (friction coefficient 0.8 in the unlubricated state). .
[0032]
Such a corrosion-resistant and wear-resistant alloy is used in a wear-resistant part of a fluid device, or an erosion shield part, and a sliding part or a contact part of a dynamic device.
[0033]
In order to attach the corrosion-resistant and wear-resistant alloy of the present invention to a fluid device and a dynamic device, the composition of the corrosion-resistant and wear-resistant alloy is applied to the wear-resistant portion, the erosion shield portion, the sliding portion or the contact portion as much as possible. Wear without changing. As a mounting method, a joining method that does not melt the corrosion-resistant and wear-resistant alloy is used. As an example of the joining method, a liquid phase diffusion joining method can be used.
[0034]
More specifically, the corrosion-resistant and wear-resistant alloy of the present invention is used as a valve seat mounted on a contact surface of a valve body and a valve box provided in a piping system of a nuclear power plant or the like, or a rotation of a pump. As a contact surface material of at least one of the contact surfaces of the seat and the washer that rotate relatively around the shaft, or as a valve seat mounted on the contact surface of the valve seat and the valve provided in the cylinder head of the internal combustion engine, or It is used for at least one of the contact surfaces of both the valve lifter and the cam of the internal combustion engine.
[0035]
DETAILED DESCRIPTION OF THE INVENTION
A typical SEM photograph of the surface of a corrosion-resistant and wear-resistant alloy in which Cr and / or W is added based on cobalt is shown in FIG. 1 (where (a) is an SEM photograph, (b) is a schematic diagram thereof, FIG. (FIG. 5 is also the same), FIG. 2 shows a SEM photograph image taken at high magnification, and FIG. 3 shows a Cr surface analysis SEM photograph at the same position as FIG. 2 on the surface of the corrosion-resistant and wear-resistant alloy.
[0036]
Furthermore, FIG. 4 shows an SEM image of the metal structure on the surface of the corrosion-resistant and wear-resistant alloy that has been subjected to hot plastic processing such as forging and rolling. FIG. 5 shows a Cr surface analysis SEM photograph of the same position as in FIG. 4 on the surface of the corrosion-resistant and wear-resistant alloy.
[0037]
1, 2, and 3, the eutectic carbide 1 containing Cr and C as main components is distributed on the surface of the surface-welded alloy continuously in a network form on the base material portion 2 of the cast structure containing cobalt as a main component. ing.
[0038]
On the other hand, in FIG. 4 and FIG. 5 which are embodiments of the present invention, the eutectic carbide 1 is uniformly distributed on the surface of the corrosion-resistant and wear-resistant alloy in a granular or lump shape with respect to the base portion 2. It is discontinuous. Since the eutectic carbide 1 has changed from a network shape to a granular shape or a lump shape, the proportion of the eutectic carbide 1 in the surface is reduced.
[0039]
FIG. 6 is a schematic diagram showing the progress of repeated damage due to dissolved oxygen in a corrosion-resistant and wear-resistant alloy in which Cr and / or W is added based on cobalt.
[0040]
Corrosion and erosion of the corrosion-resistant and wear-resistant alloy proceeds because the eutectic carbide 1 is corroded by dissolved oxygen, so that the two base layer portions of the cast structure easily fall off.
[0041]
As shown in the SEA photograph in FIG. 3, the corrosion-resistant and wear-resistant alloy in which Cr and / or W is added to a normal cobalt base has a continuous eutectic carbide 1 in a network. Therefore, the corrosion of the eutectic carbide 1 due to dissolved oxygen and the dropping of the two layers of the base material portion of the cast structure occur continuously, resulting in the progress of corrosion and erosion in a dissolved oxygen atmosphere.
[0042]
In contrast, in a corrosion-resistant and wear-resistant alloy in which Cr and / or W is added to a cobalt base that has been subjected to hot plastic working, the eutectic carbide 1 exists discontinuously in a granular or massive form, and the eutectic due to dissolved oxygen. Corrosion damage of the carbide 1 is limited to the eutectic carbide 1 on the surface in contact with dissolved oxygen.
[0043]
Accordingly, after the eutectic carbide 1 on the surface is removed by corrosion, further corrosion damage does not proceed. This will be described with reference to the schematic diagram showing the state of damage suppression by dissolved oxygen in FIG.
[0044]
In order to confirm the above effect, JIS G 0575 “Sulfuric acid / copper sulfate corrosion test of stainless steel” (Straus test) was applied. A test by Takahisa, Honda et al. (Materials and Environment Vol. 47: Cobalt-base alloy welded grains) was conducted on a cobalt-based corrosion-resistant and wear-resistant alloy with a continuous distribution of eutectic carbides in a network. (Influence of heat treatment conditions on interfacial corrosion), it has been reported that surface-welded alloys of corrosion-resistant and wear-resistant alloys of cobalt-based alloys show corrosion progression.
[0045]
However, when a similar test was conducted on a corrosion-resistant and wear-resistant alloy in which Cr and / or W was added based on cobalt that had been subjected to plastic working such as forging and rolling, the surface showed almost no etching and depth. There was no progress of corrosion in the direction, and good corrosion resistance could be confirmed. The test results are shown in FIG. Moreover, the measurement result of the friction coefficient according to increase / decrease in the frequency | count of sliding is shown in FIG.
[0046]
[Table 1]
Figure 0004205505
[0047]
From the above results, in the case of a corrosion-resistant and wear-resistant alloy in which Cr and / or W is added based on cobalt in which the eutectic carbide 1 is discontinuously present in a granular or lump shape in a corrosive environment, the corrosion depth is Compared to the conventional case, it can be suppressed to about 1/30, and when the preheating temperature is raised, the depth of corrosion can be reduced by further diffusing Cr.
