JPH0510309B2 - - Google Patents

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Publication number
JPH0510309B2
JPH0510309B2 JP61223710A JP22371086A JPH0510309B2 JP H0510309 B2 JPH0510309 B2 JP H0510309B2 JP 61223710 A JP61223710 A JP 61223710A JP 22371086 A JP22371086 A JP 22371086A JP H0510309 B2 JPH0510309 B2 JP H0510309B2
Authority
JP
Japan
Prior art keywords
ceramic
ceramic substrate
metal
coating
ittria
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
JP61223710A
Other languages
English (en)
Other versions
JPS6379777A (ja
Inventor
Kimiko Sakata
Tadao Tokushima
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
KAGAKU GIJUTSUCHO KINZOKU ZAIRYO GIJUTSU KENKYU SHOCHO
Original Assignee
KAGAKU GIJUTSUCHO KINZOKU ZAIRYO GIJUTSU KENKYU SHOCHO
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by KAGAKU GIJUTSUCHO KINZOKU ZAIRYO GIJUTSU KENKYU SHOCHO filed Critical KAGAKU GIJUTSUCHO KINZOKU ZAIRYO GIJUTSU KENKYU SHOCHO
Priority to JP61223710A priority Critical patent/JPS6379777A/ja
Publication of JPS6379777A publication Critical patent/JPS6379777A/ja
Priority to US07/388,096 priority patent/US4911987A/en
Publication of JPH0510309B2 publication Critical patent/JPH0510309B2/ja
Granted legal-status Critical Current

