TW200538276A - Thin 7YSZ, interfacial layer as cyclic durability (spallation) life enhancement for low conductivity TBCs - Google Patents

Thin 7YSZ, interfacial layer as cyclic durability (spallation) life enhancement for low conductivity TBCs Download PDF

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TW200538276A
TW200538276A TW094112600A TW94112600A TW200538276A TW 200538276 A TW200538276 A TW 200538276A TW 094112600 A TW094112600 A TW 094112600A TW 94112600 A TW94112600 A TW 94112600A TW 200538276 A TW200538276 A TW 200538276A
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ceramic
coating
metal substrate
layer
group
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Nicholas E Ulion
Mladen F Trubelja
Michael J Maloney
David A Litton
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United Technologies Corp
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Description

200538276 九、發明說明： 【發明所屬之技術領域】 本發明係關於一種用於塗布至金屬零件之絕熱塗層的陶 瓷材料，其中將一安定氧化錯之界面層挿置於零件與塗層 之間。 【先前技術】 燃氣輪機引擎係用於將呈燃料形態之化學位能轉化為熱 能然後再轉化為使用於推動航空器、產生電力、泵送流體 等等之機械能之經充分發展的機構。目前改良燃氣輪機引 擎效率之主要可資利用的途徑似乎係使用較高的操作溫 度。然而，目前使用於燃氣輪機引擎中之金屬材料已相當 接近其熱安定性的上限。在新型燃氣輪機引擎之最熱的部 分中，金屬材料係在高於其熔點的氣體溫度下使用。其仍 可使用係因其經空氣冷卻。但提供空氣冷卻會使引擎效率 降低。 / 因此’已廣泛地發展配合經冷卻燃氣輪機航空器硬體使 用的絕熱塗層。經由使用絕熱塗層（TBC)，可實質上降低冷 部空氣的需要量，因而提供相對的效率增加。一種利用於 保濩燃氣輪機引擎零件之常用的TBC包含59重量百八比
Gd2〇3 _ w Zr〇2。此種基於㈤士之取雖然提供低導熱 性，但其可能呈現較習知之經氧化纪安定氧化錯⑽如， 7YSZ)低的耐散裂性。咸信此易散裂性係源自系統 較低的破裂靭度特性。 ’、、、之 經發現加入一起始、薄層（標稱0.5-1密爾（mU))的不同安 101136.doc 200538276 定氧化錯（例如，7YSZ)可增進Gd_Zi^、統的耐散裂性。雖然 尚未7G全明瞭其原因，但此種增加的耐散裂性可能係源自 7YSZ之杈咼的破裂靭度，而使其可抵抗於TBC/黏合塗層 (或更特疋5之為氧化鋁層）界面所產生的應力。中間 層之另一可能的有利效應可能係與消除在氧化釓與形成於 基板合金或黏合塗層表面上之氧化鋁外殼之間之潛在不利
