JP3684008B2

JP3684008B2 - Intermetallic compound composite and method for producing the same

Info

Publication number: JP3684008B2
Application number: JP31992596A
Authority: JP
Inventors: 雅礼加藤; 康広五戸; 孝幸深澤
Original assignee: Toshiba Corp
Current assignee: Toshiba Corp
Priority date: 1996-11-29
Filing date: 1996-11-29
Publication date: 2005-08-17
Anticipated expiration: 2016-11-29
Also published as: JPH10158776A

Description

【０００１】
【発明の属する技術分野】
本発明は、ガスタービン、ジェットエンジン、高温バルブ等の高温耐熱部材に有用な金属間化合物を用いた材料に関する。
【０００２】
【従来の技術】
Ａ−Ｂ二元系金属間化合物のうち、ｆｃｃ，ｈｃｐ又はｂｃｃに属する構造をとるＡ₃ Ｂ形金属間化合物及びＡＢ形金属間化合物は、塑性変形が可能であり、靭性も高いことから、耐熱性構造用部材として広く利用されている。
【０００３】
しかしながら、金属間化合物は、一旦金属を溶融した後に冷却することによって得るため、かなりの高温と時間とを要するというコスト面での欠点があった。そこで、より簡単かつ安価に金属間化合物を製造する方法として、特開平第５−１１７７１６号公報には、原料金属粉末をメカニカルアロイング法により微粉砕した後、プラズマ焼結法により焼結する方法が提案されている。しかし、この方法では、微粉末生成過程及び焼結過程の２つの行程があるため、コストの低減にはそれほど寄与しない。
【０００４】
また、ガスタービン部材のような高温条件下で使用するには、金属間化合物は耐酸化性及び耐食性に劣るという欠点があった。これを克服するためには、酸素含有雰囲気中で熱処理して表面のみを酸化させ保護膜とすることが考えられるが、熱処理で得られる膜の厚さは数十μｍ程度であり、保護膜としては十分とは言えない。さらに、金属間化合物自体が摩耗しやすいという欠点も有った。
【０００５】
【発明が解決しようとする課題】
上述したように、従来の金属間化合物には、製造コストが高いという点、耐酸化性および耐食性か劣る、及び摩耗しやすいという問題点があった。本発明は、この様な従来技術の課題を解決するためになされたもので、高温における高強度、高靭性及び高摩擦特性を保持し、且つ、耐酸化性を有する金属材料を安価に提供することを目的とするものである。
【０００６】
【課題を解決するための手段】
上記目的を達成するために、本発明者らは鋭意研究を重ねた結果、金属粉末と酸化物粉末からる成形体をマイクロ波加熱することで、低温かつ短時間で金属間化合物を含有する材料が得られ、これが金属間化合物の複合体および表面に耐酸化被膜が形成された金属間化合物複合体であることを見出し、本発明の金属間化合物複合体及びその製造方法を発明するに至った。
【０００７】
本発明の金属間化合物複合体は、Ｔｉ，Ｚｒ，Ｈｆより選ばれる金属とＣｕ，Ｃｏ，Ｓｎ，Ｎｉ，Ｚｎより選ばれる金属とからなる金属間化合物を含有するマトリックスに、Ｃｕ，Ｃｏ，Ｓｎ，Ｎｉ，Ｚｎより選ばれる金属の酸化物が複合化されるものである。
【０００８】
又、本発明の他の金属間化合物複合体は、Ｔｉ，Ｚｒ，Ｈｆより選ばれる金属とＣｕ，Ｃｏ，Ｓｎ，Ｎｉ，Ｚｎより選ばれる金属とからなる金属間化合物を含有するマトリックスに、Ｃｕ，Ｃｏ，Ｓｎ，Ｎｉ，Ｚｎより選ばれる金属の酸化物が複合化され、Ｔｉ，Ｚｒ，Ｈｆより選ばれる金属の酸化物を含有する表面層を有するものである。
【０００９】
本発明に係る金属間化合物複合体の製造方法は、Ｔｉ，Ｚｒ，Ｈｆより選ばれる金属の酸化物の粉末とＣｕ，Ｃｏ，Ｓｎ，Ｎｉ，Ｚｎより選ばれる金属の粉末とを混合し成形して成形体を得て、非酸化性雰囲気下あるいは真空下でマイクロ波を用いて該成形体を加熱するものである。
【００１０】
又、本発明に係る金属間化合物複合体の他の製造方法は、Ｔｉ，Ｚｒ，Ｈｆより選ばれる金属の酸化物の粉末とＣｕ，Ｃｏ，Ｓｎ，Ｎｉ，Ｚｎより選ばれる金属の粉末とを混合し成形して成形体を得て、酸化性雰囲気下でマイクロ波を用いて該成形体を加熱するものである。
【００１２】
【発明の実施の形態】
Ｔｉ，Ｚｒ，Ｈｆといった金属元素（以下、第１の金属と称する）の酸化物は、マイクロ波の吸収率が４００〜１０００℃の間で急激に高くなる特長を有する。マイクロ波は吸収率の高い材料を選択的に加熱する性質が有るため、これらの酸化物と金属粉末が共存する成形体をマイクロ波で加熱すると、上記の酸化物が選択的に加熱され、成形体温度が５００℃程度であっても、局所的に１０００℃を超える高温となる場合もある。また、これらの酸化物は高温では酸素が解離し易く、金属粉末がＣｕ，Ｃｏ，Ｓｎ，Ｎｉ，Ｚｎといった金属（以下、第２の金属と称する）である場合、第１の金属の酸化物から解離した酸素と周囲の第２の金属とが反応して酸化物を形成するとともに、解離した第１の金属も周囲の第２の金属と反応して金属間化合物となる。その結果、金属間化合物と第２の金属の酸化物との複合体が得られる。この金属間化合物複合体は、金属間化合物マトリックス中にセラミックス粒子が分散した構造を有し、金属間化合物のみの材料と比較して強度及び耐摩耗性が向上する。
【００１３】
又、成形体のマイクロ波加熱を真空中あるいは不活性ガス雰囲気中で行う場合には、均一な金属間化合物複合体が得られるのに対し、酸化性雰囲気で行う場合には、成形体の表層部分が酸化される。この結果、原料と同じ第１の金属の酸化物と第２の金属の酸化物との複合体の表面層が得られる。この表面層の厚さは雰囲気中の酸素含有量により制御することができ、全て酸化物とすることも可能である。
【００１４】
以下に本発明を詳細に説明する。
【００１５】
まず、Ｔｉ，Ｚｒ，Ｈｆより選ばれる第１の金属の酸化物の粉末とＣｕ，Ｃｏ，Ｓｎ，Ｎｉ，Ｚｎより選ばれる金属の粉末とを混合し、圧縮成形により成形体を得る。混合粉末の調製は、具体例としては、アセトン等の液媒を用いて３〜１０時間程度ボールミルで混合した後にロータリーエバポレーター等を用いて液媒を除去し、篩を通して粒度を調整する等のことによって行うことができる。使用する金属酸化物粉末と金属粉末の混合割合によって生成する金属間化合物の組成は変化し、第１の金属の酸化物１に対し第２の金属をモル比３〜５となるように混合するのが好ましい。第２の金属がこの範囲より少ないと金属間化合物が生成されず、多い場合にはマトリクス中の金属間化合物の量が少なく第２の金属を多量に含むようになる。使用する原料粉末は必要に応じて適宜所望の粒径に調製すれば良く、０．１〜１０μｍ程度のものは金属間化合物の生成が良好であり、粉末の取り扱いも行い易く、好ましい。得られた混合粉末は、金型に所定量充填して加圧成形することにより、成形体が得られる。加圧成形は、例えば、１００〜１０００kg／cm^２程度の圧力で一軸加圧した後に、１〜１０ｔ／cm^２程度の圧力で冷間等方静水圧成形を適用することにより、所望の形状に適切に行うことができる。
【００１６】
得られた成形体は、断熱材で周囲を覆ってマイクロ波加熱装置のアプリケーター内に配置して加熱するのが好ましい。成形体から上述の金属間化合物複合体を製造する際に使用するマイクロ波の周波数は０．３〜３０ＧＨｚの範囲が好ましく、２０〜３０ＧＨｚであればより好ましい。マイクロ波は、加熱温度が１２００℃以上、好ましくは１４００℃以上となるように照射する。加熱温度が高すぎると、成形体を覆う断熱材が溶融する可能性があるので好ましくない。このため、加熱温度は、好ましくは１２００〜１７００℃、より好ましくは１４００〜１６００℃に設定する。又、加熱時間は５分以上、望ましくは３０分以上とする。
【００１７】
