JP4684298B2 - 白金金属で改質されたγ−Ni+γ’−Ni3Al合金組成物と反応性元素を含有する耐高温性コーティングの製造方法 - Google Patents
白金金属で改質されたγ−Ni+γ’−Ni3Al合金組成物と反応性元素を含有する耐高温性コーティングの製造方法 Download PDFInfo
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Description
(a)支持体上へ白金族金属の層を沈着させることによって白金族金属沈着化支持体を形成させ、次いで
(b)白金族金属沈着化支持体層上へ、Hf、Y、La、Ce、Zr及びこれらの混合物から選択される反応性元素を沈着させることによって該白金族金属沈着化支持体上に表面改質領域を形成させる(この場合、該表面改質領域は、Pt族金属、Ni、Al及び反応性元素を、γ−Ni+γ’−Ni3Al相組成が形成されるような相対濃度で含有する)。
(a)超合金支持体上へ白金層を沈着させることによって白金沈着化支持体を形成させ、
(b)白金沈着化支持体を加熱処理に付し、次いで
(c)得られた白金沈着化支持体上へパックを沈着させることによって該支持体上に表面改質領域を形成させる(この場合、該パックは、該表面改質領域がPt、Ni、Hf及びAlを、γ−Ni+γ’−Ni3Al相組成が形成されるような相対濃度で含有するのに十分な量のHfを含有すると共に、表面改質領域がHfを0.8重量%よりも多くて5重量%よりも少ない量で含有する)。
1)Niに基づく超合金製の支持体に対して、相組成(phase constitution)と熱膨張挙動の点で適合性(compatibility)を示す。
2)コーティング層中での相転移(即ち、βからマルテンサイト又はγ’への不安定化)又はコーティング/支持体の相互拡散ゾーンにおける相転移(即ち、脆い位相的最密(TCP)相、例えば、σ相等の形成)を制限する性能を有さない。
3)Alを支持体からコーティングへ濃度勾配で拡散させるための化学的駆動力が存在する。
4)部分的には、0.8〜5重量%の好ましい反応性元素の存在に起因してTGOスケールの成長速度が非常に遅い。
図1は、熱障壁コーティングを有する金属製物品の一部を示す模式的断面図である。
図2Aは、熱処理前のPt層で被覆された金属製物品の一部を示す模式的断面図である。
図2Bは、超合金製支持体を熱処理に付すと共に、常套の熱障壁コーティングを沈着させた後の図2Aに示す金属製物品の一部を示す模式的断面図である。
図3は、本発明によるPt族金属によって改質されたγ−Ni+γ’−Ni3Al合金組成物の1つの実施態様を示すNi−Al−Pt状態図(1100℃)の一部を示す状態図である。
図5は、反応性金属の含有量を高めた表面改質領域を有する白金族金属層を含む金属製物品の一部を示す模式的断面図である。
図6は、熱障壁コーティングを有する図5に示す金属製物品の一部を示す模式的断面図である。
図7A及び図7Bは、厚さが異なるPt層を有するCMSX−4超合金製支持体を熱処理に付して得られたPtによって改質されたγ−Ni+γ’−Ni3Alコーティングの断面画像を示す。
図8A、図8B及び図8Cは、化学蒸着パック中のAl含有量を変化させて得られたPtによって改質されたγ−Ni+γ’−Ni3Alコーティングの断面画像を示す。
図10は、CMSX−4超合金製支持体上に沈着させたNi22Al30Pt合金コーティングの酸化挙動を示すプロットである。
図11は、CMSX−4超合金製支持体上に沈着させた反応性金属で改質されたγ−Ni+γ’−Ni3Alコーティングの断面画像を示す。
図12は、CMSX−10超合金製支持体上に沈着させた反応性金属で改質されたγ−Ni+γ’−Ni3Alコーティングの断面画像を示す。
図13は、反応性金属で改質されたγ−Ni+γ’−Ni3Alコーティングの1150℃における酸化剥落を示すグラフである。
図14は、レネ(Rene)−N5超合金製支持体上に沈着させた反応性金属で改質されたγ−Ni+γ’−Ni3Alコーティングの断面画像を示す。
図15は、図14に示すコーティングのEPMA分析のプロットを示す。
実施例1
テトラ−アミン白金水素ホスフェート([Pt(NH3)4]HPO4)を用いて電着浴を調製した。超合金製支持体としては、大きさが約15×10×1mmのCMSX−4を使用した。
電流密度:約0.5A/dm2
温度:約95℃
pH:約10.5(NaOHを用いて調整)
電着時間:約0.5時間
陽極と陰極間の距離:約5cm
陽極:Pt
陽極対陰極の表面積比:約2