交互作用有關。不管作用的機構為何，經顯示加入薄7YSZ 中間層可補償基於Gd-Zr之TBC之較低的破裂靭度，而增進 •耐散裂性。 除了耐散裂性之外，亦需產生呈現耐侵蝕性的Tbc。當 由引擎所吸取或釋出之微細顆粒在引擎操作過程中以相當 面速度衝擊TBC時，會發生侵蝕。此導致TBC自其表面向下 的磨損。典型上，僅有非常小的Tbc顆粒會被一定的衝擊 事件敍掉’由於僅有微細的顆粒有進入輪機中之傾向， 而大顆粒則會在壓縮機中被離心出。此種侵蝕事件會於每 • 個事件中釋出相當小塊的TBC，而使TBC之厚度局部地輕微 降低。呈現較低破裂靭度之較低導熱性的TBC(諸如59 GdZr) 易受侵I虫。
然而，雖然基於Gd-Zr之TBC，尤其係59重量百分比 Gd2〇3_41 Zr〇2，呈現相對上低的導熱性係數，但仍有需要 呈現再更低之導熱性的TBC。此種TBC可能呈現較現有系統 低的耐散裂及侵蝕性。此種耐散裂性理想上將表現在TBC 自下方零件分離之抵抗力以及包含TBC之不同層彼此分離 的抵抗力上。 101136.doc 200538276 一般而言’金屬材料具有超越陶瓷材料的熱膨脹係數。 因此，在發展成功的絕熱塗層中所必需解決的一個問題為 使陶瓷材料的熱膨脹係數與金屬基板更密切配合，以致在 加熱時，當基板膨脹時，陶瓷塗層材料不會龜裂。氧化锆 具有而熱膨脹係數，此係氧化錯可於金屬基板上成功作為 絕熱材料的主要原因。 儘管目前電子束物理蒸氣沈積氧化銼基塗層的使用相當 成功，但仍持續需要呈現優良隔熱能力的改良塗層，尤其 係當對塗層密度正規化時絕緣能力改良的塗層。當設計燃 氣輪機引擎，尤其係旋轉零件時，重量始終係關鍵的因素。 陶瓷絕熱塗層並非負荷承受材料，因此其會增加重量但不 會增加強度。亟需一種增加最少重量，同時仍可提供最大 隔熱能力的陶瓷絕熱材料。此外，明顯地對於長壽命、安 定性、經濟等等有正常的需求。 因此，品要一種包括提供較低導熱性，但呈現適當财散 裂性之絕熱塗層的經塗布零件。 【發明内容】 因此本灸明之一目的為提供用於塗布至金屬零件之絕 熱塗層的陶究材料，其中將一7YSZ之界面層挿置於零件與 塗層之間，以提高塗層的耐散裂性。 根據本發明，耐散裂性金屬物件包括一金屬基板，至少 一包含氧化鍅基質及至少一選自由La、Ce、Pr、Nd、Sm、 Eu、Gd、Tb、Dy、Ho、Er、Tm、Yb、Lu、&、^、γ、
Mo及C、稀土氧化物、銃、及銦所組成之群之其他元素的 101136.doc 200538276 陶竞絕熱塗層，及位於至少一部分的基板上且在 與至少-陶兗絕熱塗層之間的陶究黏合塗層，#中陶二黏 合塗層包括經氧化妃安定氧化錯（Ysz)。 進一步根據本發明，耐散裂性金屬物件包括至少一具低 於約1 · 5瓦/米C之導熱性的陶瓷絕熱塗層。 進一步根據本發明，一種降低金屬物件之散裂的方法包 括下列步驟··提供一金屬基板，將金屬基板塗布至少一包 含氧化錯基質及至少一選自由La、Ce、Pr、Nd、Sm、Eu、
Gd、Tb、Dy、Ho、Er、Tm、Yb、Lu、Sc、In、γ、M。及 c、 稀土氧化物、銃、及銦所組成之群之其他元素的陶瓷絕熱 塗層，及將一陶瓷黏合塗層挿置於金屬基板與至少一陶瓷 絕熱塗層之間，其中陶瓷黏合塗層包括經氧化釔安定氧化 锆（YSZ)。 進一步根據本發明，耐散裂性金屬物件包括一金屬基 板，至少一包含氧化锆基質及至少一選自由La、Ce、Pr、
Nd、Sm、Eu、Gd、Tb、Dy、Ho、Er、Tm、Yb、Lu、Sc、