窒素等の非酸化性雰囲気下で上記のマイクロ波加熱を行うと、図１に模式的に示すような上記第１の金属及び第２の金属からなる金属間化合物（図中参照符号１）と第２の金属の酸化物（図中参照符号２）との複合体が生成されるが、大気などの酸化性雰囲気中で加熱すると、複合体の表面で酸化が進行し、金属間化合物が酸化され第１の金属の酸化物と第２の金属の酸化物が生成される。この結果、図２に示すように、第１の金属及び第２の金属からなる金属間化合物（図中参照符号１）と第２の金属の酸化物（参照符号２）とによる複合体の表面に、第２の金属の酸化物（参照符号２）及び第１の金属の酸化物（参照符号３）を含む酸化膜（参照符号４）が形成される。この様な酸化膜の厚さは雰囲気中の酸化性ガスの分圧に依存し、例えば通常のガス置換に従って１０^-3〜１０^-4torr程度に減圧した後に窒素あるいはアルゴンなどの不活性ガスを導入した場合には残留する酸化性ガスは無視できる程度であり酸化膜は実質的に形成されない。
【００１８】
【実施例】
以下、実施例を用いて本発明をさらに詳細に説明する。
【００１９】
（実施例１）
ＴｉＯ₂ 粉末とＣｕ粉末とをモル比が１：３となるように秤量し、アセトンを分散媒として、ナイロンボールによるボールミル混合を行った。混合後、ロータリーエバポーレーターを用いて乾燥を行い、５００μｍの篩を通して粒度を調整した。得られた混合粉末を金型に充填し、２００kg／cm² の圧力で一軸加圧した後、２ｔ／cm² の圧力で冷間等方静水圧成形を行った。得られた成形体の周囲を断熱材で覆ってマイクロ波加熱装置のアプリケーター内に配置し、２８ＧＨｚ，１５ｋｗのマイクロ波によりＮ₂ 雰囲気下で３０分間８００℃に加熱した。得られた焼結体をＸ線回析により同定した結果、ＣｕＴｉとＣｕＯが生成していた。得られた焼結体の断面を顕微鏡写真で撮影した像は図１と同様のものであった。
【００２０】
（実施例２）
ＴｉＯ₂ 粉末とＣｕ粉末とをモル比が１：５となるように秤量した以外は、実施例１と同様の条件で混合、乾燥、成形、マイクロ波加熱を行った。得られた焼結体の生成相をＸ線回析により同定した結果、Ｃｕ₃ ＴｉとＣｕＯが生成していた。得られた焼結体の断面を顕微鏡写真で撮影した像は図１と同様のものであった。
【００２１】
（実施例３）
加熱雰囲気を大気とした以外は、実施例１と同様の条件で混合、乾燥、成形、マイクロ波加熱を行った。得られた焼結体の生成相をＸ線回析により同定した結果、内部にはＣｕＴｉとＣｕＯが、表層にはＴｉＯ₂ とＣｕＯが生成していた。得られた焼結体の断面を顕微鏡写真で撮影した像は図２と同様のものであった。
【００２２】
（実施例４）
加熱雰囲気を大気とした以外は、実施例２と同様の条件で混合、乾燥、成形、マイクロ波加熱を行った。得られた焼結体の生成相をＸ線回析により同定した結果、内部にはＣｕ₃ ＴｉとＣｕＯが、表層にはＴｉＯ₂ とＣｕＯが生成していた。得られた焼結体の断面を顕微鏡写真で撮影した像は図２と同様のものであった。
【００２３】
（実施例５）
ＴｉＯ₂ 粉末に代えてＺｒＯ₂ 粉末を使用した以外は、実施例１と同様の条件で混合、乾燥、成形、マイクロ波加熱を行った。得られた焼結体の生成相をＸ線回析により同定した結果、ＣｕＺｒとＣｕＯが生成していた。得られた焼結体の断面を顕微鏡写真で撮影した像は図１と同様のものであった。
【００２４】
（実施例６）
ＴｉＯ₂ 粉末に代えてＺｒＯ₂ 粉末を使用した以外は、実施例２と同様の条件で混合、乾燥、成形、マイクロ波加熱を行った。得られた焼結体の生成相をＸ線回析により同定した結果、Ｃｕ₃ ＺｒとＣｕＯが生成していた。得られた焼結体の断面を顕微鏡写真で撮影した像は図１と同様のものであった。
【００２５】
（実施例７）
加熱雰囲気を大気とした以外は、実施例５と同様の条件で混合、乾燥、成形、マイクロ波加熱を行った。得られた焼結体の生成相をＸ線回析により同定した結果、内部にはＣｕＺｒとＣｕＯが、表層にはＺｒＯ₂ とＣｕＯが生成していた。得られた焼結体の断面を顕微鏡写真で撮影した像は図２と同様のものであった。
【００２６】
（実施例８）
加熱雰囲気を大気とした以外は、実施例６と同様の条件で混合、乾燥、成形、マイクロ波加熱を行った。得られた焼結体の生成相をＸ線回析により同定した結果、内部にはＣｕ₃ ＺｒとＣｕＯが、表層にはＺｒＯ₂ とＣｕＯが生成していた。得られた焼結体の断面を顕微鏡写真で撮影した像は図２と同様のものであった。
【００２７】
（実施例９）
ＴｉＯ₂ 粉末に代えてＨｆＯ₂ 粉末を使用した以外は、実施例１と同様の条件で混合、乾燥、成形、マイクロ波加熱を行った。得られた焼結体の生成相をＸ線回析により同定した結果、ＣｕＨｆとＣｕＯが生成していた。得られた焼結体の断面を顕微鏡写真で撮影した像は図１と同様のものであった。
【００２８】
（実施例１０）
ＴｉＯ₂ 粉末をＨｆＯ₂ 粉末を使用した以外は、実施例２と同様の条件で混合、乾燥、成形、マイクロ波加熱を行った。得られた焼結体の生成相をＸ線回析により同定した結果、Ｃｕ₃ ＨｆとＣｕＯが生成していた。得られた焼結体の断面を顕微鏡写真で撮影した像は図１と同様のものであった。
【００２９】
（実施例１１）
加熱雰囲気を大気とした以外は、実施例９と同様の条件で混合、乾燥、成形、マイクロ波加熱を行った。得られた焼結体の生成相をＸ線回析により同定した結果、内部にはＣｕＨｆとＣｕＯが、表層にはＨｆＯ₂ とＣｕＯが生成していた。得られた焼結体の断面を顕微鏡写真で撮影した像は図２と同様のものであった。
【００３０】
（実施例１２）
加熱雰囲気を大気とした以外は、実施例１０と同様の条件で混合、乾燥、成形、マイクロ波加熱を行った。得られた焼結体の生成相をＸ線回析により同定した結果、内部にはＣｕ₃ ＨｆとＣｕＯが、表層にはＨｆＯ₂ とＣｕＯが生成していた。得られた焼結体の断面を顕微鏡写真で撮影した像は図２と同様のものであった。
【００３１】
（実施例１３）
Ｃｕ粉末に代えてＣｏ粉末を使用した以外は、実施例１と同様の条件で混合、乾燥、成形、マイクロ波加熱を行った。得られた焼結体の生成相をＸ線回析により同定した結果、ＣｏＴｉとＣｏＯが生成していた。得られた焼結体の断面を顕微鏡写真で撮影した像は図１と同様のものであった。
【００３２】
（実施例１４）
Ｃｕ粉末に代えてＣｏ粉末を使用した以外は、実施例２と同様の条件で混合、乾燥、成形、マイクロ波加熱を行った。得られた焼結体の生成相をＸ線回析により同定した結果、Ｃｏ₃ ＴｉとＣｏＯが生成していた。得られた焼結体の断面を顕微鏡写真で撮影した像は図１と同様のものであった。
【００３３】
（実施例１５）
加熱雰囲気を大気とした以外は、実施例１３と同様の条件で混合、乾燥、成形、マイクロ波加熱を行った。得られた焼結体の生成相をＸ線回析により同定した結果、内部にはＣｏＴｉとＣｏＯが、表層にはＴｉＯ₂ とＣｏＯが生成していた。得られた焼結体の断面を顕微鏡写真で撮影した像は図２と同様のものであった。
【００３４】
（実施例１６）
加熱雰囲気を大気とした以外は、実施例１４と同様の条件で混合、乾燥、成形、マイクロ波加熱を行った。得られた焼結体の生成相をＸ線回析により同定した結果、内部にはＣｏ₃ ＴｉとＣｏＯが、表層にはＴｉＯ₂ とＣｏＯが生成していた。得られた焼結体の断面を顕微鏡写真で撮影した像は図２と同様のものであった。
【００３５】
（実施例１７）
ＴｉＯ₂ 粉末に代えてＺｒＯ₂ 粉末を使用した以外は、実施例１３と同様の条件で混合、乾燥、成形、マイクロ波加熱を行った。得られた焼結体の生成相をＸ線回析により同定した結果、ＣｏＺｒとＣｏＯが生成していた。得られた焼結体の断面を顕微鏡写真で撮影した像は図１と同様のものであった。
【００３６】
（実施例１８）
ＴｉＯ₂ 粉末に代えてＺｒＯ₂ 粉末を使用した以外は、実施例１４と同様の条件で混合、乾燥、成形、マイクロ波加熱を行った。得られた焼結体の生成相をＸ線回析により同定した結果、Ｃｏ₃ ＺｒとＣｏＯが生成していた。得られた焼結体の断面を顕微鏡写真で撮影した像は図１と同様のものであった。
【００３７】
（実施例１９）
加熱雰囲気を大気とした以外は、実施例１７と同様の条件で混合、乾燥、成形、マイクロ波加熱を行った。得られた焼結体の生成相をＸ線回析により同定した結果、内部にはＣｏＺｒとＣｏＯが、表層にはＺｒＯ₂ とＣｏＯが生成していた。得られた焼結体の断面を顕微鏡写真で撮影した像は図２と同様のものであった。
【００３８】
（実施例２０）