Ptで被覆されたサンプルを熱処理に付すことにより、内側へのPtの拡散と外側へのAl+Niの拡散によってPtで改質されたコーティングが得られた。沈着されたPt層の厚さがコーティングの微細構造、組成及びγとγ’の相対的な割合に対して影響を及ぼすことが判明した。図7は、電着されたPt層の厚さが異なるCMSX−4サンプルを熱処理に付すことによって得られたコーティングを示す。図7Aにおいては、薄いPt層(約2μm)により、Ptで改質されたγとγ’コーティング(γが主要相である)がもたらされることが示されている。これに対して、図7Bに示すように、より厚いPt層(約7μm)からは、Ptで改質されたγとγ’コーティング(γ’が主要相である)が形成される。
パック中のAl粉末の含有量は、支持体中へのアルミニウムの取り込み量に影響を及ぼす。Alの公称含有量が約12原子%のCMSX−4中のAlは、熱処理中において、Ptに富む表面へ向けて外側へも拡散することができる。従って、パックのセメンテーション工程によって、約22原子%のAlを含有するコーティングを得るためには、少量のAlが必要なだけである。
Hfはγ’相へ分配されることが知られており、また、最終的に存在するHfの臨界含有量は、十分に高いHfの沈着速度が得られるような量でなければならない。この実施例によれば、パック中に5重量%のHfを含有させることによって、γ+γ’コーティング中のHfの含有量が検出可能な量(約0.3原子%よりも多い量)になることが判明した(図8C参照)。Hfを1原子%よりも多く含有するγ’に基づくコーティングは、ハフニウムの沈着条件を調整することによって沈着された。
温度は、Alの沈着度を決定する要因となる。Alを約1重量%含有するパックを用いると共に、比較的高い温度を採用する場合には、Alの供給量は十分に高くなり、γ+γ’コーティングを得るという観点からは望ましくないθ−NiAlが形成された。アルミニウム沈着温度が約900℃よりも高くなると、緻密なθ−NiAlコーティングが形成された。熱処理(例えば、1100℃で1〜4日間の熱処理等)によって、該コーティングからγ’相への変態をもたらすことは困難であった。
図10は、Ni−Al−Pt合金の薄膜層(約60ミクロン)がCMSX−4超合金製支持体へ拡散結合していることを示す。この層は優れた耐酸化性を有すると共に、超合金製支持体に対して優れた適合性(compatibility)を示す。
図11及び12は、2種の異なる超合金製支持体、即ち、CMSX−4製支持体(図11)及びCMSX−10製支持体(図12)上に形成された反応性金属で改質されたNi−Al−Ptコーティングを示す。これらのコーティングは、相互拡散領域(即ち、コーティング−基材合金移行領域)中に最小の位相的最密(topologically closed-packed;tcp)相を有する。
図13は、反応性金属の濃度を高めた反応性金属で改質されたNi−Al−Ptコーティングを用いることによって得ることができる優れた耐酸化性を示す。図中のプロットは、β−NiAlコーティング、0.01原子%のHfを含有する反応性金属で改質されたNi−Al−Ptコーティング(RR)、及び0.5原子%のHfを含有する反応性金属で改質されたNi−Al−Ptコーティング(ISU)を比較するものである。ISUコーティングは1000サイクルよりも多い回数の剥離試験に対し耐性を示したが、β−NiAlコーティング及びRRコーティングはそれぞれ約50サイクル及び約100サイクルの剥離耐性を示すに過ぎなかった。
12 金属製支持体
14 熱障壁コーティング
16 ボンディングコート
18 保護スケール層
20 トップコート
100 高温度用物品
102 金属製支持体
104 白金族金属層
106 表面改質領域
200 表面改質層
202 セラミック層
204 トップコート
206 酸化物スケール層
Claims (10)
- 下記の工程(a)〜(c)を含む耐酸化性物品の製造方法:
(a)Ni及びAlを含有する超合金製支持体上へ白金族金属の層を沈着させることによって白金族金属沈着化支持体を形成させ、
(b)Hf、Y、La、Ce、Zr及びこれらの混合物から選択される反応性元素を含有するパックを準備し、次いで
(c)該パック中の反応性元素を該白金族金属沈着化支持体上に沈着させることによって表面改質領域を形成させる(この場合、該パックは、該表面改質領域が白金族金属、Ni、Al及び反応性元素を、γ−Ni+γ’−Ni3Al相組成が優勢に形成されるような相対濃度で含有するのに十分な量の反応性元素を含有すると共に、該表面改質領域が反応性元素を1〜3重量%の量で含有する) - γ’−Ni3Alが表面改質領域中の主要な相である請求項1記載の方法。