In、Y、Mo及C、稀土氧化物、銳、及銦所組成之群之其他 元素的陶瓷絕熱塗層，一位於金屬基板與至少一陶瓷絕熱 塗層之間的陶瓷黏合塗層（其中陶瓷黏合塗層包括經氧化 釔安定氧化錘（YSZ))，一挿置於金屬基板與陶瓷黏合塗層 之間的熱成長氧化物（TGO)層，及一位於TGO層與金屬基板 之間的金屬黏合塗層。 本發明之一或多個具體實施例的細節記述於附圖及以下 的說明中。本發明之其他特徵、目的、及優點將可由說明 101136.doc -9- 200538276 及圖式’及由申請專利範圍而明白。 【實施方式】 因此’本發明之教示為提供—種具有—金屬基板的金屬 物件，以燃氣輪機引擎組件較佳，其包括一陶竞絕熱塗層 ()及插置於陶瓷TBC與金屬基板之間之安定氧化錯 的陶瓷黏合塗層。-較佳的陶瓷黏合塗層係7YSZ，雖然其 他的、、至氧化釔女疋氧化锆，例如，包含約重量％氧化釔 # <安定氧化鍅亦可㈣。所有情況中之"TBC：包含經加 入或多種下列兀素之氧化錯基質：La、Ce、pr、Nd、^、
Eu、Gd、Tb、Dy、Ho、Er、Tm、Yb、Lu、Sc、In、γ、
Mo及C '稀土氧化物、銳、及銦’其中該等元素係以卜5〇 莫耳％(及2-40莫耳％較佳kM2〇3氧化物存在，其中以係指 所列的元素。經氧化釔安定氧化鍅（YSZ)呈現期望的機械完 整f生，而使其可承受當其所附著之金屬物件經熱循環時所 產生的應力。結果，YSZ之陶瓷黏合塗層作為在金屬物件 φ 與陶:是TBC之間的安定化橋樑，因而提高陶莞TBC的耐散裂 性。 < 參照圖1，其說明本發明之金屬零件1〇的組態，其係由形 成金屬物件之金屬基板丨丨、陶瓷TBC、及陶瓷黏合塗層所 組成。此物件亦可包括一在基板與陶瓷黏合塗層之間的金 屬黏合塗層，諸如貼面（MCrA1 γ)黏合塗層或亦可包含貴金 屬的鋁化物。或者，基板可包括可形成黏附氧化鋁層，且 因此不需要金屬黏合塗層的材料。金屬基板〗丨形成待塗布 陶瓷TBC 15的部分。金屬基板u係由鋼、超合金、鈦合金 101136.doc -10 · 200538276 及銅合金形成較佳。如所指示，將包含經氧化釔安定氧化 錘（YSZ)之陶瓷黏合塗層13沈積於金屬基板丨丨之外表面。陶 瓷黏合塗層13之厚度在0.5及3密耳之間較佳，厚度大約1密 耳最佳。同樣地，將陶究TB C塗布至陶竟黏合塗層13的最 外層。 陶瓷TBC 15可利用各種製程塗布至陶瓷黏合塗層13。此 等製程包括，但不限於，熱喷霧製程諸如於空氣中電漿喷 _ 霧（APS)、低壓電漿喷霧（LPPS)、高速氧燃料製程（HV〇F)、 通道爆震槍（via detonation gun)(D搶）、及濺鍍。沈積陶瓷 TBC 1 5之一較佳方法包括電子束物理蒸氣沈積（EBpVD)。 由於使用EBPVD產生適用於極端溫度應用之結構，因此更 適用於塗布熱段輪機組件，因而使用EBpVD提供特定的優 點。熱喷霧加工提供塗布複雜形狀之大組件的優點，且更 適用於塗布諸如燃燒器的組件。 在燃氣輪機應用中，金屬基板u之背側19將經冷卻空氣 •(未示於圖中）冷卻，而陶瓷TBC 15之外表面21將暴露至高 溫。熱流將自外表面21流至經冷卻的表面背側19，且熱流 量實質上將因陶瓷TBC 15而降低。 參照圖2，其說明本發明之金屬零件10的另一具體實施 例。金屬零件10再加入插置於金屬基板丨丨與陶瓷黏合塗層 13之間的熱成長氧化物（TG0)17。如前，陶瓷黏合塗層13 之厚度在大約0.5及3·〇密耳之間較佳，厚度大約1〇密耳最 佳。 參照圖5,其說明另一具體實施例，其中將金屬黏合塗層 101136.doc 200538276 51塗布於金屬基板π與陶瓷黏合塗層13之間。金屬黏合塗 層51包括含鋁之塗層。選擇此金屬塗層之組合物，以致在 操作過程中將一連續、薄的緩慢成長氧化鋁層形成於金屬 黏合塗層上。此氧化鋁在技藝中被普遍稱為熱成長氧化物 或TGO。典型的金屬黏合塗層51包括利用APS、lpps、陰 極電弧、及其他技術沈積之NiCoCrAlY貼面塗層，以及經 由電鍍Pt，然後蒸氣塗布NiAi及將塗層擴散熱處理形成 (Ni，Pt)Al而形成的（Ni，Pt)Al塗層。