TWI537402B - 具有ｄｌｃ（類鑽碳）塗層的組件及施加ｄｌｃ塗層的方法 - Google Patents

具有ｄｌｃ（類鑽碳）塗層的組件及施加ｄｌｃ塗層的方法 Download PDF

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TWI537402B
TWI537402B TW101117560A TW101117560A TWI537402B TW I537402 B TWI537402 B TW I537402B TW 101117560 A TW101117560 A TW 101117560A TW 101117560 A TW101117560 A TW 101117560A TW I537402 B TWI537402 B TW I537402B
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克里斯多福 歐
勞倫特 巴比倫
菲力浦 莫林皮瑞爾
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Description

具有DLC(類鑽碳)塗層的組件及施加DLC塗層的方法
本發明係關於DLC(類鑽碳)塗層的技術領域，特別是關於摩擦組件。
本發明對於降低例如活塞桿、凸輪軸、閥升桿、汽缸、活塞環等及更通常在負荷之下所有摩擦情況的磨擦係數具有特別有利的應用。為了降低此種摩擦，熟悉本技藝者係完全明瞭對組件或所論及的組件施用DLC塗層的可能性。
本發明也有以黑色塗層提供表面之需求的應用，而該塗層並非要降低摩擦。
熟悉本技藝者通常也已知DLC薄膜在元件上的低附著會在特定應用上帶來真實問題。為了增進附著的一種技術解決方案包含使用例如以矽或鉻為基礎之含金屬的附著層。已提出各種技術的解決方案。
例如文件WO 2011/018252說明具有以附著層、含金屬的DLC塗層及不含金屬的DLC塗層所組成之塗層的摩擦組件。該附著層較佳為最大厚度為1 μm的鉻塗層，而該含金屬的DLC塗層較佳以WCC碳化鎢所製。各層與塗層的厚度比例限制在特定範圍內的值，使得超出這些範圍時，若DLC的厚度太小，元件的服務壽命會縮短，且若DLC的厚度太大，元件會過早磨損而有剝離或剝落的風 險。
文件WO0179585揭示具有附著層、過渡層及類鑽碳層的多層系統。該附著層包含第四、第五或第六次族元素與矽，而過渡層包含碳及至少一種第四、第五或第六次族元素與矽。上層主要以類鑽碳所製。該系統的硬度為至少15 GPa且附著強度至少為HF3。
一般而言，觀察到與DLC膜中的內部應力有關之DLC膜自此底塗層的分層，且該膜越厚時，分層增多。也明顯的是此附著的底塗層以分開的步驟加以形成，且增加方法的費用並使該方法更為複雜。
本發明已設定自身的目標為以簡單、可靠、有效及有效率的方式克服這些缺點。
本發明想要解決的問題為製造具有增進附著性的DLC膜，而不使用以先前技藝教導為基礎之含金屬的附著性底塗層(例如矽或鉻)。
為了解決該問題，已設計並完或具有WC-C組成物梯度、不具含金屬的底塗層、及具有DLC表面層之層的金屬組件，其特徵在於刮痕測試中的黏合行為。
上述問題較有利以下述方法加以解決：-將組件以微波蝕刻； -對該組件施加WC-C組成物梯度層；-使用微波電漿，對該WC-C層施加DLC塗層。
微波蝕刻使其能獲得比調整離子流之使用二極體蝕刻更有效的蝕刻(不論待處理的組件之幾何形狀)。也能在低的回火溫度下將組件蝕刻，而不會使其劣化。也觀察到使用微波DLC塗層使其施用處理時間能比習用的DLC塗層降低大約50%。
有利的是，產生氬電漿，以獲得在0.05至0.5 Pa的壓力範圍內進行蝕刻。
如另一觀點，使用磁控管PVD技術，製造WC-C組成物梯度層。以第一純WC層開始，接著以烴氣體、例如C2H2的線性變化，最終接著為WC-C層。該WC-C組成物梯度層的厚度為0.3至10μm，且除了需要較大厚度者例如活塞環以外，對大多數的應用較有利為0.8μm。
如另一觀點，DLC塗層的厚度為1至20μm。
本發明也關於具有DLC塗層的摩擦組件，其施用於經微波蝕刻組件所具有的WC-C組成物梯度層。
如所示，先前技藝說明DLC塗層，其在每一情況下包含以純Cr所製的附著性底塗層，例如接著為以碳化鎢為底的層，其中碳含量逐漸增加，直到獲得摻雜鎢的DLC層，確保未摻雜金屬之沈積的DLC附著之目標。
在本發明的上下文中，製造具有一或多個附著性底塗層之DLC塗層與如本發明觀點不使用附著層之DLC塗層，為比較該二塗層所獲得的結果，已執行測試。
將物質沈積在含金屬的基板上，為了消除任何表面的氧化物使增進塗層的附著，該基板已預先經離子蝕刻。各種離子蝕刻技術皆為熟悉本技藝者所熟知，亦即主要為二極體蝕刻、三極體電漿蝕刻及ECR微波蝕刻。
二極體蝕刻包含在氬氣中、1至10 Pa的壓力下，對基板施以數百伏特的負電壓(<-500V)。在這些條件下，組件的周圍有發光放電，且電漿中的氬正離子撞擊基板的表面，使得表面噴濺及消除氧化物。