[0048]
As a result, the corrosion-resistant and wear-resistant alloy in which the eutectic carbide 1 is discontinuously present in a granular or massive form can suppress corrosion due to dissolved oxygen, and as a result, erosion can also be suppressed.
[0049]
Further, when the preheating temperature of the corrosion-resistant and wear-resistant alloy in which Cr and / or W is added based on cobalt is about 600 ° C. and about 700 ° C., the preheating temperature at which Cr diffuses more is compared. When the temperature is about 700 ° C., the granular or massive eutectic carbide 1 itself has high corrosion resistance. When the preheating temperature is increased at the time of joining and the base material is joined, the corrosion resistance and resistance to abrasion are further improved. It can be a wearable alloy.
[0050]
Nickel-based Fe and / or Cr-added corrosion-resistant and wear-resistant alloys and iron-based Cr and / or Ni-added corrosion-resistant and wear-resistant alloys are also heated in the state of being heated below the solidus temperature. By performing interplastic processing, the corrosion resistance and wear resistance alloy can be improved in the same manner as the above-described corrosion-resistant and wear-resistant alloys to which cobalt-based Cr and / or W is added. A moving surface can be provided.
[0051]
In addition, with respect to the corrosion-resistant and wear-resistant alloy in which Cr and / or Ni is added to the iron base, the above-described cobalt-based Cr and / or the above-described cobalt-based Cr and / or by performing hot plastic working in a state of being heated to a temperature below the solidus temperature Alternatively, like the corrosion-resistant and wear-resistant alloy to which W is added, corrosion resistance and wear resistance can be improved, and at the same time, a low friction sliding surface can be provided.
[0052]
The material components of the corrosion-resistant and wear-resistant alloy in which Cr and / or W is added based on cobalt as described above are 0.1 to 3.5% C, 25% or less Ni, 25 to 35% Cr in weight ratio. 5% or less Fe, 20% or less W, 1.5% or less Mo, 1.5% or less Si, the balance Co and inevitable impurities.
[0053]
Further, the material components of the corrosion-resistant and wear-resistant alloy in which Fe and / or Cr are added based on nickel are 0.1 to 2.5% C, 3 to 9% Si, 7 to 25% Cr, It consists of 0.5-5% B, 2-6% Fe, 1-5% W, 17% or less Mo, the balance Ni and inevitable impurities.
[0054]
In addition, the material components of the corrosion-resistant and wear-resistant alloy in which Cr and / or Ni is added to the iron base are 0.1 to 1.5% C, 0.3 to 4% Si, and 4 to 9% by weight. It consists of Ni, 3% or less Mo, 6 to 10% Mn, 15 to 25% Cr, the remainder Fe and inevitable impurities.
[0055]
When such a corrosion-resistant and wear-resistant alloy material is subjected to hot plastic processing as described above, the corrosion-resistant and wear-resistant alloy can be improved. In addition, the surface of the low-friction corrosion-resistant and wear-resistant alloy can be improved. Is obtained.
[0056]
The coefficient of friction was determined by measuring the friction of the surface of the corrosion-resistant and wear-resistant alloy. The metal components of the corrosion-resistant and wear-resistant alloy used for the friction measurement have the metal components shown in Table 2 below, and the eutectic carbides in the corrosion-resistant and wear-resistant alloy are in the form of multiple grains or multiple blocks. Had a discontinuous distribution morphology.
[0057]
[Table 2]
Figure 0004205505
[0058]
The corrosion-resistant and wear-resistant alloy of the present invention is used for various devices as follows. That is, FIG. 10 shows a piping system of a nuclear power plant. In the piping system, the water supply system 10 is provided with a large number of gate valves and check valves in the water supply pipe 11. The gate valve and check valve attached to the water supply pipe 11 are small and very large compared to other devices such as the water supply pump 12 and the water heaters 13 and 14 attached in the middle of the water supply pipe 11. Therefore, the illustration of the gate valve and the check valve is omitted in FIG.
[0059]
In the nuclear power plant, high-temperature high-pressure steam obtained in the reactor pressure vessel 16 is introduced into the high-pressure turbine 18 through the main steam pipe 15. Next, the steam discharged from the high-pressure turbine 18 is introduced into the low-pressure turbine 19, and the generator 20 is driven by the rotational force of these turbines. The steam that has passed through the high-pressure turbine 18 and the low-pressure turbine 19 is discharged from the high-pressure turbine 18 and the low-pressure turbine 19, condensed in the main ascites unit 22 and the ground steam condenser 21, and turned into water. The water supply system 10 having a valve returns to the reactor pressure vessel 16 through the water supply pipe 11 through the water supply pump 12 and the respective water supply heaters 13 and 14.
[0060]
The example which applied this invention to the gate valve among the valves employ | adopted as the piping of the water supply system 46 is demonstrated below.
[0061]
FIG. 11 shows a longitudinal section of the gate valve provided in the water supply pipe 11 of the water supply system 10. As shown in FIG. 12, a ring base plate 31 of a cobalt base alloy is mounted as a valve seat on the valve body 30 side of the gate valve. Similarly, a ring-shaped plate 31 made of a cobalt base alloy is also mounted on the sliding surface of the valve seat 33 on the valve box 32 side.
[0062]
The cobalt base alloy contains 1.0 wt% C-30.0 wt% Cr-3.9 wt% W based on cobalt, and the cobalt base alloy is obtained by hot forging and hot rolling. The inside eutectic carbide is in the form of a plurality of grains or lumps of 30 μm or less. The ring-shaped cobalt base alloy plate 31 was joined to the valve seat 33 on the valve box 32 side and the valve seat part of the valve body 30 by liquid phase diffusion joining as shown in FIG.