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Description

【発明の詳細な説明】
〔産業上の利用分野〕 本発明は、セラミツクス基板表面に複合化中間
層をプラズマ溶射(真空溶射を含む)し、該中間
層を介してその中間層表面に異種セラミツクスあ
るいは金属を溶射することによつて、母材及び被
覆材の選択自由度を保持し、前記セラミツクス基
板上に絶縁性、誘電性、導電性等種々の機能をも
たせ、しかも被覆層形成中あるいは使用中に剥離
の生じない密着性に優れたセラミツクス基板上へ
の被覆体の製造法に関する。 〔従来の技術〕 従来からセラミツクス基板にセラミツクスを被
覆することによつて、その母材となるセラミツク
ス材が有する特性に絶縁性あるいは導電性等種々
の機能を付加して機能的に優れた材料を作成する
試みが行われている。 しかし、このような材料の大きな欠点は、母材
と被覆材との接着強度が小さいため、外部からの
応力が母材に十分に伝達されず被覆材自身に応力
が掛り被覆材が破壊したり、剥離する現象を起こ
し、当初の目的を達成出来るものではなかつた。 そこで母材と被覆材の接着の向上を図るため
に、各種の手段が講じられている。例えばセラミ
ツクス表面をブラストして粗面を形成して溶射し
たり、また金属基板上へのセラミツクス溶射法の
類推から、下地溶射として、Ni−Al、Ni−Al−
Mo、Ni−Cr−Al−Y、Co−Cr−Ar−Y等が用
いられると考えられているが、これは基板と被覆
体との間の材料物性を考慮したものではない。 半導体分野では、母材にセラミツクス材を採用
し、金属をCVDや真空蒸着やスパツタリング法
で被覆して導電性を持たせたり、積層膜を作るな
どマイクロエレクトロニクスの分野で1μm以下の
薄膜は作られていたが、1μm以上の厚さを持つ強
固な被覆は類例をみず、前記同様、その密着性に
問題があつた。 〔発明が解決しようとする課題〕 従来のセラミツクス基板上の被覆体の製造法に
よれば、母材と被覆材の接着面が単に機械的な噛
合いであつたり、下地溶射をしても母材と被覆材
の組合わせによつては、熱膨張係数の差が大きい
ため、母材と被覆材の境界面に熱的応力歪が発生
し、またもろい金属間化合物が出来たりして本質
的な密着性の解決法にはならなかつた。その為、
3〜4Kg/mm2の強度が常識的であつた。 〔問題点を解決するための手段及び作用〕 本発明は、上記に鑑みてなされたものであり、
基板材及び当該基板材が有する機能に加えて、被
覆材が有する機能を付加して選択自由度を大きく
保持しながら、特に密着性に優れたセラミツクス
基板上への被覆体の製造法を提供するために、セ
ラミツクス基板材と金属あるいは溶射複合セラミ
ツクスとの間に酸化物と前記金属主成分粉末ある
いは溶射セラミツクス主成分粉末とからなる複合
体である中間層を介在させて、具体的にはセラミ
ツクス基板上に中間層を直接溶射(真空溶射も含
む)し、その上に複合セラミツクス粉を溶射被覆
し、前記セラミツクス基板と中間層との界面で
は、化学的な反応層及び投錨効果により、一方前
記中間層と溶射金属との界面では同種金属の相互
拡散あるいはもろくない異種金属間化合物によつ
て、あるいは前記中間層と溶射セラミツクスとの
界面では反応層によつて接合する様に基板と被覆
体の多様な組合わせに対応したセラミツクス基板
上への被覆体の製造法を提供するものである。 〔実施例〕 以下、本発明によるセラミツクス基板上への被
覆体の製造法を詳細に説明する。 本発明は、セラミツクス基板上に金属あるいは
前記セラミツクスと異種セラミツクスをプラズマ
溶射(この場合真空溶射も含む)する際に、当該
構成体の中間に複合化中間層を介在させ、該複合
化中間層と前記構成体の界面において、その組合
わせに起因する特有の接合体を有することによつ
て密着性のよいセラミツクス基板上への被覆体の
製造法を提供するものである。 本発明によると、基板、中間層及び被覆体の各
構成体の材料はその組合わせにより種々選択され
るものであるが、基板セラミツクス及び被覆体用
金属は特に限定しないが、被覆用セラミツクス材
料は、例えば、基板との熱膨張率の差を小さく押
さえたり、あるいは溶射性の向上を図るため、複
合化して、その組合わせにより生ずる特有の性質
も制御することが必要である。 一方、前記複合化中間層は、基板セラミツクス
上への金属溶射に当たつてはセラミツクス基板が
酸化物(Al2O3系、ZrO2系、SiO2系、TiO2系、
Nb2O5系、MgO系等)、炭化物(TiC系、NbC
系、WC系)あるいは窒化物(AlN系、TiC系、
NbC系)の場合にあつては、溶射金属主成分あ
るいは活性金属にイツトリア(Y2O32〜20Mol
%)単独若しくはイツトリア(Y2O3)に基板セ
ラミツクス成分の一部を添加したもの、あるいは
又、溶射金属主成分に低級酸化物を添加したもの
を中間層として選択される。 また、セラミツクス基板上への異種セラミツク
ス溶射についても、上記同様の複合化中間層が選
択される(表−1参照)。 更に、セラミツクス基板がSiC系、Si3N4系の
場合にあつては、活性金属(Ti、Al、Nb、Cu)
を中間層として溶射するか、あるいは又、前記活
性金属にイツトリア(Y2O30〜20Mol%)単独、
若しくはイツトリア(Y2O3)にAl2O3、SiO2
CaO、ZrO2、MgO、CeO2等を添加したものを中
間層として選択される。 以上の各構成体の組合わせによつて基板セラミ
ツクスの加工処理(投錨)をした表面に前記複合
化中間層をArガス、HeガスあるいはAr−N2
ス等不活性ガスを介して所定条件で溶射し、その
後、基板セラミツクスと異なつた機能、例えば、
絶縁性、誘電性、磁性、導電性、耐熱性、耐摩耗
性および伝熱性等を有する被覆用の金属(例え
ば、鉄系材料、非鉄系材料、Al合金、Cu合金、
貴金属、耐熱性材料等)、あるいは異種セラミツ
クスを前記同様所定条件によつて溶射し、セラミ
ツクス基板上に所定の機能を有する被覆体を生成