加熱雰囲気を大気とした以外は、実施例１８と同様の条件で混合、乾燥、成形、マイクロ波加熱を行った。得られた焼結体の生成相をＸ線回析により同定した結果、内部にはＣｏ₃ ＺｒとＣｏＯが、表層にはＺｒＯ₂ とＣｏＯが生成していた。得られた焼結体の断面を顕微鏡写真で撮影した像は図２と同様のものであった。
【００３９】
（実施例２１）
ＴｉＯ₂ 粉末に代えてＨｆＯ₂ 粉末を使用した以外は、実施例１３と同様の条件で混合、乾燥、成形、マイクロ波加熱を行った。得られた焼結体の生成相をＸ線回析により同定した結果、ＣｏＨｆとＣｏＯが生成していた。得られた焼結体の断面を顕微鏡写真で撮影した像は図１と同様のものであった。
【００４０】
（実施例２２）
ＴｉＯ₂ 粉末に代えてＨｆＯ₂ 粉末を使用した以外は、実施例１４と同様の条件で混合、乾燥、成形、マイクロ波加熱を行った。得られた焼結体の生成相をＸ線回析により同定した結果、Ｃｏ₃ ＨｆとＣｏＯが生成していた。得られた焼結体の断面を顕微鏡写真で撮影した像は図１と同様のものであった。
【００４１】
（実施例２３）
加熱雰囲気を大気とした以外は、実施例２１と同様の条件で混合、乾燥、成形、マイクロ波加熱を行った。得られた焼結体の生成相をＸ線回析により同定した結果、内部にはＣｏＨｆとＣｏＯが、表層にはＨｆＯ₂ とＣｏＯが生成していた。得られた焼結体の断面を顕微鏡写真で撮影した像は図２と同様のものであった。
【００４２】
（実施例２４）
加熱雰囲気を大気とした以外は、実施例２２と同様の条件で混合、乾燥、成形、マイクロ波加熱を行った。得られた焼結体の生成相をＸ線回析により同定した結果、内部にはＣｏ₃ ＨｆとＣｏＯが、表層にはＨｆＯ₂ とＣｏＯが生成していた。得られた焼結体の断面を顕微鏡写真で撮影した像は図２と同様のものであった。
【００４３】
（実施例２５）
Ｃｕ粉末に代えてＮｉ粉末を使用した以外は、実施例１と同様の条件で混合、乾燥、成形、マイクロ波加熱を行った。得られた焼結体の生成相をＸ線回析により同定した結果、ＮｉＴｉとＮｉＯが生成していた。得られた焼結体の断面を顕微鏡写真で撮影した像は図１と同様のものであった。
【００４４】
（実施例２６）
Ｃｕ粉末に代えてＮｉ粉末を使用した以外は、実施例２と同様の条件で混合、乾燥、成形、マイクロ波加熱を行った。得られた焼結体の生成相をＸ線回析により同定した結果、Ｎｉ₃ ＴｉとＮｉＯが生成していた。得られた焼結体の断面を顕微鏡写真で撮影した像は図１と同様のものであった。
【００４５】
（実施例２７）
加熱雰囲気を大気とした以外は、実施例２５と同様の条件で混合、乾燥、成形、マイクロ波加熱を行った。得られた焼結体の生成相をＸ線回析により同定した結果、内部にはＮｉＴｉとＮｉＯが、表層にはＴｉＯ₂ とＮｉＯが生成していた。得られた焼結体の断面を顕微鏡写真で撮影した像は図２と同様のものであった。
【００４６】
（実施例２８）
加熱雰囲気を大気とした以外は、実施例２６と同様の条件で混合、乾燥、成形、マイクロ波加熱を行った。得られた焼結体の生成相をＸ線回析により同定した結果、内部にはＮｉ₃ ＴｉとＮｉＯが、表層にはＴｉＯ₂ とＮｉＯが生成していた。得られた焼結体の断面を顕微鏡写真で撮影した像は図２と同様のものであった。
【００４７】
（実施例２９）
ＴｉＯ₂ 粉末に代えてＺｒＯ₂ 粉末を使用した以外は、実施例２５と同様の条件で混合、乾燥、成形、マイクロ波加熱を行った。得られた焼結体の生成相をＸ線回析により同定した結果、ＮｉＺｒとＮｉＯが生成していた。得られた焼結体の断面を顕微鏡写真で撮影した像は図１と同様のものであった。
【００４８】
（実施例３０）
ＴｉＯ2 粉末に代えてＺｒＯ2 粉末を使用した以外は、実施例２６と同様の条件で混合、乾燥、成形、マイクロ波加熱を行った。得られた焼結体の生成相をＸ線回析により同定した結果、Ｎｉ₃ ＺｒとＮｉＯが生成していた。得られた焼結体の断面を顕微鏡写真で撮影した像は図１と同様のものであった。
【００４９】
（実施例３１）
加熱雰囲気を大気とした以外は、実施例２９と同様の条件で混合、乾燥、成形、マイクロ波加熱を行った。得られた焼結体の生成相をＸ線回析により同定した結果、内部にはＮｉＺｒとＮｉＯが、表層にはＺｒＯ₂ とＮｉＯが生成していた。得られた焼結体の断面を顕微鏡写真で撮影した像は図２と同様のものであった。
【００５０】
（実施例３２）
加熱雰囲気を大気とした以外は、実施例３０と同様の条件で混合、乾燥、成形、マイクロ波加熱を行った。得られた焼結体の生成相をＸ線回析により同定した結果、内部にはＮｉ₃ ＺｒとＮｉＯが、表層にはＺｒＯ₂ とＮｉＯが生成していた。得られた焼結体の断面を顕微鏡写真で撮影した像は図２と同様のものであった。
【００５１】
（実施例３３）
ＴｉＯ₂ 粉末に代えてＨｆＯ₂ 粉末を使用した以外は、実施例２５と同様の条件で混合、乾燥、成形、マイクロ波加熱を行った。得られた焼結体の生成相をＸ線回析により同定した結果、ＮｉＨｆとＮｉＯが生成していた。得られた焼結体の断面を顕微鏡写真で撮影した像は図１と同様のものであった。
【００５２】
（実施例３４）
ＴｉＯ₂ 粉末に代えてＨｆＯ₂ 粉末を使用した以外は、実施例２６と同様の条件で混合、乾燥、成形、マイクロ波加熱を行った。得られた焼結体の生成相をＸ線回析により同定した結果、Ｎｉ₃ ＨｆとＮｉＯが生成していた。得られた焼結体の断面を顕微鏡写真で撮影した像は図１と同様のものであった。
【００５３】
（実施例３５）
加熱雰囲気を大気とした以外は、実施例３３と同様の条件で混合、乾燥、成形、マイクロ波加熱を行った。得られた焼結体の生成相をＸ線回析により同定した結果、内部にはＮｉＨｆとＮｉＯが、表層にはＨｆＯ₂ とＮｉＯが生成していた。得られた焼結体の断面を顕微鏡写真で撮影した像は図２と同様のものであった。
【００５４】
（実施例３６）
加熱雰囲気を大気とした以外は、実施例３４と同様の条件で混合、乾燥、成形、マイクロ波加熱を行った。得られた焼結体の生成相をＸ線回析により同定した結果、内部にはＮｉ₃ ＨｆとＮｉＯが、表層にはＨｆＯ₂ とＮｉＯが生成していた。得られた焼結体の断面を顕微鏡写真で撮影した像は図２と同様のものであった。
【００５５】
（実施例３７）
Ｃｕ粉末に代えてＳｎ粉末を使用した以外は、実施例１と同様の条件で混合、乾燥、成形、マイクロ波加熱を行った。得られた焼結体の生成相をＸ線回析により同定した結果、ＳｎＴｉとＳｎＯが生成していた。得られた焼結体の断面を顕微鏡写真で撮影した像は図１と同様のものであった。
【００５６】
（実施例３８）
Ｃｕ粉末に代えてＳｎ粉末を使用した以外は、実施例２と同様の条件で混合、乾燥、成形、マイクロ波加熱を行った。得られた焼結体の生成相をＸ線回析により同定した結果、Ｓｎ₃ ＴｉとＳｎＯが生成していた。得られた焼結体の断面を顕微鏡写真で撮影した像は図１と同様のものであった。
【００５７】
（実施例３９）
加熱雰囲気を大気とした以外は、実施例３７と同様の条件で混合、乾燥、成形、マイクロ波加熱を行った。得られた焼結体の生成相をＸ線回析により同定した結果、内部にはＳｎＴｉとＳｎＯが、表層にはＴｉＯ₂ とＳｎＯが生成していた。得られた焼結体の断面を顕微鏡写真で撮影した像は図２と同様のものであった。
【００５８】
（実施例４０）
加熱雰囲気を大気とした以外は、実施例３８と同様の条件で混合、乾燥、成形、マイクロ波加熱を行った。得られた焼結体の生成相をＸ線回析により同定した結果、内部にはＳｎ₃ ＴｉとＳｎＯが、表層にはＴｉＯ₂ とＳｎＯが生成していた。得られた焼結体の断面を顕微鏡写真で撮影した像は図２と同様のものであった。
【００５９】
（実施例４１）
ＴｉＯ₂ 粉末に代えてＺｒＯ₂ 粉末を使用した以外は、実施例３７と同様の条件で混合、乾燥、成形、マイクロ波加熱を行った。得られた焼結体の生成相をＸ線回析により同定した結果、ＳｎＺｒとＳｎＯが生成していた。得られた焼結体の断面を顕微鏡写真で撮影した像は図１と同様のものであった。
【００６０】
（実施例４２）
ＴｉＯ₂ 粉末に代えてＺｒＯ₂ 粉末を使用した以外は、実施例３８と同様の条件で混合、乾燥、成形、マイクロ波加熱を行った。得られた焼結体の生成相をＸ線回析により同定した結果、Ｓｎ₃ ＺｒとＳｎＯが生成していた。得られた焼結体の断面を顕微鏡写真で撮影した像は図１と同様のものであった。
【００６１】
（実施例４３）