[0063]
As shown in FIG. 12, the valve body 30 of the gate valve has a disk-like shape with a thick upper part and a thin lower part, and is driven up and down in conjunction with the vertical movement of the valve stem, The flow of water or water vapor flowing in the box 32 is opened and closed.
[0064]
A specific example of mounting the ring-shaped cobalt base alloy plate 31 on the valve body 30 will be described below. That is, after providing a step on the left and right surfaces of the valve body 30 of the gate valve and providing the protrusions 34 protruding left and right, the joining insert material was placed in the recessed portion generated by providing the step. Next, a ring-shaped plate 31 having a thickness of about 7 mm was placed on the surface of the joining insert material so as to fit into the protrusions 34. Thereafter, only the insert material for joining was melted, and the ring-shaped plate 31 was attached to the valve body 30 by liquid phase diffusion joining.
[0065]
The insert material used for liquid phase diffusion bonding is a Ni-based alloy containing 4.5 wt% Si and 3 wt% B, and is completely melted at about 1040 ° C. or higher. The liquid phase diffusion bonding conditions are as follows: bonding temperature: 1100 ° C., holding time: 1 h, degree of vacuum: 1-2 × 10-FourTorr, pressure: 15g / cm2 It was. Cooling after joining was performed by removing heat from about 1100 ° C. to 650 ° C. by about 150 ° C./h, from about 650 ° C. to 425 ° C. at about 100 ° C./h, and by air cooling at 425 ° C.
[0066]
An annular protrusion 35 is also machined on the valve seat 33. An insert material for joining was placed in a recessed portion around the protrusion. A ring-shaped plate 31 having a thickness of about 7 mm was fitted on the protrusion 35 and placed on the surface of the joining insert material. Thereafter, only the insert material for joining was melted, and the ring-shaped plate 31 was attached to the valve seat 7 by liquid phase diffusion joining. The material of the ring-shaped plate 31 and the insert material for joining, the liquid phase diffusion joining conditions, and the cooling conditions after joining are the same as those for joining the plate 31 to the valve body 30.
[0067]
The valve body 30, the plate 31, and the valve seat 33 are not melted at a joining temperature of 1100 ° C. The material on the valve body 30 side where the plate 31 is mounted and the material of the valve seat 33 is carbon steel S25C for mechanical structure. The thermal expansion coefficient of the carbon steel for machine structure S25C is smaller than that of the Co-based alloy. As shown in FIG. 12, ring-shaped projections 34 and 35 (steps) having a height of 2 mm are provided on the surfaces of the valve body 30 and the valve seat 33 that are in contact with the ring-shaped plate 6 to be joined. It was. As a result, it is possible to easily align the plate 31 and the valve body 30 and the valve seat 33 at the time of joining, and at the same time, to increase the resistance to the shearing force applied to the sliding part and the joining part when the gate valve is operated. it can.
[0068]
The plates 31 that serve as valve seats on the valve body 30 side of FIG. 12 are each circular when viewed from the left and right sides of the paper, and the ring-shaped plates 31 are convex circular on the left and right sides of the valve body 30. The protrusion 34 is joined in contact with the outer periphery.
[0069]
The valve seat 33 on the valve box 32 side is a cylindrical body, and the valve seat 33 is incorporated in the valve box 32. The end surface of the valve seat 33 on the valve body 30 side is a sliding surface, and the configuration of the end surface is such that the ring-shaped plate 31 is in contact with the outer periphery of the ring-shaped protrusion 35 when viewed from the left side with respect to the paper surface. Phase diffusion bonded. The heights of both protrusions 34 and 35 are 2 mm, which is smaller than the thickness 7 mm of the ring-shaped plate 31.
[0070]
In the gate valve manufactured by such a method, the mutual contact surface between the valve body and the valve box is constituted by the plate 31. In the Co-based alloy that is the material of the plate 31, the eutectic carbides in the alloy are dispersed in a discontinuous distribution in the form of a plurality of grains or lumps after the liquid phase diffusion bonding. The phenomenon that the eutectic carbide is continuously corroded by the atmosphere that produces the corrosive environment is suppressed. for that reason. Since the drop of the base of the cast structure in the Co-based alloy is suppressed, the progress of corrosion and erosion of the valve seat is suppressed, and the deterioration of the leakage resistance performance of the gate valve is prevented.
[0071]
In this example, the Co-based alloy plate 31 was used as the ring-shaped corrosion-resistant and wear-resistant alloy. However, as described above, the corrosion-resistant / anti-resistant material in which Fe and / or Cr was added to the base of nickel. Eutectics in alloys obtained by hot forging or hot rolling of wear-resistant alloys, corrosion-resistant and wear-resistant alloys based on iron and containing Cr and / or Ni, and alloys having the components shown in Table 2 above. Ni-based alloys and Fe-based alloys having a non-continuous distribution of carbides can be used as well.
[0072]
In this example, a low melting point Ni-based alloy was used as the insert material, but a Fe-based or Co-based low melting point insert material can also be used. Further, by applying the same thing as the embodiment of the present invention not only to a gate valve but also to a sliding part or a contact part such as a valve seat part of a check valve, a safety valve, a ball valve, etc. This has the effect of suppressing the deterioration of leakage resistance and controllability and operating performance.
[0073]
In such an embodiment, there is an effect that the normal function of the valve used in the nuclear power plant can be maintained for a long time, and the reliability of the nuclear power plant can be improved by the effect.
[0074]
In a plant having a piping system in which a valve according to this embodiment is incorporated in a piping, even if hydrogen peroxide water for the purpose of water quality adjustment is injected into the piping, sliding parts such as valve seats of the valve due to the effect of dissolved oxygen Corrosion and erosion can be suppressed, which is effective for improving plant safety.