如前所指，在不存在金 屬黏合塗層5 1時’在金屬基板11與陶瓷黏合塗層丨3之間形 成丁 GO層17。對於具有金屬黏合塗層51之系統，此TG〇層 17係形成於金屬黏合塗層51與陶瓷黏合塗層13之間。tg〇 層17厚度在作為陶瓷塗布部分上典型上係〇1_〇 5微米厚， 且於使用時成長至1 〇微米厚。由於氧擴散通過氧化鋁之速 度相當慢，因而TGO層17可提供超合金零件抗氧化性。 參照圖3，其說明本發明之金屬零件丨〇的另一具體實施 例。除了將包含7YSZ之陶瓷黏合塗層13插置於陶瓷TB(： 15 與金屬基板11之間之外，另塗布一外部陶瓷塗層3丨。外部 陶瓷塗層31形成金屬基板u的最外部塗層。由於其包含 ysz，因而外部陶变塗層31具有固有的良好機械完整性， 且其可進一步增進對金屬零件1〇在操作中所受到之應力的 耐散裂性。此外，外部陶瓷塗層31使金屬零件1〇之最外部 表面被侵蝕的傾向減小。外部陶瓷塗層31之厚度在大約〇·5 及3·0密耳之間較佳，厚度大約1〇密耳更佳。 參照圖4，其說明本發明之金屬零件1〇的另一具體實施 101136.doc -12- 200538276 例，其中將至少兩層陶瓷TBC 15、15，沈積於金屬基板u 上’及更明確言之係沈積於陶瓷黏合塗層13上，使金屬基 板11與陶瓷TBC 15、15’隔離。一包含YSZ之陶瓷層33分隔 兩陶瓷TBC 15、15,。在兩陶瓷TBC 15之間之包含YSZ(以 7YSZ較佳）之陶瓷層33可使機械完整性提高，藉此使陶兗 TBC 15、15’彼此附著。結果，整體提高多個陶瓷TBc 15、 15’的耐散裂性。陶瓷層33之厚度在〇.5及3 〇密耳之間較 佳，大約1·0密耳最佳。 進行使用兩電子束搶的EB-PVD塗布試驗，其中將各種組 合物塗布至金屬基板11以形成絕熱陶瓷。測量各組合物之 耐散裂性，以得到各組合物之散裂的基線值。接下來，將 厚度大約1密爾之YSZ陶瓷黏合塗層（明確言之為7YSZ黏合 塗層）插置於金屬基板11與絕熱陶瓷之間。再次測量耐散裂 性並與基線值作比較。包含EBPVD塗布之TBC之組合物及 其之形成方法如下： -7YSZ與Mo層積（一槍恒定蒸鍍7YSZ，另一搶在7YSZ 與Mo之間交替）。 - 具均勻Mo之7YSZ(—槍恒定蒸鍍7YSZ，另一搶恒定 蒸鍍Mo)。 -7YSZ與C層積（一槍恒定蒸鍍7YSZ，另一搶在7YSZ 與C之間交替）。 - 具均勻C之7YSZ(—槍恒定蒸鍍7YSZ，另一搶恒定蒸 鍍C) 〇 -59 GdZr與Mo層積（一槍恒定蒸鍍59 GdZr，另一搶在 101136.doc • 13 - 200538276 59 GdZr與Mo之間交替）。 - 具均勻Mo之59 GdZr (—搶恒定蒸鍍59 GdZr，另一搶 恒定蒸鍍Mo)。 -59 GdZr與C層積（一搶恒定蒸鍍59 GdZr，另一搶在 7YSZ與C之間交替）。 - 具均勻C之59 GdZr (—搶恒定蒸鍍59 GdZr，另一搶 恒定蒸鍍C)。 在所有情況中，使用大約1密耳厚之純7YSZ陶瓷黏合塗 > 層使耐散裂性改良至相等或較基線為佳。經測得7YSZ陶瓷 黏合塗層增進組合物之耐散裂性係在15〇及3〇〇小時之間。 已說明本發明之一或多個具體實施例。然而，當明瞭可 不脫離本發明之精神及範嘴而進行各種修改。因此，其他 具體實施例係在以下申請專利範圍的範疇内。 【圖式簡單說明】 圖1描繪本發明之挿置於陶瓷塗層與金屬基板之間的陶 > 瓷黏合塗層。 圖2描緣本發明之挿置於陶瓷塗層與熱成長氧化物（TGO) 塗層之間的陶瓷黏合塗層。 圖3描繪本發明之一具體實施例，其中塗布一外部陶瓷塗 層。 圖4描繪本發明之一具體實施例，其中將一 YSZ之陶瓷層 插置於兩陶瓷絕熱塗層之間。 圖5描繪本發明之挿置於TGO塗層與金屬基板之間的金 屬黏合塗層。 101136.doc -14- 200538276 於各個圖式中之類似的元件編號及名稱指示類似的元 件。 【主要元件符號說明】 10 金屬零件 11 金屬基板 13 陶瓷黏合塗層 15、15， 陶瓷TBC 17 熱成長氧化物（TGO) 19 金屬基板之背側 21 陶瓷TBC之外表面 31 外部陶瓷塗層 33 陶瓷層 51 金屬黏合塗層 101136.doc -15-