使用三極體電漿技術時，以電漿放大器在較低壓力下(0.1至1 Pa)製造濃密的氬電漿。對基板施以負偏壓而加速氬正離子，並將表面蝕刻。對於此類型的方法，負電壓必須介於-250 V至-500 V，以達到最大的蝕刻效率。
ECR微波蝕刻使其能在壓力範圍為0.05至0.5 Pa下製造氬電漿。對組件施以偏壓，較佳為-50 V至-250V的負電壓。
每一個這些蝕刻技術皆用於這些測試。在蝕刻之後，以磁控管陰極噴濺在一些試片上製造純鉻附著性底塗層，以獲得大約為0.1至0.2μm的鉻厚度。然後以磁控管陰極噴濺使在所有試片上沈積碳化鎢，逐漸增加烴流量，使其能提濃沈積的碳至原子濃度超過50%，以使最終的DLC塗層附著。除了實例9及10之含鎢層的厚度增加至1.5μm之外，含鎢層的厚度大約為0.5μm且DLC大約為2μm厚。
下表摘錄測試的條件。
所有塗層均以附著描述其特徵。使用刮痕測試方法。提醒讀者此方法包含以例如使用於HRC壓痕測試的鑽石刮擦沈積物質的表面。當試片在鑽石之下以定速平移移動時，施以逐漸增加的負荷。如此能夠在決定剝落力(臨界負荷)以及剝落模式的基礎下，使其能獲得增加負荷的刮痕(圖1)。剝落模式指出在塗層中的斷裂位置。有二種主要的剝落類型：
-附著性剝落(圖2)
-黏合性剝落(圖3)
有混合附著性破裂與黏合性破裂的混合模式，其稱為黏合性/附著性剝落(圖4)。
附著性剝落對應於裂縫沿著界面的傳播，且因而與組件的表面平行，而黏合性剝落以相對於界面的斜角通過塗層而傳播。附著性剝落的特徵在於缺乏塗層的附著。當應力超過構成塗層之物質的斷裂極限(機械強度)時，便發生黏合性剝落。
就附著性的外形(facies)而言，臨界負荷的特徵在於附著力。
就黏合性失敗而言，其特徵在於塗層斷裂的強度而非其附著。臨界負荷不僅為沈積物質的特徵，也為其厚度與基板硬度的特徵。
使用第二個方法以評估附著。包含在2 kg負荷下，使用維氏(Vickers)鑽石將沈積物質壓痕。
下表摘錄一系列的實驗，包括在基板上所獲得的刮痕測試結果，該基板以工具鋼(硬度64 HRC)所製，就實例9及10而言，無鉻底塗層之總沈積厚度為2.5μm及具鉻底塗層則為2.7μm，且總厚度為3.5μm。實例11及12具有厚的堆疊，其顯示本發明的堅固性。實例11包含4μm厚之以鎢為底的層，其上已沈積8μm厚的DLC。就實例12而言，鎢層的厚度增加至9.7μm，且其DLC表面層增加至19.2μm。
C=黏合性
A=附著性
CA=黏合性/附著性
NTR=沈積物質無分離
上表顯示，就二極體蝕刻及如先前技藝的教導而言，鉻底塗層使其能夠獲得強附著性(實例1)，且當不含該塗層時，在WC及鋼之間的界面出現失敗(實例2)。
當在無鉻底塗層時而刮擦，使用三極體蝕刻技術導致沈積物質的行為改變(實例4及5)。臨界負荷比二極體蝕刻增加(實例2)且剝落模式改變(實例4及5)。
觀察到的剝落顯示中間的剝落模式。
根據本發明，使用ECR微波蝕刻技術顯示在無鉻底 塗層的情況下其能夠獲得與先前技藝相當類似的機械行為(實例8)。要注意的是，如三極體蝕刻技術，降低壓力導致增進的刮痕測試效能(實例7及8)。
實例9及10顯示對黏合性剝落的抗性隨著含鎢底塗層的厚度而增加，如臨界負荷值所證明。在此二實例中，碳化鎢與梯度層的厚度為1.5μm。更特別的是，實例9的碳化鎢厚度增加至1μm，對應於碳濃度梯度的厚度為0.5μm。實例10的碳化鎢厚度為0.2μm，而碳濃度梯度層則增加至1.3μm。
實例11及12說明本發明的解決方法之堅固性。已知增加真空中沈積之薄硬層的厚度導致其內部壓縮應力增加。無論如何，在刮痕測試時的行為仍具黏合性，且臨界負荷的增加為鎢系層厚度增加的結果。
除蝕刻技術外，該結果顯示當蝕刻壓力降低時，無鉻底塗層所製的層在附著方面的增進。蝕刻過程中的壓力縮減與實際技術本身有關。二極體技術一般無法產生低如0.5 Pa的電漿壓力。
因此，如本發明使用適當的蝕刻技術，能夠降低氬的壓力且製造無鉻底塗層之DLC型附著堆疊，此結果與熟悉本技藝者與先前技術解決方案所廣泛認定之事物相違背。
如本發明的方法具有許多優點：
除了簡化所需設備及降低其成本以外，消除附著性底塗層也消除一個界面，所以增進塗層的可靠性與堅固性。
也很明顯的是如所進行的測試顯示，鉻的底塗層容易遮蔽特定蝕刻類型的缺陷，不同於碳化鎢，碳化鎢為了進行與以鉻的底塗層沈積的物質一樣良好的附著性而明顯要求更有效的蝕刻。
而且，使用2 kg負荷的維氏壓痕在各種類型沈積物質的附著性方面不能顯示出任何差異。雖然使用的負荷為2 kg(20 N)，維氏鑽石造成的變形不足以導致沈積物質的分離，如實例2所示，然而以刮痕測試方法仍然證明該附著為缺陷。
以下更詳細地解釋本發明，參考所附的圖形，其中：
-圖1為使用刮痕測試方法的塗層分解剖面圖。
-圖2為附著性剝落的情況下，沿著圖1中的A-A線的橫切面圖。
-圖3為黏合性剝落的情況下，沿著圖1中的A-A線的橫切面圖。圖4為黏合性/附著性剝落的情況下，沿著圖1中的A-A線的橫切面圖。