[0075]
In particular, when the valve of this embodiment is used in the piping of the water supply system of a nuclear power plant, the corrosion removal of the eutectic carbides of the Co-based alloy adopted for the valve seat and the accompanying cobalt water supply system Can be prevented from spreading and spreading. For this reason, cobalt that flows out and diffuses from the water supply system to each system and activation of the cobalt can be suppressed, and the radiation exposure of workers in the nuclear power plant can be significantly reduced.
[0076]
The corrosion-resistant and wear-resistant alloy of the present invention can be used in an internal combustion engine as follows. That is, an internal combustion engine using gasoline as fuel includes a cylinder 40 for burning gasoline as shown in FIGS. The upper portion of the cylinder 40 is blocked by a cylinder head 41. The cylinder head 41 includes an intake port and an exhaust port, and each intake port and the exhaust port can be opened and closed by a valve 42.
[0077]
The valve 42 is driven to open and close by a valve mechanism provided in the cylinder head 41. The valve operating mechanism includes a spring 43 provided around the drive shaft of the valve 42, a valve lifter 44 connected to the upper end of the drive shaft, an adjusting shim 45 provided on the valve lifter 44, and an adjustment thereof. The cam 46 is in contact with the upper surface of the tongue shim 45, and power transmission means for rotationally driving the cam 46 using engine output.
[0078]
In the valve mechanism, the cam 46 is rotated using a part of the output of the engine. The movement of the cam 46 pushes down the valve lifter 44 through the adjusting shim 45 against the spring 43. By pushing down, the valve 42 is separated downward from the valve seat 47 of each intake port and exhaust port, and the intake port or exhaust port to which the lube 42 is attached opens.
[0079]
When the cam 46 further rotates, the valve 42 contacts the valve seat 47 and the valve 42 is closed. The contact portion between the valve seat 47 and the valve 42 functions as a seal portion so that the gas in the cylinder 40 does not leak.
[0080]
In the valve mechanism having such a movement, friction due to the sliding motion occurs between the adjusting shim 45 and the cam 46. Friction also occurs between the valve 42 and the valve seat 47. Since the valve operating mechanism is driven against these frictions, the engine output is lost, and the engine efficiency is reduced.
[0081]
Therefore, as shown in FIGS. 14 and 15, a Co-based alloy 48 is bonded to the contact portion between the engine valve 42 and the valve seat 47 as a corrosion-resistant and wear-resistant alloy by a liquid phase diffusion bonding 49. The joining method is performed in the same manner as the liquid phase diffusion joining described above, and the cooling conditions after joining are also as described above. The Co-based alloy 48 is hot-forged at least before joining and has a metal structure having eutectic carbides composed of a plurality of grains or lumps in a cobalt base portion.
[0082]
Similarly, a Co-base alloy having a plurality of granular or spherical eutectic carbides formed on the base material portion at the upper end of the valve lifter 45 was subjected to liquid phase diffusion bonding to form an adjusting shim 4.
[0083]
The components of the insert material used for the Co-base alloy 48 and liquid phase diffusion bonding have the components shown in Table 3.
[0084]
[Table 3]
Figure 0004205505
[0085]
In the liquid phase diffusion bonding, the insert material melts, but the Co-based alloy 48, the valve 42, and the valve seat 47 do not melt. Therefore, the Co-based alloy 48 after bonding can maintain a metal structure in which a plurality of granular or massive eutectic carbides are dispersed in a discontinuous distribution in the base material.
[0086]
Thus, even after the bonding, the eutectic carbide can exist in the Co-base alloy 48 or in the surface in the form of particles or spheres. Thus, the eutectic carbide exists in the Co-based alloy 48 in the form of particles or lumps, and the exposure of the eutectic carbide is limited, and as a result, damage is suppressed.
[0087]
That is, when the Co-based alloy 48 in which the eutectic carbide is dispersed and present in a discontinuous distribution in a granular or massive form is exposed to a corrosive environment due to sulfur, the granular or massive eutectic carbide in contact with the corrosive environment is The surface that falls off from the surface due to corrosion or sliding action and comes into contact with the corrosive environment becomes the surface of only the base material portion where no eutectic carbide exists. Accordingly, the phenomenon in which corrosion and dropout occur alternately and repeatedly is prevented, and damage is suppressed.
[0088]
The friction coefficient of the Co-based alloy 48 having a eutectic carbide composition in the form of particles or lump is normal temperature, high surface pressure (about 2000 kg / cm2 ) When measured under a load condition and displayed as a developed material and plotted in a graph, as shown in FIG. 9, about 1/2 to 2/2 of the friction coefficient of a conventional Co-based alloy having a network-like eutectic carbide. 3 is confirmed to be low.
[0089]
The engine valve 42 is assumed to be used at high temperatures (maximum of about 500 to 600 ° C.) and under a high number of sliding times, but the low friction coefficient is confirmed by the test results under high surface pressure under these test conditions. In addition, the coefficient of friction is governed by the ratio of shear strength / hardness, but this material has almost no temperature dependence of the ratio of shear strength / hardness and is considered to be unchanged if the composition of the material is the same. Therefore, it is considered that the effect of low friction can be obtained even under high temperature and high sliding frequency.
[0090]
For comparison of corrosion resistance, Strauss test and erosion test in dilute sulfuric acid were performed. As a result, the Co-based alloy 48 (development material) having eutectic carbides that are granular or spherically formed has a Co-base alloy having eutectic carbides that are network-shaped as shown in Table 1 in the Strauss test. Compared to the alloy, it exhibits corrosion resistance 30 times or more, and in the erosion test in dilute sulfuric acid, as shown in the characteristic curve of the developed material shown in FIG. -30 times durability performance was shown.
[0091]
As a result, in this embodiment, by realizing high corrosion resistance, low wear resistance and low friction, the durability of the valve system can be improved and the power loss can be reduced. You can improve your power.