Claims (1)

  1. 200538276 十、申請專利範圍： 1. 一種耐散裂性金屬物件，包括： 一金屬基板； ,、w 口卞Vi 游丞’貝汉玉7 — 疋 自由 La、Ce、Pr、Nd、Sm、Eu、㈤、几、以、、&、 Tm、Yb、Lu、Sc、Τβ v 、、Mo及C、稀土氧化物、銃、 及銦所組成之群之其他元素；及 :位於該金屬基板與該至少一陶瓷絕熱塗層之間的陶 究霉口塗層其中该陶兗黏合塗層包括經氧化紀安定氧 化錯Cysz)。 2. 3. 如請求項1之物件，其中該金屬基板係選自由鋼、超合 金、鈦合金及鋼合金所組成之群。 求項1之物件，其中將-熱成長氧化物(TG0)層挿置 於Μ金屬基板與該陶瓷黏合塗層之間。 4·如請求項1之物件，其中 3·〇密耳（mU)之間之厚度 U具在大約〇.5及 ,,^ . ε Μ大約1·〇密耳較佳。 5·如喷求項1之物件，苴中將一 -絕熱陶究之-外表面，兮陶兗塗層塗布至該至少 ^A t ^ ^外部陶瓷黏合塗層包含氧化 锆基質及至少_選自由Sm、 6. 土氧化物、紀、銳、銦及〜所二、LU、M。、稀 如請求们之物件，直中將^所組成之群之其他元素。 、、、邑熱塗層的兩者之^ 1 网免 7. 如請臾心 4是層包含YSZ。 月求員6之物件，其中該 之間之屋疮 更層具在大約〇·5及3·〇密耳 之；度，以大約U密耳較佳。 斗 101136.doc 200538276 月求員1之物件’其中該至少一陶瓷絕熱塗層係利用選 自由熱喷霧、錢鍍、及電子束物王里蒸氣沈積（EBpvD)所組 成之群之方法塗布，且其中該至少—陶竞絕熱塗層具低 於約1.5瓦/米它之導熱性。 9·如请求項1之物件，其中該物件界定一燃氣輪機引擎组 件。
    10·如口月求項1之物件，其另包括一位於該TG〇層與該金屬基 板之間的金屬黏合塗層。 11. 如凊求項10之物件’其中該金屬黏合塗層係由選自由貼 面（MCrA1Y)及銘化物所組成之群之材料所形成，且其中 該金屬基板係由可形成氧化銘層之錄基超合金所形成。 12. -種降低金屬物件之散裂之方法，其包括下列步驟： 提供一金屬基板； 村该金屬基板塗布 J旯、、、色熟塗層，該陶瓷絕熱 塗層包含氧化錯基質及至少-選自由La、Ce、Pr、Nd、 Sm、Eu、Gd、Tb、Dy、H〇、Er Tm、Yb、Lu、Sc in、 ΓΜ°及C、稀土氧化物、銳、及銦所組成之群之其他元 素；及 將一陶兗黏合塗層掉置於該金屬基板與該至少一 :熱塗層之間’其中該陶究黏合塗層包括經氧 氧化鍅（YSZ)。 13.如請求項12之方法，j：中兮杯 置且右/… …插置该陶究黏合塗層包括插 置具有在大約0.5及3·0密耳之nm ώ ^ 間之厚度，以大約i.o密耳較 佳之該陶瓷黏合塗層。 101136.doc 200538276 14如請求項12之方法’其中該提供步驟包括提供選自由 15.=二：鈦合金及銅合金所組成之群之該金屬基板。 月·、之方法’其包括提供-挿置於該金屬基板盘 該陶瓷黏合塗層之間之執#且& 〃 曰〈間之熱成長氧化物(TG〇)層的額 驛。 如”:求項12之方法，其包括將一外部陶瓷塗層塗布至該 至少一絕熱陶瓷之一外表面的額外步驟，該外部陶瓷黏 合塗層包含氧化鍅基質及至少一選自由^〜卜則、 Sm、Eu、Gd、Tb、Dy、H〇、ErTm Yb Lu Sc in、 γ' Mo及c、稀土氧化H銦及其組合所組成之群之 其他元素。 月长項12之方法’其包括將一陶究層插置於該至少一 陶究絕熱塗層之兩者之間的額外步驟，該 YSZ。 18.