加熱雰囲気を大気とした以外は、実施例４１と同様の条件で混合、乾燥、成形、マイクロ波加熱を行った。得られた焼結体の生成相をＸ線回析により同定した結果、内部にはＳｎＺｒとＳｎＯが、表層にはＺｒＯ₂ とＳｎＯが生成していた。得られた焼結体の断面を顕微鏡写真で撮影した像は図２と同様のものであった。
【００６２】
（実施例４４）
加熱雰囲気を大気とした以外は、実施例４２と同様の条件で混合、乾燥、成形、マイクロ波加熱を行った。得られた焼結体の生成相をＸ線回析により同定した結果、内部にはＳｎ₃ ＺｒとＳｎＯが、表層にはＺｒＯ₂ とＳｎＯが生成していた。得られた焼結体の断面を顕微鏡写真で撮影した像は図２と同様のものであった。
【００６３】
（実施例４５）
ＴｉＯ₂ 粉末に代えてＨｆＯ₂ 粉末を使用した以外は、実施例３７と同様の条件で混合、乾燥、成形、マイクロ波加熱を行った。得られた焼結体の生成相をＸ線回析により同定した結果、ＳｎＨｆとＳｎＯが生成していた。得られた焼結体の断面を顕微鏡写真で撮影した像は図１と同様のものであった。
【００６４】
（実施例４６）
ＴｉＯ₂ 粉末に代えてＨｆＯ₂ 粉末を使用した以外は、実施例３８と同様の条件で混合、乾燥、成形、マイクロ波加熱を行った。得られた焼結体の生成相をＸ線回析により同定した結果、Ｓｎ₃ ＨｆとＳｎＯが生成していた。得られた焼結体の断面を顕微鏡写真で撮影した像は図１と同様のものであった。
【００６５】
（実施例４７）
加熱雰囲気を大気とした以外は、実施例４５と同様の条件で混合、乾燥、成形、マイクロ波加熱を行った。得られた焼結体の生成相をＸ線回析により同定した結果、内部にはＳｎＨｆとＳｎＯが、表層にはＨｆＯ₂ とＳｎＯが生成していた。得られた焼結体の断面を顕微鏡写真で撮影した像は図２と同様のものであった。
【００６６】
（実施例４８）
加熱雰囲気を大気とした以外は、実施例４６と同様の条件で混合、乾燥、成形、マイクロ波加熱を行った。得られた焼結体の生成相をＸ線回析により同定した結果、内部にはＳｎ₃ ＨｆとＳｎＯが、表層にはＨｆＯ₂ とＳｎＯが生成していた。得られた焼結体の断面を顕微鏡写真で撮影した像は図２と同様のものであった。
【００６７】
（実施例４９）
Ｃｕ粉末に代えてＺｎ粉末を使用した以外は、実施例１と同様の条件で混合、乾燥、成形、マイクロ波加熱を行った。得られた焼結体の生成相をＸ線回析により同定した結果、ＺｎＴｉとＺｎＯが生成していた。得られた焼結体の断面を顕微鏡写真で撮影した像は図１と同様のものであった。
【００６８】
（実施例５０）
Ｃｕ粉末に代えてＺｎ粉末を使用した以外は、実施例２と同様の条件で混合、乾燥、成形、マイクロ波加熱を行った。得られた焼結体の生成相をＸ線回析により同定した結果、Ｚｎ₃ ＴｉとＺｎＯが生成していた。得られた焼結体の断面を顕微鏡写真で撮影した像は図１と同様のものであった。
【００６９】
（実施例５１）
加熱雰囲気を大気とした以外は、実施例４９と同様の条件で混合、乾燥、成形、マイクロ波加熱を行った。得られた焼結体の生成相をＸ線回析により同定した結果、内部にはＺｎＴｉとＺｎＯが、表層にはＴｉＯ₂ とＺｎＯが生成していた。得られた焼結体の断面を顕微鏡写真で撮影した像は図２と同様のものであった。
【００７０】
（実施例５２）
加熱雰囲気を大気とした以外は、実施例５０と同様の条件で混合、乾燥、成形、マイクロ波加熱を行った。得られた焼結体の生成相をＸ線回析により同定した結果、内部にはＺｎ₃ ＴｉとＺｎＯが、表層にはＴｉＯ₂ とＺｎＯが生成していた。得られた焼結体の断面を顕微鏡写真で撮影した像は図２と同様のものであった。
【００７１】
（実施例５３）
ＴｉＯ₂ 粉末に代えてＺｒＯ₂ 粉末を使用した以外は、実施例４９と同様の条件で混合、乾燥、成形、マイクロ波加熱を行った。得られた焼結体の生成相をＸ線回析により同定した結果、ＺｎＺｒとＺｎＯが生成していた。得られた焼結体の断面を顕微鏡写真で撮影した像は図１と同様のものであった。
【００７２】
（実施例５４）
ＴｉＯ₂ 粉末に代えてＺｒＯ₂ 粉末を使用した以外は、実施例５０と同様の条件で混合、乾燥、成形、マイクロ波加熱を行った。得られた焼結体の生成相をＸ線回析により同定した結果、Ｚｎ₃ ＺｒとＺｎＯが生成していた。得られた焼結体の断面を顕微鏡写真で撮影した像は図１と同様のものであった。
【００７３】
（実施例５５）
加熱雰囲気を大気とした以外は、実施例５３と同様の条件で混合、乾燥、成形、マイクロ波加熱を行った。得られた焼結体の生成相をＸ線回析により同定した結果、内部にはＺｎＺｒとＺｎＯが、表層にはＺｒＯ₂ とＺｎＯが生成していた。得られた焼結体の断面を顕微鏡写真で撮影した像は図２と同様のものであった。
【００７４】
（実施例５６）
加熱雰囲気を大気とした以外は、実施例５４と同様の条件で混合、乾燥、成形、マイクロ波加熱を行った。得られた焼結体の生成相をＸ線回析により同定した結果、内部にはＺｎ₃ ＺｒとＺｎＯが、表層にはＺｒＯ₂ とＺｎＯが生成していた。得られた焼結体の断面を顕微鏡写真で撮影した像は図２と同様のものであった。
【００７５】
（実施例５７）
ＴｉＯ₂ 粉末に代えてＨｆＯ₂ 粉末を使用した以外は、実施例４９と同様の条件で混合、乾燥、成形、マイクロ波加熱を行った。得られた焼結体の生成相をＸ線回析により同定した結果、ＺｎＨｆとＺｎＯが生成していた。得られた焼結体の断面を顕微鏡写真で撮影した像は図１と同様のものであった。
【００７６】
（実施例５８）
ＴｉＯ₂ 粉末に代えてＨｆＯ₂ 粉末を使用した以外は、実施例５０と同様の条件で混合、乾燥、成形、マイクロ波加熱を行った。得られた焼結体の生成相をＸ線回析により同定した結果、Ｚｎ₃ ＨｆとＺｎＯが生成していた。得られた焼結体の断面を顕微鏡写真で撮影した像は図１と同様のものであった。
【００７７】
（実施例５９）
加熱雰囲気を大気とした以外は、実施例５７と同様の条件で混合、乾燥、成形、マイクロ波加熱を行った。得られた焼結体の生成相をＸ線回析により同定した結果、内部にはＺｎＨｆとＺｎＯが、表層にはＨｆＯ₂ とＺｎＯが生成していた。得られた焼結体の断面を顕微鏡写真で撮影した像は図２と同様のものであった。
【００７８】
（実施例６０）
加熱雰囲気を大気とした以外は、実施例５８と同様の条件で混合、乾燥、成形、マイクロ波加熱を行った。得られた焼結体の生成相をＸ線回析により同定した結果、内部にはＺｎ₃ ＨｆとＺｎＯが、表層にはＨｆＯ₂ とＺｎＯが生成していた。得られた焼結体の断面を顕微鏡写真で撮影した像は図２と同様のものであった。
【００７９】
（評価）
得られた実施例１〜６０の焼結体の試験片について、ＪＩＳ−１６０１Ｒに基づく３点曲げ試験を行い、室温における強度を測定した。また、各々の試験片について、鉄系の材料を相手材としてディスク−オン−ディスク法により摩擦試験を行った。さらに、各々の試験片を１５００℃の大気中に１０００時間放置して耐酸化性の試験を行った。
【００８０】
上記３つの試験を、従来法により作製された金属間化合物のみの試験片についても行い、これによる値に対する上記実施例１〜６０各々による値の比を比強度、比摩耗量及び比重量変化として求めた。結果を表１に示す。
【００８１】
【表１】

上記の結果から明らかなように、本発明に係る金属間化合物複合体は高い強度を有し、摩耗量及び酸化による重量変化が少ない。この傾向は、酸化物の表面層を形成したときに一段と顕著になる。
【００８２】
【発明の効果】
以上説明したように、本発明によれば、高温における高強度、高靭性及び高摩擦特性を保持し、且つ、耐酸化性を有する金属間化合物複合体を提供でき、この材料は安価に製造することができるので、産業上極めて有用である。
【図面の簡単な説明】
【図１】本発明に係る焼結体の断面を顕微鏡写真で撮影した像を模式的に示した図。
【図２】本発明に係る他の焼結体の断面を顕微鏡写真で撮影した像を模式的に示した図。
【符号の説明】
１金属間化合物
２第２の金属の酸化物
３第１の金属の酸化物
４酸化物膜[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a material using an intermetallic compound that is useful for a high-temperature heat-resistant member such as a gas turbine, a jet engine, or a high-temperature valve.