[0092]
The Co-based alloy employed in the present embodiment may be a Co-based alloy having the components shown in Table 2, and is a hot-forged Ni-based alloy or Fe-based alloy having the components shown in Table 3 in a lump shape. Alternatively, even if a Ni-based alloy or Fe-based alloy having granular eutectic carbide is made and replaced with the Co-based alloy 48, the overall engine efficiency and output can be improved and the durability can be improved.
[0093]
Also in this case, when a Co-based alloy, Ni-based alloy, or Fe-based alloy is bonded to the valve 42 or the valve seat 47, the eutectic carbide is spherical or granular in the Co-based alloy, Ni-based alloy, or Fe-based alloy after the bonding. The joining means and joining conditions are selected so that they can exist. The joining means to be selected is preferably liquid phase diffusion joining.
[0094]
In the present embodiment, a high temperature is obtained by liquid phase diffusion bonding of a Co-base alloy, Ni-base alloy, or Fe-base alloy having a massive or granular eutectic carbide at a portion having a sealing function between the valve 42 and the valve seat 47 of the engine. While maintaining the hardness, it is possible to provide a sealing surface that is tough, rich in wear resistance and corrosion resistance, and has low friction.
[0095]
Therefore, the durability of the engine of the internal combustion engine is improved by preventing the corrosion caused by the sulfur content in gasoline, which is the fuel of the engine, cracking starting from the corroded part, and deterioration of the sealing performance due to erosion. In addition to being able to prevent the engine efficiency from being lowered, the provision of a low-friction seal surface can also prevent the engine efficiency from being lowered due to friction, thereby contributing to an improvement in engine output.
[0096]
When the outer periphery of the valve lifter 44 constituting the valve mechanism of the engine is mounted by liquid phase diffusion bonding with the Co-base alloy, Ni-base alloy, or Fe-base alloy of Table 2 or Table 3 having a massive or granular eutectic carbide. Furthermore, the durability of the engine can be improved and the engine efficiency can be prevented from decreasing.
[0097]
A Co-based alloy having a eutectic carbide in a network form is used as a conventional example, and a Co-based alloy having the components shown in Table 2 in which a eutectic carbide is granular or lump and dispersed in a discontinuous distribution in a substrate. When the two alloys are compared, there is a difference in performance as shown in Table 4 below.
[0098]
[Table 4]
Figure 0004205505
[0099]
As described above, since there is a difference in the performance of the alloy between the conventional example and the present example, if the alloy of the present example is joined to the valve lifter by liquid phase diffusion bonding, engine output loss due to friction of the valve mechanism is reduced. it can. In addition, if the alloy of this embodiment is joined to a valve or a seat by liquid phase diffusion bonding, the soundness of the valve or the seat can be maintained for a long time because there is no corrosion sensitivity in an SOx atmosphere and the impact value is high. .
[0100]
The corrosion-resistant and wear-resistant alloy of the present invention can be used in pump equipment as follows. That is, in the pump facility shown in FIG. 16, when the shaft 50 is rotated by an electric motor or the like, the impeller 51 fixed to the shaft 50 rotates in the pump casing 52. Due to the rotation of the impeller 51, the fluid X flowing into the pump casing 52 becomes high pressure and is discharged out of the pump casing 52.
[0101]
A mechanical seal is employed at the boundary between the liquid X and the gas Y so that the liquid X does not leak to the gas Y side. The mechanical seal is illustrated in FIG. The mechanical seal in FIG. 17 has the following configuration.
[0102]
That is, the eyeglasses 55 disposed around the shaft 50 inside the seal box 53 integral with the pump casing 52 are fixed to the shaft 50 by the knock 54. A spring 56, a pusher 57, a packing 58, and a washer 59 are provided around the shaft 50 inside the glasses 55.
[0103]
On the other hand, a seal cover 60 provided around the shaft 50 is attached to the end of the seal box 53. A seat 61 disposed around the shaft 50 is attached to the seal cover 60.
[0104]
Since the pusher 57, the packing 58, and the washer 59 are pushed to the right by the spring 56, the washer 59 is pressed against the sheet 61 and the sealed end surface S. In this way, the washer 59 is pressed against the sheet 61 with the spring 56 to seal the liquid X from leaking to the gas Y side.
[0105]
The spectacles 55, the spring 56, the pusher 57, the packing 58, and the washer 59 rotate together with the shaft 50, but the sheet 61 does not rotate, so that frictional heat is generated on the sealed end surface S, and seizure of the sealed end surface S occurs. Promotes wear and corrosion. Therefore, a mechanical seal using a material with low friction and high corrosion resistance is required for the sealed end face.
[0106]
In order to satisfy this need, in this embodiment, a corrosion- and wear-resistant alloy plate 62 is attached to the portion of the washer 59 that contacts the sheet 61 as shown in FIG. As the corrosion-resistant and wear-resistant alloy, any of the alloys described above may be used, and eutectic carbide is dispersed in a granular or massive form in a discontinuous distribution in the base material of the alloy. The attachment of the alloy to the washer 59 is achieved by bonding by liquid phase diffusion bonding. The bonding method and bonding conditions of the liquid phase diffusion bonding are as described above. Similarly, the same corrosion-resistant and wear-resistant alloy may be attached to the portion of the sheet 61 that contacts the washer 59, and similarly, both the washer 59 and the sheet 61 are in contact with each other. Alternatively, a similar corrosion-resistant and wear-resistant alloy may be mounted so that the corrosion-resistant and wear-resistant alloys are brought into contact with each other at the sealed end surface S.
[0107]
According to such an embodiment, the corrosion-resistant and wear-resistant alloy joined to at least one of the washer 59 or the sheet 61 is maintained in a state in which the eutectic carbides are granular or massive and dispersed in a discontinuous distribution and are not easily corroded. In addition, the friction coefficient can be kept as low as the friction coefficient of the corrosion-resistant and wear-resistant alloy shown in FIG.