    如咕求項17之方法’其中該插置該陶究層包括插置具有 在大約〇·5及3.0料之^厚度，以大約iq料較佳 陶瓷層。 19.如請求項12之方法’其中該將該金屬基板塗布該至少一 陶竟絕熱塗層包括利用選自由熱噴霧、㈣、及電子束 物理蒸氣沈積（EBPVD)所組成之群之方法塗布該至少一 陶瓷絕熱塗層。 該金屬基板塗布該至少一 約1·5瓦/米。C之導熱性之 2〇·如請求項12之方法，其中該將 陶竟絕熱塗層包括塗布具低於 該至少一陶瓷絕熱塗層。 101136.doc 200538276 2 1 · —種耐散裂性金屬物件，包括·· 一金屬基板； I’ 陶瓷絕熱塗層’其包含氧化錯基質及至少一選 自由 La、Ce、Pr、Nd、Sm、Eu、Gd、Tb、Dy、Ho、Er、 Tm Yb、Lu、Sc、In、Y、Mo及 C、稀土 氧化物、銃、 及銦所組成之群之其他元素； 一位於該金屬基板與該至少一陶瓷絕熱塗層之間之陶 瓷黏合塗層，其中該陶瓷黏合塗層包括經氧化釔安定氧 化錯（YSZ); 挿置於4金屬基板與該陶瓷黏合塗層之間之熱成長 氧化物（TGO)層；及 位於”亥TGO層與該金屬基板之間之金屬黏合塗層。 22·如#求項21之物件，其中該金屬基板係選自由鋼、超合 金、鈇合金及鋼合金所組成之群。 23.如睛求項21之物件，盆中古女_这 八T ”亥陶是黏合塗層具在大約0.5及 3·〇密耳之間之厚度，以大約1〇密耳較佳。 2 4 ·如晴求項21之物件，苴中將一 八 寻外部陶瓷塗層塗布至該至 少一絕熱陶瓷之一外夹面，姑AL α ~外部陶瓷黏合塗層包含氧 化锆基質及至少一選自由Sm、 、Yb、Ce、Lu、Mo、 稀土氧化物、紀、銳、銦及复 及其組合所組成之群之其他元 素0 25.如請求項21之物件’其中將-陶究層插置於該至少一陶 :光絕熱塗層的兩者之間，該陶究層包含拟。 26·如請求項25之物件，以該以層具在大和及3.0密耳 101136.doc 200538276 之間之厚度，以大的 ^大約ι·ο密耳較佳。 27.如請求項21之物 ^ A L , ^ ，、干該至少一陶瓷絕熱塗層係利用 選自由熱喷霧、濟辦 ^ 、又、及電子束物理蒸氣沈積（EBPVD) 所組成之群之方沐泠士 塗布’且其中該至少一陶瓷絕熱塗層 具低於約1.5瓦/米。c之導熱性。 2 8 ·如咕求項21之物件，其中該物件界定一燃氣輪機引擎組 件0 29·如請求項21之物件，其中該金屬黏合塗層係由選自由貼 面（MCrAlY)及鋁化物所組成之群之材料所形成，且其中 該金屬基板係由可形成氧化鋁層之鎳基超合金所形成。
    101136.doc
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