[0002]
[Prior art]
Of the A-B binary intermetallic compounds, A has a structure belonging to fcc, hcp or bcc. _Three B-type intermetallic compounds and AB-type intermetallic compounds are widely used as heat-resistant structural members because they can be plastically deformed and have high toughness.
[0003]
However, since the intermetallic compound is obtained by once melting the metal and then cooling it, there is a cost disadvantage in that it requires a considerably high temperature and time. Therefore, as a method for producing an intermetallic compound more easily and inexpensively, JP-A-5-117716 discloses a method in which a raw metal powder is finely pulverized by a mechanical alloying method and then sintered by a plasma sintering method. Has been proposed. However, in this method, there are two processes, a fine powder generation process and a sintering process, so that it does not contribute much to cost reduction.
[0004]
Further, when used under a high temperature condition such as a gas turbine member, the intermetallic compound has a defect that it is inferior in oxidation resistance and corrosion resistance. In order to overcome this, it is conceivable to heat-treat in an oxygen-containing atmosphere and oxidize only the surface to form a protective film. However, the thickness of the film obtained by the heat treatment is about several tens of μm. Is not enough. Furthermore, there is a drawback that the intermetallic compound itself is easily worn.
[0005]
[Problems to be solved by the invention]
As described above, the conventional intermetallic compounds have the problems of high production costs, inferior oxidation resistance and corrosion resistance, and easy wear. The present invention has been made to solve such problems of the prior art, and provides a metal material having high strength, high toughness and high friction characteristics at high temperatures and having oxidation resistance at low cost. It is for the purpose.
[0006]
[Means for Solving the Problems]
In order to achieve the above-mentioned object, the present inventors have conducted intensive research, and as a result, a material containing an intermetallic compound at a low temperature and in a short time by microwave heating a molded body made of a metal powder and an oxide powder. Was found to be an intermetallic compound complex and an intermetallic compound complex having an oxidation-resistant film formed on the surface, leading to the invention of the intermetallic compound complex of the present invention and the method for producing the same. .
[0007]
The intermetallic compound composite of the present invention comprises a metal selected from Ti, Zr, and Hf and a metal selected from Cu, Co, Sn, Ni, and Zn. Consist of Metal selected from Cu, Co, Sn, Ni, Zn for matrix containing intermetallic compound of The oxide is compounded.
[0008]
Another intermetallic compound composite of the present invention includes a metal selected from Ti, Zr, and Hf and a metal selected from Cu, Co, Sn, Ni, and Zn. Consist of Metal selected from Cu, Co, Sn, Ni, Zn for matrix containing intermetallic compound of A metal selected from Ti, Zr, and Hf in which oxides are compounded of It has a surface layer containing an oxide.
[0009]
The method for producing an intermetallic compound composite according to the present invention is a metal selected from Ti, Zr, and Hf. of An oxide powder and a metal powder selected from Cu, Co, Sn, Ni, and Zn are mixed and molded to obtain a molded body, and the molded body is obtained using a microwave in a non-oxidizing atmosphere or under vacuum. Is to heat.
[0010]
Another method for producing an intermetallic compound composite according to the present invention is a metal selected from Ti, Zr, and Hf. of An oxide powder and a metal powder selected from Cu, Co, Sn, Ni, and Zn are mixed and molded to obtain a molded body, and the molded body is heated using a microwave in an oxidizing atmosphere. It is.
[0012]
DETAILED DESCRIPTION OF THE INVENTION
An oxide of a metal element such as Ti, Zr, and Hf (hereinafter referred to as a first metal) has a feature that the microwave absorption rate is rapidly increased between 400 to 1000 ° C. Since microwaves have the property of selectively heating materials with high absorptance, when the molded body in which these oxides and metal powder coexist is heated with microwaves, the above oxides are selectively heated and molded. Even if the body temperature is about 500 ° C., the temperature may locally exceed 1000 ° C. These oxides easily dissociate oxygen at high temperatures, and when the metal powder is a metal such as Cu, Co, Sn, Ni, Zn (hereinafter referred to as a second metal), the oxide of the first metal The dissociated oxygen reacts with the surrounding second metal to form an oxide, and the dissociated first metal also reacts with the surrounding second metal to become an intermetallic compound. As a result, a composite of the intermetallic compound and the second metal oxide is obtained. This intermetallic compound composite has a structure in which ceramic particles are dispersed in an intermetallic compound matrix, and has improved strength and wear resistance as compared with a material containing only an intermetallic compound.
[0013]
In addition, when microwave heating of the molded body is performed in a vacuum or in an inert gas atmosphere, a uniform intermetallic compound composite is obtained, whereas when it is performed in an oxidizing atmosphere, the surface layer of the molded body is obtained. Part is oxidized. As a result, a surface layer of a composite of the first metal oxide and the second metal oxide, which is the same as the raw material, is obtained. The thickness of the surface layer can be controlled by the oxygen content in the atmosphere, and can be all oxides.
[0014]
The present invention is described in detail below.
[0015]
First, the first metal selected from Ti, Zr, and Hf of An oxide powder and a metal powder selected from Cu, Co, Sn, Ni, and Zn are mixed, and a compact is obtained by compression molding. As a specific example, the mixed powder is prepared by mixing with a ball mill for about 3 to 10 hours using a liquid medium such as acetone, and then removing the liquid medium using a rotary evaporator and adjusting the particle size through a sieve. Can be done by. The composition of the intermetallic compound produced | generated changes with the mixing ratio of the metal oxide powder and metal powder to be used, and the 2nd metal is mixed so that it may become 3-5 molar ratio with respect to the oxide 1 of a 1st metal. Is preferred. When the amount of the second metal is less than this range, no intermetallic compound is generated. When the amount of the second metal is large, the amount of the intermetallic compound in the matrix is small and the second metal is contained in a large amount. The raw material powder to be used may be suitably adjusted to a desired particle size as necessary, and those having a particle size of about 0.1 to 10 μm are preferable because they produce good intermetallic compounds and are easy to handle the powder. The obtained mixed powder is filled into a mold in a predetermined amount and subjected to pressure molding to obtain a molded body. For example, the pressure molding is 100 to 1000 kg / cm. ² 1 to 10 t / cm after uniaxially pressing at a moderate pressure ² By applying cold isostatic pressing with a moderate pressure, the desired shape can be appropriately achieved.
[0016]
The obtained molded body is preferably heated by being placed in an applicator of a microwave heating apparatus while being covered with a heat insulating material. The frequency of the microwave used when producing the above-mentioned intermetallic compound composite from the molded body is preferably in the range of 0.3 to 30 GHz, and more preferably 20 to 30 GHz. The microwave is irradiated so that the heating temperature is 1200 ° C. or higher, preferably 1400 ° C. or higher. If the heating temperature is too high, the heat insulating material covering the molded body may be melted, which is not preferable. For this reason, the heating temperature is preferably set to 1200 to 1700 ° C, more preferably 1400 to 1600 ° C. The heating time is 5 minutes or longer, preferably 30 minutes or longer.
[0017]
When the above microwave heating is performed in a non-oxidizing atmosphere such as nitrogen, an intermetallic compound (reference numeral 1 in the figure) composed of the first metal and the second metal as schematically shown in FIG. A complex with the second metal oxide (reference numeral 2 in the figure) is produced, but when heated in an oxidizing atmosphere such as the atmosphere, oxidation proceeds on the surface of the complex, and the intermetallic compound is oxidized. As a result, an oxide of the first metal and an oxide of the second metal are generated. As a result, as shown in FIG. 2, the surface of the composite of the intermetallic compound composed of the first metal and the second metal (reference numeral 1 in the figure) and the oxide of the second metal (reference numeral 2). In addition, an oxide film (reference numeral 4) including the second metal oxide (reference numeral 2) and the first metal oxide (reference numeral 3) is formed. The thickness of such an oxide film depends on the partial pressure of the oxidizing gas in the atmosphere. ^-3 -10 ^-Four When an inert gas such as nitrogen or argon is introduced after the pressure is reduced to about torr, the remaining oxidizing gas is negligible and an oxide film is not substantially formed.