[0108]
Therefore, improvement in corrosion resistance and reduction in friction can be achieved in a corrosive environment such as sulfur content and dissolved oxygen in the sealed end surface S. Therefore, according to the present Example, the performance of a mechanical seal can be maintained for a long time, and a highly reliable mechanical seal can be provided. Since the performance of the mechanical seal can be maintained for a long time, the reliability of the pump employing the mechanical seal and the plant employing the pump is also improved.
[0109]
Conventionally, the washer 59 is used by depositing a Co-based alloy on the sealing end surface S of the washer 59, and the sheet 61 is made of baked phenol-impregnated carbon, phenol-molded carbon, or white-impregnated carbon. Compared to such a conventional example, the corrosion resistance and the eutectic carbide in the washer 59 or the sheet 61 or both the washer 59 and the sheet 61 are dispersed in a discontinuous distribution in the base material in a granular or lump shape. Table 5 shows a comparison of the performance of the Co-based alloy of the present example, in which a wear-resistant alloy (Co-based alloy) is mounted by liquid phase diffusion bonding. The Co-based alloy of this example in Table 5 has the components shown in Table 2, and the eutectic carbide in the alloy is granular or massive and dispersed in the alloy in a discontinuous distribution.
[0110]
[Table 5]
Figure 0004205505
[0111]
Due to such a difference in performance, the mechanical seal according to the present embodiment can suppress seizure, wear, and corrosion on the sealed end surface S. In addition, the present embodiment can provide a mechanical seal that can withstand high compressive stress and impact value, which is unprecedented. Further, in this embodiment, the eutectic carbides are dispersed in a non-continuous distribution in a spherical or massive form in the base material of the corrosion-resistant and wear-resistant alloy even after the corrosion-resistant and wear-resistant alloy plate 62 is joined to the washer 59 or the like. Since it can exist, the corrosion resistance is high and leakage at the sealed end surface S can be reliably suppressed, and the occurrence of erosion at the sealed end surface S due to the leakage can also be suppressed. Thus, according to the present embodiment, a high-performance mechanical seal can be provided.
[0112]
When the pump facility shown in FIG. 16 is operated, the washer 59 rotates together with the rotary shaft 50, and the plate 62 attached to the washer 59 rotates while contacting the non-moving seat 61 attached to the pump casing 52. . The contact between the plate 62 and the sheet 61 provides a seal between the rotary shaft 50 that is a rotating member and the pump casing 52 that is a fixed member, thereby preventing liquid leakage. The washer 59, the plate 62, and the seat 61 constitute a mechanical seal device in the pump facility. The washer 59 (main body portion) and the plate 62 (corrosion resistant / abrasion resistant alloy portion) constitute a first seal portion, and the sheet 61 constitutes a second seal portion. You may install a 1st seal part in the pump casing 52, and a 2nd seal part may be installed in the rotating shaft 50 side. Furthermore, the second seal portion installed in the pump casing 52 may have the same configuration as the first seal portion.
[0113]
The plate 62 rotates at a high speed while always contacting the seat 61 by the action of the spring 56 in order to ensure the sealing performance. For this reason, there is a concern about the wear, seizure, and corrosion of the plate 62 that forms the sealing surface, but the plate 62 is excellent in wear resistance and slidability because the eutectic carbide is granular or lump as described above. Therefore, it hardly wears. Further, since the plate 62 is also excellent in corrosion resistance, corrosion due to contact with a liquid can be prevented. For this reason, the maintenance frequency of the mechanical seal device is reduced, and the life of the mechanical seal device is extended. This leads to a reduction in maintenance work of the pump equipment. Further, since the plate 62 made of the corrosion-resistant and wear-resistant alloy having the above-mentioned granular or massive eutectic carbide has a small friction coefficient of about 0.16, the rotational power of the rotating shaft 50 is reduced by the plate 62 and the sheet 61. The rate of change to heat energy at the contact portion of the is significantly reduced. That is, the loss of rotational power of the rotating shaft 50 is reduced.
[0114]
A mechanical seal device including a corrosion-resistant and wear-resistant alloy having a granular or massive eutectic carbide like the plate 62 in this embodiment is not limited to the pump equipment as in this embodiment, which is a fluid booster, The present invention can be applied to a compressor or a blower that pressurizes a gas that needs to be sealed with a casing. A compressor and a blower are a kind of fluid booster. Furthermore, the present invention can be applied to a turbine through which steam flows. In other words, as a mechanical seal device that seals between the rotating shaft of the turbine and the casing, a mechanical seal device having a corrosion-resistant and wear-resistant alloy having granular or massive eutectic carbide at the contact portion is applied to the pump equipment. To do. The pump equipment, the above-described compressor, blower, and turbine are rotating devices through which fluid flows.
[0115]
  The concept of the preferred invention including the pump equipment, the compressor, the blower and the turbine shown in FIG. 16 is shown below.ItYou can also grasp.
[0116]
  InsideA rotating device comprising a casing through which a fluid flows, a rotating shaft inserted into the casing, and a mechanical seal device for sealing between the rotating shaft and the casing,
  The mechanical seal device includes a first seal portion that rotates together with the rotating shaft, and a second seal portion that is attached to the casing and contacts the first seal portion,
  At least one of the first seal part and the second seal part is a corrosion-resistant and wear-resistant alloy part in which a granular or massive eutectic carbide is dispersed in the base part of the metal microstructure, and contacts the other seal part. A rotating device having a corrosion-resistant and wear-resistant alloy part and a main body, wherein the corrosion-resistant and wear-resistant alloy part is diffusion bonded to the main body.