することができる。 以上述べた本願によりセラミツクス基板上への
被覆体の製造法を構成する各々の材料の組合わせ
及びその界面での反応を表示したのが表−1であ
る。
【表】
【表】 このようにして、得られたセラミツクス被覆体
の性質は、特に粉末組成の適当な選択及び粉末の
物理的性質の制御および溶射条件の選択によつて
制御することができ、これらの選択により所望な
性質を有する材料をえることができる。更に、本
発明によると、セラミツクス基板表面に単一の材
料の被覆体を構成する必要はなく、目的に応じて
機能性を持たせた金属及び異種セラミツクスを組
合わせパターン化あるいは積層して機能性を持た
せることが可能である。 実施例 1 ジルコニア系セラミツクス基板上に、複合化中
間層Fe−25Mol%FeOを溶射条件Arガス100SC
FH(STandard Cubic Feet/Hourの略)、Heガ
ス20SCFH、50V、700A、溶射距離100mmで3分間
溶射後、Feを溶射条件Arガス100SCFH、Heガス
20SCFH、50V、700A、溶射距離100mmで3分間溶
射した(第1図)。 実施例 2 アルミナ系セラミツクス基板上に、複合化中間
層Ti−5Mol%Y2O3を溶射条件Arガス100SCFH、
Heガス20SCFH、50V、700A、溶射距離100mmで
3分間溶射した表面を研摩したもの(第2図)。 実施例 3 アルミナ系セラミツクス基板上に、複合化中間
層Cu−5Mol%Y2O3を溶射条件Arガス100SCFH、
Heガス20SCFH、50V、700A、溶射距離100mmで
3分間溶射後、Cuを溶射条件Arガス100SCFH、
Heガス20SCFH、50V、700A、溶射距離100mmで
3分間溶射した(第3図)。 実施例 4 チタニア系セラミツクス基板上に、複合化中間
層Al−5Mol%Y2O3を溶射条件Arガス100SCFH、
Heガス20SCFH、50V、650A、溶射距離100mmで
3分間溶射後、Al合金(Al−Mg−Si系)粉末を
溶射条件Arガス100SCFH、Heガス20SCFH、50V、
650A、溶射距離110mmで3分間溶射した(第4
図)。 実施例 5 アルミナ系セラミツクス基板上に、複合化中間
層Al−ZrO2を溶射した後、部分安定化ジルコニ
ア(PSZ)を、溶射条件Arガス100SCFH、Heガ
ス20SCFH、50V、700A、溶射距離100mmで3分間
溶射した(第5図)。 実施例 6 部分安定化ジルコニア(PSZ)基板上に、複合
化中間層Ti−ZrO2粉末を溶射し、更にTiCを溶
射したもの(第6図)。 実施例 7 アルミナ系セラミツクス基板上に、複合化中間
層Al2O3−10Mol%Y2O3を溶射後、TiNを溶射し
たもの(第7図)。 実施例 8 チタニア系セラミツクス基板上に、複合化中間
層Ti−10Mol%Y2O3を溶射後、WCを溶射した
もの(第8図)。 実施例 9 アルミナ系セラミツクス基板上に、複合化中間
層Ti−5Mol%Y2O3を溶射後、SiC−5Mol%
Y2O5を溶射したもの(第9図)。 実施例 10 SiC系セラミツクス基板上に、複合化中間層Ti
−5Mol%Y2O3を溶射後、Si3N4−10Mol%Y2O3
を溶射したもの(第10図)。 以上の実施例1〜10の被覆体に治具を接着剤
(アルダイトA1)で取り付けてテストピースを作
製して引張強度を測定したが、何れも接着剤の部
分で破断したため、7Kg/mm2以上の引張強度を持
ち、従来の引張強度の3〜4Kg/mm2程度に比べ何
れも接着性がよかつた。 また、図1〜10は以上の実施例1〜10の溶射
表面に走査電子顕微鏡(SEM像)を示した写真
である接合状態を光学顕微鏡写真で示したもので
ある。 発明の効果 以上説明した通り、本発明のセラミツクス基板
上への被覆体の製造法によれば、セラミツクス基
板材と金属あるいは溶射セラミツクスとの間に酸
化物と前記金属主成分粉末あるいは溶射セラミツ
クス主成分粉末とを混合した複合体である中間層
を介在させて、具体的にはセラミツクス基板上に
中間層を直接溶射(真空溶射も含む)するか、あ
るいは塗布後に加熱処理し、その上に複合セラミ
ツクス粉を溶射被覆し、前記セラミツクス基板と
中間層との界面では、反応層及び投錨効果によ
り、一方前記中間層と溶射金属との界面では同種
金属相互拡散あるいは異種金属間化合物によつ
て、あるいは前記中間層と溶射セラミツクスとの
界面では反応層によつて接合する様に各構成体を
種々選択するようにしたため、基板材及び当該基
板材が有する機能に加えて、被覆材が有する機能
を付加して選択自由度を大きく保持しながら、特
に密着性に優れたセラミツクス基板上への被覆体
の製造法を提供することができる。
【図面の簡単な説明】
第1図はジルコニア系セラミツクス基板上に中
間層Fe−FeOを溶射し、更に炭素鋼(Fe)粉末
を溶射被覆した試料表面の走査型電子顕微鏡
(SEM像)、第2図はアルミナ系セラミツクス基
板上に中間層Ti−Y2O3を溶射し、更にTi合金を
溶射した試料表面のSEM像、第3図はアルミナ
系セラミツクス基板上にCu−Y2O3の中間層と
し、更にCuを溶射した試料表面のSEM像、第4
図はチタニア系セラミツクス基板上にAl−Y2O3
の中間層を、更にAl合金を溶射した試料表面の
SEM像、第5図はアルミナ系セラミツクス基板
上にAl−ZrO2の中間層を、更に部分安定化ジル
コニア(PSZ)を溶射した試料表面のSEM像、
第6図はPSZ基板上にTi−ZrO2の中間層を、更
にTiNを溶射した試料表面のSEM像、第7図は
アルミナ系セラミツクス基板上にTi−Y2O3の中
間層を、更にTiNを溶射した試料表面のSEM像、
第8図はアルミナ系セラミツクス基板上にTi−
Y2O3溶射後、WCを溶射した試料表面のSEM像、
第9図はアルミナ系セラミツクス基板上にTi−
Y2O3溶射後、SiC−Y2O3を溶射した試料表面の
SEM像、第10図はアルミナ系セラミツクス基
板上にTi−Y2O3溶射後、Si3N4−Y2O3を溶射し
た試料表面のSEM像。