[0018]
【Example】
Hereinafter, the present invention will be described in more detail with reference to examples.
[0019]
(Example 1)
TiO ₂ The powder and Cu powder were weighed so that the molar ratio was 1: 3, and ball mill mixing with nylon balls was performed using acetone as a dispersion medium. After mixing, drying was performed using a rotary evaporator, and the particle size was adjusted through a 500 μm sieve. The obtained mixed powder is filled into a mold, and 200 kg / cm. ² After uniaxial pressing at a pressure of 2 t / cm ² Cold isostatic pressing was performed at a pressure of The periphery of the obtained molded body was covered with a heat insulating material and placed in an applicator of a microwave heating apparatus, and N was applied by a microwave of 28 GHz and 15 kw. ₂ Heated to 800 ° C. for 30 minutes under atmosphere. As a result of identifying the obtained sintered body by X-ray diffraction, CuTi and CuO were produced. An image obtained by photographing a cross section of the obtained sintered body with a micrograph was the same as that shown in FIG.
[0020]
(Example 2)
TiO ₂ Mixing, drying, molding, and microwave heating were performed under the same conditions as in Example 1 except that the powder and Cu powder were weighed so that the molar ratio was 1: 5. As a result of identifying the formed phase of the obtained sintered body by X-ray diffraction, Cu _Three Ti and CuO were generated. An image obtained by photographing a cross section of the obtained sintered body with a micrograph was the same as that shown in FIG.
[0021]
(Example 3)
Mixing, drying, molding, and microwave heating were performed under the same conditions as in Example 1 except that the heating atmosphere was air. As a result of identifying the formed phase of the obtained sintered body by X-ray diffraction, CuTi and CuO are contained inside, and TiO is contained on the surface layer. ₂ And CuO were produced. An image obtained by photographing a cross section of the obtained sintered body with a micrograph was the same as that shown in FIG.
[0022]
(Example 4)
Mixing, drying, molding, and microwave heating were performed under the same conditions as in Example 2 except that the heating atmosphere was air. As a result of identifying the formed phase of the obtained sintered body by X-ray diffraction, Cu was contained inside. _Three Ti and CuO, the surface layer is TiO ₂ And CuO were produced. An image obtained by photographing a cross section of the obtained sintered body with a micrograph was the same as that shown in FIG.
[0023]
(Example 5)
TiO ₂ ZrO instead of powder ₂ Except for using the powder, mixing, drying, molding, and microwave heating were performed under the same conditions as in Example 1. As a result of identifying the production phase of the obtained sintered body by X-ray diffraction, CuZr and CuO were produced. An image obtained by photographing a cross section of the obtained sintered body with a micrograph was the same as that shown in FIG.
[0024]
(Example 6)
TiO ₂ ZrO instead of powder ₂ Mixing, drying, molding, and microwave heating were performed under the same conditions as in Example 2 except that the powder was used. As a result of identifying the formed phase of the obtained sintered body by X-ray diffraction, Cu _Three Zr and CuO were generated. An image obtained by photographing a cross section of the obtained sintered body with a micrograph was the same as that shown in FIG.
[0025]
(Example 7)
Mixing, drying, molding, and microwave heating were performed under the same conditions as in Example 5 except that the heating atmosphere was air. As a result of identifying the formed phase of the obtained sintered body by X-ray diffraction, CuZr and CuO are contained inside, and ZrO is contained in the surface layer. ₂ And CuO were produced. An image obtained by photographing a cross section of the obtained sintered body with a micrograph was the same as that shown in FIG.
[0026]
(Example 8)
Mixing, drying, molding, and microwave heating were performed under the same conditions as in Example 6 except that the heating atmosphere was air. As a result of identifying the formed phase of the obtained sintered body by X-ray diffraction, Cu was contained inside. _Three Zr and CuO, ZrO on the surface layer ₂ And CuO were produced. An image obtained by photographing a cross section of the obtained sintered body with a micrograph was the same as that shown in FIG.
[0027]
Example 9
TiO ₂ HfO instead of powder ₂ Except for using the powder, mixing, drying, molding, and microwave heating were performed under the same conditions as in Example 1. As a result of identifying the production phase of the obtained sintered body by X-ray diffraction, CuHf and CuO were produced. An image obtained by photographing a cross section of the obtained sintered body with a micrograph was the same as that shown in FIG.
[0028]
(Example 10)
TiO ₂ HfO powder ₂ Mixing, drying, molding, and microwave heating were performed under the same conditions as in Example 2 except that the powder was used. As a result of identifying the formed phase of the obtained sintered body by X-ray diffraction, Cu _Three Hf and CuO were generated. An image obtained by photographing a cross section of the obtained sintered body with a micrograph was the same as that shown in FIG.
[0029]
(Example 11)
Mixing, drying, molding, and microwave heating were performed under the same conditions as in Example 9 except that the heating atmosphere was air. As a result of identifying the formed phase of the obtained sintered body by X-ray diffraction, CuHf and CuO are contained inside, and HfO is contained in the surface layer. ₂ And CuO were produced. An image obtained by photographing a cross section of the obtained sintered body with a micrograph was the same as that shown in FIG.
[0030]
(Example 12)
Mixing, drying, molding, and microwave heating were performed under the same conditions as in Example 10 except that the heating atmosphere was air. As a result of identifying the formed phase of the obtained sintered body by X-ray diffraction, Cu was contained inside. _Three Hf and CuO, HfO on the surface ₂ And CuO were produced. An image obtained by photographing a cross section of the obtained sintered body with a micrograph was the same as that shown in FIG.
[0031]
(Example 13)
Mixing, drying, molding, and microwave heating were performed under the same conditions as in Example 1, except that Co powder was used instead of Cu powder. As a result of identifying the production phase of the obtained sintered body by X-ray diffraction, CoTi and CoO were produced. An image obtained by photographing a cross section of the obtained sintered body with a micrograph was the same as that shown in FIG.
[0032]
(Example 14)
Mixing, drying, molding, and microwave heating were performed under the same conditions as in Example 2 except that Co powder was used instead of Cu powder. As a result of identifying the formed phase of the obtained sintered body by X-ray diffraction, Co _Three Ti and CoO were generated. An image obtained by photographing a cross section of the obtained sintered body with a micrograph was the same as that shown in FIG.
[0033]
(Example 15)
Mixing, drying, molding, and microwave heating were performed under the same conditions as in Example 13 except that the heating atmosphere was air. As a result of identifying the formed phase of the obtained sintered body by X-ray diffraction, CoTi and CoO are contained inside, and TiO is contained on the surface layer. ₂ And CoO were generated. An image obtained by photographing a cross section of the obtained sintered body with a micrograph was the same as that shown in FIG.
[0034]
(Example 16)
Mixing, drying, molding, and microwave heating were performed under the same conditions as in Example 14 except that the heating atmosphere was air. As a result of identifying the formation phase of the obtained sintered body by X-ray diffraction, _Three Ti and CoO, the surface layer is TiO ₂ And CoO were generated. An image obtained by photographing a cross section of the obtained sintered body with a micrograph was the same as that shown in FIG.
[0035]
(Example 17)
TiO ₂ ZrO instead of powder ₂ Except for using the powder, mixing, drying, molding, and microwave heating were performed under the same conditions as in Example 13. As a result of identifying the production phase of the obtained sintered body by X-ray diffraction, CoZr and CoO were produced. An image obtained by photographing a cross section of the obtained sintered body with a micrograph was the same as that shown in FIG.
[0036]
(Example 18)
TiO ₂ ZrO instead of powder ₂ Except for using the powder, mixing, drying, molding, and microwave heating were performed under the same conditions as in Example 14. As a result of identifying the formed phase of the obtained sintered body by X-ray diffraction, Co _Three Zr and CoO were generated. An image obtained by photographing a cross section of the obtained sintered body with a micrograph was the same as that shown in FIG.
[0037]
(Example 19)
Mixing, drying, molding, and microwave heating were performed under the same conditions as in Example 17 except that the heating atmosphere was air. As a result of identifying the formed phase of the obtained sintered body by X-ray diffraction, CoZr and CoO were contained inside, and ZrO was contained in the surface layer. ₂ And CoO were generated. An image obtained by photographing a cross section of the obtained sintered body with a micrograph was the same as that shown in FIG.
[0038]
(Example 20)
Mixing, drying, molding, and microwave heating were performed under the same conditions as in Example 18 except that the heating atmosphere was air. As a result of identifying the formation phase of the obtained sintered body by X-ray diffraction, _Three Zr and CoO, ZrO on the surface layer ₂ And CoO were generated. An image obtained by photographing a cross section of the obtained sintered body with a micrograph was the same as that shown in FIG.
[0039]
(Example 21)
TiO ₂ HfO instead of powder ₂ Except for using the powder, mixing, drying, molding, and microwave heating were performed under the same conditions as in Example 13. As a result of identifying the production phase of the obtained sintered body by X-ray diffraction, CoHf and CoO were produced. An image obtained by photographing a cross section of the obtained sintered body with a micrograph was the same as that shown in FIG.