[0117]
In the above rotating device, the mechanical seal device that seals between the rotating shaft and the casing is attached to the casing and contacts the first seal portion that rotates together with the rotating shaft. A second seal portion, and at least one of the first seal portion and the second seal portion is a corrosion-resistant and wear-resistant alloy portion in which granular or massive eutectic carbides are dispersed in the base portion of the metal microstructure. And having a corrosion-resistant and wear-resistant alloy part that contacts the other seal part, and a main body part, and the corrosion-resistant and wear-resistant alloy is diffusion bonded to the main body part. Since the seal part has a corrosion-resistant and wear-resistant alloy part diffusion-bonded to the main body part, the diffusion-bonded corrosion-resistant and wear-resistant alloy part has a granular or massive eutectic carbide as described above. There is no reticulated eutectic carbide. For this reason, it is possible to suppress seizure of the seal end face due to frictional heat generated at the contact portion between the first seal portion and the second seal portion, wear of the seal end surface, and promotion of corrosion of the seal material. The corrosion resistance and wear resistance of the parts are improved, the frequency of maintenance of the mechanical seal device having the first seal portion and the second seal portion is reduced, and the life of the mechanical seal device is also extended. This leads to a reduction in maintenance work for the rotating device. In addition, since the above corrosion-resistant and wear-resistant alloy part has a small coefficient of friction, it is possible to reduce the heat energy generated at the contact part between the first seal part and the second seal part. This leads to a reduction in power loss for rotating the rotating shaft of the rotating device.
[0125]
【The invention's effect】
  The present inventionAccording toCorrosion and wear resistant alloysPump equipment and valvesWhen used in sliding parts and contact parts, it is accompanied by corrosion damage of eutectic carbides in a corrosive environment.SoThe sliding portion and the contact portion are less rough, and the frictional resistance of the sliding portion and the contact portion can be favorably maintained. as a result,Has a low friction sliding surface and contact surfacePump equipment and valvesCan be provided.
[Brief description of the drawings]
FIG. 1 is an SEM photograph (a) and a schematic diagram (b) showing a metal structure of a surface of a corrosion-resistant and wear-resistant alloy in which Cr and / or W is added based on cobalt.
2A is a partially enlarged view of the metal structure of the corrosion-resistant and wear-resistant alloy of FIG. 1, and FIG.
FIGS. 3A and 3B are a schematic view and a schematic diagram (b) showing a metal structure represented by surface analysis of a surface of a corrosion-resistant and wear-resistant alloy in which Cr and / or W is added based on cobalt.
FIG. 4A is a schematic diagram (b) showing a metal structure on the surface of a corrosion-resistant / abrasion-resistant alloy in which Cr and / or W is added based on cobalt subjected to hot plastic working.
FIG. 5A is a schematic view showing a metal structure represented by surface analysis of a surface of a corrosion-resistant and wear-resistant alloy in which Cr and / or W is added to cobalt based on hot plastic working. (B).
FIG. 6 is a schematic view showing a state of repeated progress of damage due to dissolved oxygen in a corrosion-resistant and wear-resistant alloy in which Cr and / or W is added based on cobalt.
FIG. 7 is a schematic view showing a state of inhibiting damage due to dissolved oxygen in a corrosion-resistant and wear-resistant alloy in which Cr and / or W is added to cobalt that has been subjected to hot plastic working.
FIG. 8 is an SEM photograph showing a metal structure obtained as a result of a Strauss test of a corrosion-resistant and wear-resistant alloy in which Cr and / or W is added to cobalt which has been subjected to hot plastic working.
FIG. 9 is a graph showing a coefficient of friction by a sliding test of a corrosion-resistant and wear-resistant alloy in which Cr and / or W is added to cobalt which has been subjected to hot plastic working.
FIG. 10 is a piping system diagram of a nuclear power plant.
FIG. 11 is a longitudinal sectional view of a gate valve employed in a piping system of a nuclear power plant.
12 is a cross-sectional view showing a contact state of each valve seat between a valve element and a valve box in the gate valve of FIG.
FIG. 13 is an overall view showing a partial cross-sectional view of the internal combustion engine.
14 is an enlarged cross-sectional view of the vicinity of the valve shown in FIG.
15 is an enlarged cross-sectional view of a contact portion between the valve and the seat of FIG.
FIG. 16 is a cross-sectional view of a pump.
17 is a cross-sectional view of the vicinity of the mechanical seal of the pump of FIG.
[Explanation of symbols]
DESCRIPTION OF SYMBOLS 1 ... Eutectic carbide, 2 ... Base part of casting structure, 10 ... Water supply system, 30 ... Valve body, 31, 62 ... Plate, 32 ... Valve box, 33 ... Valve seat, 41 ... Cylinder head, 42 ... Valve, 50 ... shaft, 51 ... impeller, 52 ... pump casing, 53 ... seal box, 59 ... washer, 61 ... seat.