Claims (1)

  1. 【特許請求の範囲】 1 セラミツクス基板表面に金属で被覆されたセ
    ラミツクス基板の被覆体において、 前記セラミツク基板と前記金属の被覆体との中
    間に、 (a) 被覆金属主成分に、イツトリアを添加したも
    の (b) 被覆金属主成分に、イツトリアと基板セラミ
    ツクスの一部を添加したもの (c) 被覆金属主成分に、低級酸化物を添加したも
    の (d) 活性金属にイツトリアを添加したもの (e) 活性金属にイツトリアと基板セラミツクスの
    一部を添加したもの (f) 活性金属にイツトリアにAl2O3、SiO2
    CaO、ZrO2、MgO、CeO2のいづれかを添加し
    たもの のいづれかの複合化中間層の界面において投錨及
    び化学的に接合する溶射工程と、 積層した前記複合化中間層の表面に金属の被覆
    層において複合化中間層と前記金属の界面におい
    ては両構成体に存する同種金属の相互拡散又は異
    種金属間化合物の接合する工程とを特徴とするセ
    ラミツクス基板上への被覆体の製造法。 2 複合化中間層は (a) 溶射金属の主成分と2〜20Mol%イツトリア (b) 溶射金属の主成分と2〜20mol%イツトリア
    及び0〜10mol%基板セラミツクス主成分 (c) 溶射金属の主成分と10〜80mol%の低級酸化
    物 のいづれかからなる特許請求の範囲第1項に記載
    のセラミツクス基板上への被覆体の製造法。 3 複合化中間層はセラミツクス基板がSiCある
    いはSi3N4であるときは、 (a) 活性金属に2〜20mol%イツトリア (b) 活性金属と2〜20mol%イツトリアに0〜
    10mol%のAl2O3、CaO、SiO2、ZrO2、MgO、
    CeO2のいづれかを添加したもの のいづれかから成る特許請求の範囲第1項に記載
    のセラミツクス基板上への被覆体の製造法。 4 セラミツクス基板表面に異種複合セラミツク
    スで被覆されたセラミツクス基板の被覆体におい
    て、 前記セラミツクス基板と、被覆複合セラミツク
    スの中間に、 (a) 被覆セラミツクスにイツトリアを添加したも
    の (b) 被覆セラミツクスにイツトリアと基板セラミ
    ツクスの一部を添加したもの のいづれかの複合化中間層を溶射し、界面におい
    て投錨及び化学的に接合する工程と、 積層した前記複合化中間層の表面に被覆複合セ
    ラミツクスを溶射し、複合化中間層と被覆複合セ
    ラミツクスの界面では化学的に接合する工程とを
    特徴とするセラミツクス基板上への被覆体の製造
    法。 5 被覆複合セラミツクスは酸化物系、炭化物系
    及び窒化物系からなる特許請求の範囲第4項に記
    載のセラミツクス基板上への被覆体の製造法。
JP61223710A 1986-09-24 1986-09-24 セラミツクス基板上への被覆体の製造法 Granted JPS6379777A (ja)

Priority Applications (2)

Application Number Priority Date Filing Date Title
JP61223710A JPS6379777A (ja) 1986-09-24 1986-09-24 セラミツクス基板上への被覆体の製造法
US07/388,096 US4911987A (en) 1986-09-24 1989-08-01 Metal/ceramic or ceramic/ceramic bonded structure

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP61223710A JPS6379777A (ja) 1986-09-24 1986-09-24 セラミツクス基板上への被覆体の製造法

Publications (2)

Publication Number Publication Date
JPS6379777A JPS6379777A (ja) 1988-04-09
JPH0510309B2 true JPH0510309B2 (ja) 1993-02-09

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Application Number Title Priority Date Filing Date
JP61223710A Granted JPS6379777A (ja) 1986-09-24 1986-09-24 セラミツクス基板上への被覆体の製造法

Country Status (2)

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US (1) US4911987A (ja)
JP (1) JPS6379777A (ja)

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Also Published As

Publication number Publication date
US4911987A (en) 1990-03-27
JPS6379777A (ja) 1988-04-09

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