- γ’−Ni3Alが表面改質領域中の単独相である請求項1記載の方法。
- 白金族金属がPtであり、反応性元素がHfである請求項1から3いずれかに記載の方法。
- 白金族金属の層が3μm〜12μmの厚さを有する請求項1から4いずれかに記載の方法。
- 表面改質領域が、Cr、Co、Mo、Ta、Re及びこれらの任意の混合物から成る群から選択される金属をさらに含有する請求項1から5いずれかに記載の方法。
- 反応性元素を650℃〜1100℃の温度で沈着させる請求項1から6いずれかに記載の方法。
- 反応性元素を750℃の温度で沈着させる請求項1から6いずれかに記載の方法。
- パックが、i)塩化アンモニウム及びフッ化アンモニウムから成る群から選択される活性剤0.5重量%〜4重量%、 ii)Hf含有源1重量%〜5重量%、 iii)酸化アルミニウム、酸化ケイ素、酸化イットリウム及び酸化ジルコニウムから成る群から選択される充填剤(充填剤の含有量は、パック全体を100重量%にするのに必要な量である。)から成る請求項1から8いずれかに記載の方法。
- セラミック製コーティングを物品上へ沈着させる工程をさらに含む請求項1から9いずれかに記載の方法。
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US11/012,873 US7531217B2 (en) | 2004-12-15 | 2004-12-15 | Methods for making high-temperature coatings having Pt metal modified γ-Ni +γ′-Ni3Al alloy compositions and a reactive element |
PCT/US2005/045927 WO2006076130A2 (en) | 2004-12-15 | 2005-12-15 | METHODS FOR MAKING HIGH-TEMPERATURE COATINGS HAVING PT METAL MODIFIED Ϝ-Ni + Ϝ’-Ni3 AL ALLOY COMPOSITIONS AND A REACTIVE ELEMENT |
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JP (1) | JP4684298B2 (ja) |
CN (1) | CN101233262A (ja) |
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JPS5873761A (ja) * | 1974-11-07 | 1983-05-04 | ゼネラル・エレクトリツク・コンパニ− | 耐高熱性を有する金属被膜形成用粉末組成物 |
JPH07247803A (ja) * | 1994-03-14 | 1995-09-26 | Toshiba Corp | タービンブレードの製造方法 |
JPH08225959A (ja) * | 1994-12-24 | 1996-09-03 | Rolls Royce Plc | 超合金物品への断熱被膜の被覆方法及び断熱被膜 |
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AU2005324336B9 (en) | 2010-03-11 |
US7531217B2 (en) | 2009-05-12 |
WO2006076130A2 (en) | 2006-07-20 |
JP2008524446A (ja) | 2008-07-10 |
EP1825025A2 (en) | 2007-08-29 |
CA2597898A1 (en) | 2006-07-20 |
US20110197999A1 (en) | 2011-08-18 |
US20060127695A1 (en) | 2006-06-15 |
US20090226613A1 (en) | 2009-09-10 |
BRPI0519084A2 (pt) | 2008-12-23 |
AU2005324336A1 (en) | 2006-07-20 |
AU2005324336B2 (en) | 2010-02-11 |
MX2007007096A (es) | 2008-01-11 |
CN101233262A (zh) | 2008-07-30 |
WO2006076130A3 (en) | 2006-10-26 |
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