Claims (6)

ケーシングと、前記ケーシング内に挿入された回転軸と、前記回転軸に設けられ流体を昇圧する流体昇圧手段と、前記回転軸と前記ケーシングとの間のシールを行うメカニカルシール装置とを備えたポンプ設備であって、
前記メカニカルシール装置は、前記回転軸と一緒に回転する第1シール部と、前記ケーシングに取付けられて前記第1シール部に接触する第2シール部とを備え、
前記第1シール部及び前記第2シール部の少なくとも一方は、他方のシール部と接触する耐蝕・耐摩耗性合金部を有し、
前記耐蝕・耐摩耗性合金部は、重量比で . 03C, . 59Ni,29 . 73Cr, . 67Fe, . 86W, . 07Mo, . 59Siと、残部Coおよび不可避不純物を含むCrおよびWを添加したコバルトベース素材、及び重量比で1 . 0%のC,2 . 4%のNi,29 . 4%のCr,2 . 7%のFe,3 . 9%のW,0 . 1%のMo,0 . 6%のSiと、残部のCoおよび不可避不純物を含むCrおよびWを添加したコバルトベース素材のいずれかをインゴットまたはスラブに鋳造した中間素材を、650℃以上、固相線温度以下で熱間塑性加工を施すことにより、前記中間素材中の網目状共晶炭化物と、これに囲まれた基材部とからなる組織のうち、前記共晶炭化物を複数の粒状に形成して非連続分布とし、摩擦係数が0.1〜0.5、時効効果処理を施さないHRCが43〜45である耐蝕・耐摩耗性合金で構成されていることを特徴とするポンプ設備。
A pump comprising a casing, a rotating shaft inserted into the casing, a fluid pressurizing unit provided on the rotating shaft for boosting a fluid, and a mechanical seal device for sealing between the rotating shaft and the casing Equipment,
The mechanical seal device includes a first seal portion that rotates together with the rotating shaft, and a second seal portion that is attached to the casing and contacts the first seal portion,
At least one of the first seal part and the second seal part has a corrosion-resistant and wear-resistant alloy part that contacts the other seal part,
The corrosion-resisting and wear-resisting alloy portion 1 by weight. 0.3% of C, 2. 59% of the Ni, 29. 73% of the Cr, 2. 67% of the Fe, 3. 86% of the W, 0. 07% of Mo, 0. and 59% of Si, the balance of Co and cobalt-based material of Cr and W contain inevitable impurities was added, and a weight ratio 1.0% of C, 2. 4% of the Ni , 29.4% of Cr, 2. 7% of the Fe, 3. 9 percent W, 0. adding Cr and W containing 1% of Mo, 0. 6% of the Si, the remainder of Co and inevitable impurities An intermediate material obtained by casting any one of the above-described cobalt base materials into an ingot or slab is subjected to hot plastic processing at a temperature of 650 ° C. or higher and a solidus temperature or lower, thereby forming a network eutectic carbide in the intermediate material, Among the structure consisting of the base material part surrounded by Pump equipment characterized by being formed of a corrosion-resistant and wear-resistant alloy having a non-continuous distribution, a friction coefficient of 0.1 to 0.5, and an HRC of 43 to 45 without aging effect treatment .
前記耐蝕・耐摩耗性合金部は、摩擦係数が0.1〜0.3である請求項1に記載のポンプ設備。  The pump equipment according to claim 1, wherein the corrosion-resistant and wear-resistant alloy part has a friction coefficient of 0.1 to 0.3. 前記耐蝕・耐摩耗性合金部は、摩擦係数が0.16〜0.19である請求項1に記載のポンプ設備。  The pump equipment according to claim 1, wherein the corrosion-resistant and wear-resistant alloy part has a friction coefficient of 0.16 to 0.19. 弁体及び弁箱を備え、両者の接触面にそれぞれ弁座を有する弁において、
前記弁座は基体の表面に耐蝕・耐摩耗性合金部を設けており、
前記耐蝕・耐摩耗性合金部は、重量比で . 03C, . 59Ni,29 . 73Cr, . 67Fe, . 86W, . 07Mo, . 59Siと、残部Coおよび不可避不純物を含むCrおよびWを添加したコバルトベース素材、及び重量比で1 . 0%のC,2 . 4%のNi,29 . 4%のCr,2 . 7%のFe,3 . 9%のW,0 . 1%のMo,0 . 6%のSiと、残部のCoおよび不可避不純物を含むCrおよびWを添加したコバルトベース素材のいずれかをインゴットまたはスラブに鋳造した中間素材を、650℃以上、固相線温度以下で熱間塑性加工を施すことにより、前記中間素材中の網目状共晶炭化物と、これに囲まれた基材部とからなる組織のうち、前記共晶炭化物を複数の粒状に形成して非連続分布とし、摩擦係数が0.1〜0.5、時効効果処理を施さないHRCが43〜45である耐蝕・耐摩耗性合金で構成されることを特徴とする弁。
In a valve comprising a valve body and a valve box, each having a valve seat on the contact surface thereof,
The valve seat is provided with a corrosion-resistant and wear-resistant alloy part on the surface of the base,
The corrosion-resisting and wear-resisting alloy portion 1 by weight. 0.3% of C, 2. 59% of the Ni, 29. 73% of the Cr, 2. 67% of the Fe, 3. 86% of the W, 0. 07% of Mo, 0. and 59% of Si, the balance of Co and cobalt-based material of Cr and W contain inevitable impurities was added, and a weight ratio 1.0% of C, 2. 4% of the Ni , 29.4% of Cr, 2. 7% of the Fe, 3. 9 percent W, 0. adding Cr and W containing 1% of Mo, 0. 6% of the Si, the remainder of Co and inevitable impurities An intermediate material obtained by casting any one of the above-described cobalt base materials into an ingot or slab is subjected to hot plastic processing at a temperature of 650 ° C. or higher and a solidus temperature or lower, thereby forming a network eutectic carbide in the intermediate material, Among the structure consisting of the base material part surrounded by A valve formed of a corrosion-resistant and wear-resistant alloy having a non-continuous distribution, a friction coefficient of 0.1 to 0.5, and an HRC of 43 to 45 that is not subjected to aging effect treatment.
前記耐蝕・耐摩耗性合金部は、摩擦係数が0.1〜0.3である請求項4に記載の弁。  The valve according to claim 4, wherein the corrosion-resistant and wear-resistant alloy part has a friction coefficient of 0.1 to 0.3. 前記耐蝕・耐摩耗性合金部は、摩擦係数が0.16〜0.19である請求項4に記載の弁。  The valve according to claim 4, wherein the corrosion-resistant and wear-resistant alloy part has a friction coefficient of 0.16 to 0.19.
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