Claims (9)

  1. 一種金屬組件，其具有WC-C組成物梯度層與DLC(類鑽碳)表面層，且不包括含金屬的底塗層及不包括離子植入層，其特徵在於刮痕測試中的黏合行為。
  2. 如申請專利範圍第1項之組件，其以施加至WC-C組成物梯度層之DLC塗層覆蓋，其中該組件已經過微波蝕刻。
  3. 一種對金屬組件施加DLC塗層的方法，其特徵在於以下步驟：-將組件以微波蝕刻，-對該組件施加WC-C組成物梯度層，-使用微波電漿，對該WC-C層施加DLC塗層。
  4. 如申請專利範圍第3項之方法，其中產生氬電漿，以在0.05至0.5Pa的壓力範圍內進行蝕刻。
  5. 如申請專利範圍第3項之方法，其中該WC-C組成物梯度層係以磁控管PVD製造。
  6. 如申請專利範圍第5項之方法，其中以第一純WC層開始，接著以烴流量的線性變化，最終接著為WC-C層。
  7. 如申請專利範圍第5或6項之方法，其中該WC-C組成物梯度層的厚度為0.3至10μm，且有利為0.8μm。
  8. 如申請專利範圍第3項之方法，其中該DLC塗層的厚度為1至20μm。
  9. 一種以DLC塗層覆蓋的組件，其係專門使用如申 請專利範圍第3至8項中任一項之方法而獲得，其特徵在於無含金屬的底塗層且無離子植入層，且具有WC-C組成物梯度。
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