[0040]
(Example 22)
TiO ₂ HfO instead of powder ₂ Except for using the powder, mixing, drying, molding, and microwave heating were performed under the same conditions as in Example 14. As a result of identifying the formed phase of the obtained sintered body by X-ray diffraction, Co _Three Hf and CoO were generated. An image obtained by photographing a cross section of the obtained sintered body with a micrograph was the same as that shown in FIG.
[0041]
(Example 23)
Mixing, drying, molding, and microwave heating were performed under the same conditions as in Example 21 except that the heating atmosphere was air. As a result of identifying the formed phase of the obtained sintered body by X-ray diffraction, CoHf and CoO are contained inside, and HfO is contained in the surface layer. ₂ And CoO were generated. An image obtained by photographing a cross section of the obtained sintered body with a micrograph was the same as that shown in FIG.
[0042]
(Example 24)
Mixing, drying, molding, and microwave heating were performed under the same conditions as in Example 22 except that the heating atmosphere was air. As a result of identifying the formation phase of the obtained sintered body by X-ray diffraction, _Three Hf and CoO, HfO on the surface layer ₂ And CoO were generated. An image obtained by photographing a cross section of the obtained sintered body with a micrograph was the same as that shown in FIG.
[0043]
(Example 25)
Mixing, drying, molding, and microwave heating were performed under the same conditions as in Example 1 except that Ni powder was used instead of Cu powder. As a result of identifying the production phase of the obtained sintered body by X-ray diffraction, NiTi and NiO were produced. An image obtained by photographing a cross section of the obtained sintered body with a micrograph was the same as that shown in FIG.
[0044]
(Example 26)
Mixing, drying, molding, and microwave heating were performed under the same conditions as in Example 2 except that Ni powder was used instead of Cu powder. As a result of identifying the formed phase of the obtained sintered body by X-ray diffraction, Ni _Three Ti and NiO were generated. An image obtained by photographing a cross section of the obtained sintered body with a micrograph was the same as that shown in FIG.
[0045]
(Example 27)
Mixing, drying, molding, and microwave heating were performed under the same conditions as in Example 25 except that the heating atmosphere was air. As a result of identifying the formed phase of the obtained sintered body by X-ray diffraction, NiTi and NiO are contained inside, and TiO is contained on the surface layer. ₂ And NiO were produced. An image obtained by photographing a cross section of the obtained sintered body with a micrograph was the same as that shown in FIG.
[0046]
(Example 28)
Mixing, drying, molding, and microwave heating were performed under the same conditions as in Example 26 except that the heating atmosphere was air. As a result of identifying the formation phase of the obtained sintered body by X-ray diffraction, Ni inside _Three Ti and NiO, the surface layer is TiO ₂ And NiO were produced. An image obtained by photographing a cross section of the obtained sintered body with a micrograph was the same as that shown in FIG.
[0047]
(Example 29)
TiO ₂ ZrO instead of powder ₂ Except for using the powder, mixing, drying, molding, and microwave heating were performed under the same conditions as in Example 25. As a result of identifying the production phase of the obtained sintered body by X-ray diffraction, NiZr and NiO were produced. An image obtained by photographing a cross section of the obtained sintered body with a micrograph was the same as that shown in FIG.
[0048]
(Example 30)
Mixing, drying, molding, and microwave heating were performed under the same conditions as in Example 26 except that ZrO2 powder was used instead of TiO2 powder. As a result of identifying the formed phase of the obtained sintered body by X-ray diffraction, Ni _Three Zr and NiO were generated. An image obtained by photographing a cross section of the obtained sintered body with a micrograph was the same as that shown in FIG.
[0049]
(Example 31)
Mixing, drying, molding, and microwave heating were performed under the same conditions as in Example 29 except that the heating atmosphere was air. As a result of identifying the formed phase of the obtained sintered body by X-ray diffraction, NiZr and NiO are contained inside, and ZrO is contained in the surface layer. ₂ And NiO were produced. An image obtained by photographing a cross section of the obtained sintered body with a micrograph was the same as that shown in FIG.
[0050]
(Example 32)
Mixing, drying, molding, and microwave heating were performed under the same conditions as in Example 30, except that the heating atmosphere was air. As a result of identifying the formation phase of the obtained sintered body by X-ray diffraction, Ni inside _Three Zr and NiO, ZrO on the surface layer ₂ And NiO were produced. An image obtained by photographing a cross section of the obtained sintered body with a micrograph was the same as that shown in FIG.
[0051]
(Example 33)
TiO ₂ HfO instead of powder ₂ Except for using the powder, mixing, drying, molding, and microwave heating were performed under the same conditions as in Example 25. As a result of identifying the production phase of the obtained sintered body by X-ray diffraction, NiHf and NiO were produced. An image obtained by photographing a cross section of the obtained sintered body with a micrograph was the same as that shown in FIG.
[0052]
(Example 34)
TiO ₂ HfO instead of powder ₂ Except for using powder, mixing, drying, molding, and microwave heating were performed under the same conditions as in Example 26. As a result of identifying the formed phase of the obtained sintered body by X-ray diffraction, Ni _Three Hf and NiO were generated. An image obtained by photographing a cross section of the obtained sintered body with a micrograph was the same as that shown in FIG.
[0053]
(Example 35)
Mixing, drying, molding, and microwave heating were performed under the same conditions as in Example 33 except that the heating atmosphere was air. As a result of identifying the formed phase of the obtained sintered body by X-ray diffraction, NiHf and NiO are contained inside, and HfO is contained on the surface layer. ₂ And NiO were produced. An image obtained by photographing a cross section of the obtained sintered body with a micrograph was the same as that shown in FIG.
[0054]
(Example 36)
Mixing, drying, molding, and microwave heating were performed under the same conditions as in Example 34 except that the heating atmosphere was air. As a result of identifying the formation phase of the obtained sintered body by X-ray diffraction, Ni inside _Three Hf and NiO, HfO on the surface ₂ And NiO were produced. An image obtained by photographing a cross section of the obtained sintered body with a micrograph was the same as that shown in FIG.
[0055]
(Example 37)
Mixing, drying, molding, and microwave heating were performed under the same conditions as in Example 1 except that Sn powder was used instead of Cu powder. As a result of identifying the production phase of the obtained sintered body by X-ray diffraction, SnTi and SnO were produced. An image obtained by photographing a cross section of the obtained sintered body with a micrograph was the same as that shown in FIG.
[0056]
(Example 38)
Mixing, drying, molding, and microwave heating were performed under the same conditions as in Example 2, except that Sn powder was used instead of Cu powder. As a result of identifying the formed phase of the obtained sintered body by X-ray diffraction, Sn _Three Ti and SnO were generated. An image obtained by photographing a cross section of the obtained sintered body with a micrograph was the same as that shown in FIG.
[0057]
(Example 39)
Mixing, drying, molding, and microwave heating were performed under the same conditions as in Example 37 except that the heating atmosphere was air. As a result of identifying the formed phase of the obtained sintered body by X-ray diffraction, SnTi and SnO are contained inside, and TiO is contained on the surface layer. ₂ And SnO were produced. An image obtained by photographing a cross section of the obtained sintered body with a micrograph was the same as that shown in FIG.
[0058]
(Example 40)
Mixing, drying, molding, and microwave heating were performed under the same conditions as in Example 38 except that the heating atmosphere was air. As a result of identifying the formed phase of the obtained sintered body by X-ray diffraction, Sn was found inside. _Three Ti and SnO, the surface layer is TiO ₂ And SnO were produced. An image obtained by photographing a cross section of the obtained sintered body with a micrograph was the same as that shown in FIG.
[0059]
(Example 41)
TiO ₂ ZrO instead of powder ₂ Except for using powder, mixing, drying, molding, and microwave heating were performed under the same conditions as in Example 37. As a result of identifying the production phase of the obtained sintered body by X-ray diffraction, SnZr and SnO were produced. An image obtained by photographing a cross section of the obtained sintered body with a micrograph was the same as that shown in FIG.
[0060]
(Example 42)
TiO ₂ ZrO instead of powder ₂ Mixing, drying, molding, and microwave heating were performed under the same conditions as in Example 38 except that the powder was used. As a result of identifying the formed phase of the obtained sintered body by X-ray diffraction, Sn _Three Zr and SnO were produced. An image obtained by photographing a cross section of the obtained sintered body with a micrograph was the same as that shown in FIG.
[0061]
(Example 43)
Mixing, drying, molding, and microwave heating were performed under the same conditions as in Example 41 except that the heating atmosphere was air. As a result of identifying the formed phase of the obtained sintered body by X-ray diffraction, SnZr and SnO are contained inside, and ZrO is contained in the surface layer. ₂ And SnO were produced. An image obtained by photographing a cross section of the obtained sintered body with a micrograph was the same as that shown in FIG.
[0062]
(Example 44)
Mixing, drying, molding, and microwave heating were performed under the same conditions as in Example 42 except that the heating atmosphere was air. As a result of identifying the formed phase of the obtained sintered body by X-ray diffraction, Sn was found inside. _Three Zr and SnO, ZrO on the surface layer ₂ And SnO were produced. An image obtained by photographing a cross section of the obtained sintered body with a micrograph was the same as that shown in FIG.
[0063]
(Example 45)
TiO ₂ HfO instead of powder ₂ Except for using powder, mixing, drying, molding, and microwave heating were performed under the same conditions as in Example 37. As a result of identifying the production phase of the obtained sintered body by X-ray diffraction, SnHf and SnO were produced. An image obtained by photographing a cross section of the obtained sintered body with a micrograph was the same as that shown in FIG.
[0064]
(Example 46)
TiO ₂ HfO instead of powder ₂ Mixing, drying, molding, and microwave heating were performed under the same conditions as in Example 38 except that the powder was used. As a result of identifying the formed phase of the obtained sintered body by X-ray diffraction, Sn _Three Hf and SnO were generated. An image obtained by photographing a cross section of the obtained sintered body with a micrograph was the same as that shown in FIG.
[0065]
(Example 47)
Mixing, drying, molding, and microwave heating were performed under the same conditions as in Example 45 except that the heating atmosphere was air. As a result of identifying the formed phase of the obtained sintered body by X-ray diffraction, SnHf and SnO are contained inside, and HfO is contained in the surface layer. ₂ And SnO were produced. An image obtained by photographing a cross section of the obtained sintered body with a micrograph was the same as that shown in FIG.
[0066]
(Example 48)
Mixing, drying, molding, and microwave heating were performed under the same conditions as in Example 46 except that the heating atmosphere was air. As a result of identifying the formed phase of the obtained sintered body by X-ray diffraction, Sn was found inside. _Three Hf and SnO, HfO on the surface ₂ And SnO were produced. An image obtained by photographing a cross section of the obtained sintered body with a micrograph was the same as that shown in FIG.
[0067]
(Example 49)
Mixing, drying, molding, and microwave heating were performed under the same conditions as in Example 1 except that Zn powder was used instead of Cu powder. As a result of identifying the production phase of the obtained sintered body by X-ray diffraction, ZnTi and ZnO were produced. An image obtained by photographing a cross section of the obtained sintered body with a micrograph was the same as that shown in FIG.
[0068]
(Example 50)
Mixing, drying, molding, and microwave heating were performed under the same conditions as in Example 2 except that Zn powder was used instead of Cu powder. As a result of identifying the formed phase of the obtained sintered body by X-ray diffraction, Zn _Three Ti and ZnO were generated. An image obtained by photographing a cross section of the obtained sintered body with a micrograph was the same as that shown in FIG.
[0069]
(Example 51)
Mixing, drying, molding, and microwave heating were performed under the same conditions as in Example 49 except that the heating atmosphere was air. As a result of identifying the formed phase of the obtained sintered body by X-ray diffraction, ZnTi and ZnO are contained inside, and TiO is contained on the surface layer. ₂ And ZnO were produced. An image obtained by photographing a cross section of the obtained sintered body with a micrograph was the same as that shown in FIG.
[0070]
(Example 52)
Mixing, drying, molding, and microwave heating were performed under the same conditions as in Example 50 except that the heating atmosphere was air. As a result of identifying the formed phase of the obtained sintered body by X-ray diffraction, it was found that Zn was contained inside. _Three Ti and ZnO, the surface layer is TiO ₂ And ZnO were produced. An image obtained by photographing a cross section of the obtained sintered body with a micrograph was the same as that shown in FIG.
[0071]
(Example 53)
TiO ₂ ZrO instead of powder ₂ Except for using the powder, mixing, drying, molding, and microwave heating were performed under the same conditions as in Example 49. As a result of identifying the production phase of the obtained sintered body by X-ray diffraction, ZnZr and ZnO were produced. An image obtained by photographing a cross section of the obtained sintered body with a micrograph was the same as that shown in FIG.
[0072]
(Example 54)
TiO ₂ ZrO instead of powder ₂ Except for using the powder, mixing, drying, molding, and microwave heating were performed under the same conditions as in Example 50. As a result of identifying the formed phase of the obtained sintered body by X-ray diffraction, Zn _Three Zr and ZnO were generated. An image obtained by photographing a cross section of the obtained sintered body with a micrograph was the same as that shown in FIG.
[0073]
(Example 55)
Mixing, drying, molding, and microwave heating were performed under the same conditions as in Example 53 except that the heating atmosphere was air. As a result of identifying the formed phase of the obtained sintered body by X-ray diffraction, ZnZr and ZnO are contained inside, and ZrO is contained in the surface layer. ₂ And ZnO were produced. An image obtained by photographing a cross section of the obtained sintered body with a micrograph was the same as that shown in FIG.
[0074]
(Example 56)
Mixing, drying, molding, and microwave heating were performed under the same conditions as in Example 54 except that the heating atmosphere was air. As a result of identifying the formed phase of the obtained sintered body by X-ray diffraction, it was found that Zn was contained inside. _Three Zr and ZnO, ZrO on the surface layer ₂ And ZnO were produced. An image obtained by photographing a cross section of the obtained sintered body with a micrograph was the same as that shown in FIG.
[0075]
(Example 57)
TiO ₂ HfO instead of powder ₂ Except for using the powder, mixing, drying, molding, and microwave heating were performed under the same conditions as in Example 49. As a result of identifying the production phase of the obtained sintered body by X-ray diffraction, ZnHf and ZnO were produced. An image obtained by photographing a cross section of the obtained sintered body with a micrograph was the same as that shown in FIG.
[0076]
(Example 58)
TiO ₂ HfO instead of powder ₂ Except for using the powder, mixing, drying, molding, and microwave heating were performed under the same conditions as in Example 50. As a result of identifying the formed phase of the obtained sintered body by X-ray diffraction, Zn _Three Hf and ZnO were generated. An image obtained by photographing a cross section of the obtained sintered body with a micrograph was the same as that shown in FIG.
[0077]
(Example 59)
Mixing, drying, molding, and microwave heating were performed under the same conditions as in Example 57 except that the heating atmosphere was air. As a result of identifying the formed phase of the obtained sintered body by X-ray diffraction, ZnHf and ZnO are contained inside, and HfO is contained in the surface layer. ₂ And ZnO were produced. An image obtained by photographing a cross section of the obtained sintered body with a micrograph was the same as that shown in FIG.
[0078]
(Example 60)
Mixing, drying, molding, and microwave heating were performed under the same conditions as in Example 58 except that the heating atmosphere was air. As a result of identifying the formed phase of the obtained sintered body by X-ray diffraction, it was found that Zn was contained inside. _Three Hf and ZnO, HfO on the surface layer ₂ And ZnO were produced. An image obtained by photographing a cross section of the obtained sintered body with a micrograph was the same as that shown in FIG.
[0079]
(Evaluation)
About the obtained test piece of the sintered compact of Examples 1-60, the 3 point | piece bending test based on JIS-1601R was done, and the intensity | strength in room temperature was measured. Further, each test piece was subjected to a friction test by a disk-on-disk method using an iron-based material as a counterpart material. Further, each test piece was left in an atmosphere of 1500 ° C. for 1000 hours to perform an oxidation resistance test.
[0080]
The above three tests were also performed on a test piece of only an intermetallic compound produced by a conventional method, and the ratio of the values according to each of the above Examples 1 to 60 with respect to the values obtained thereby was defined as specific strength, specific wear amount, and specific weight change. Asked. The results are shown in Table 1.
[0081]
[Table 1]

As is clear from the above results, the intermetallic compound composite according to the present invention has high strength, and has little wear change and weight change due to oxidation. This tendency becomes more prominent when an oxide surface layer is formed.
[0082]
【The invention's effect】
As described above, according to the present invention, it is possible to provide an intermetallic compound composite that retains high strength, high toughness and high friction characteristics at high temperatures and has oxidation resistance, and this material is manufactured at low cost. It is extremely useful industrially.
[Brief description of the drawings]
FIG. 1 is a diagram schematically showing an image obtained by photographing a cross section of a sintered body according to the present invention with a micrograph.
FIG. 2 is a diagram schematically showing an image obtained by photographing a cross section of another sintered body according to the present invention with a micrograph.
[Explanation of symbols]
1 Intermetallic compound
2 Second metal oxide
3 Oxide of the first metal
4 Oxide film

Claims

Ti, Zr, oxides of metals metal and Cu selected from Hf, Co, Sn, Ni, in a matrix containing the intermetallic compound made of a metal selected from Zn, the Cu, Co, Sn, Ni, selected from Zn An intermetallic compound complex characterized in that a compound is compounded.

Ti, Zr, oxides of metals metal and Cu selected from Hf, Co, Sn, Ni, in a matrix containing the intermetallic compound made of a metal selected from Zn, the Cu, Co, Sn, Ni, selected from Zn things complexed, Ti, Zr, intermetallic matrix composite characterized by having a surface layer containing an oxide of a metal selected from Hf.

Ti, Zr, powder and Cu oxide of a metal selected from Hf, Co, Sn, Ni, to obtain a molded body by mixing and molding powder of metal selected from Zn, non-oxidizing atmosphere or vacuum The method for producing an intermetallic compound composite according to claim 1, wherein the compact is heated using microwaves.

Ti, to obtain Zr, powder and Cu oxide of a metal selected from Hf, Co, Sn, Ni, and a powder metal mixture molded to shaped bodies selected from Zn, microwave in an oxidizing atmosphere The method for producing an intermetallic compound composite according to claim 2, wherein the formed body is heated using a material.