TW201510111A - 為了相對於另一較軟之組件滑動而塗佈有一層非晶形碳的機械零件 - Google Patents
為了相對於另一較軟之組件滑動而塗佈有一層非晶形碳的機械零件 Download PDFInfo
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- 238000004630 atomic force microscopy Methods 0.000 claims abstract description 25
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 18
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- 229910002804 graphite Inorganic materials 0.000 description 1
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- 229930195733 hydrocarbon Natural products 0.000 description 1
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- 238000007373 indentation Methods 0.000 description 1
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- 229910052961 molybdenite Inorganic materials 0.000 description 1
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- 239000011733 molybdenum Substances 0.000 description 1
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 1
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- 238000012544 monitoring process Methods 0.000 description 1
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- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- UONOETXJSWQNOL-UHFFFAOYSA-N tungsten carbide Chemical compound [W+]#[C-] UONOETXJSWQNOL-UHFFFAOYSA-N 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M103/00—Lubricating compositions characterised by the base-material being an inorganic material
- C10M103/02—Carbon; Graphite
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M103/00—Lubricating compositions characterised by the base-material being an inorganic material
- C10M103/04—Metals; Alloys
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M103/00—Lubricating compositions characterised by the base-material being an inorganic material
- C10M103/06—Metal compounds
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- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
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- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
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- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/02—Pretreatment of the material to be coated
- C23C14/024—Deposition of sublayers, e.g. to promote adhesion of the coating
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- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
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- C23C14/0605—Carbon
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- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/24—Vacuum evaporation
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- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
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- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/26—Deposition of carbon only
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
- F16J—PISTONS; CYLINDERS; SEALINGS
- F16J1/00—Pistons; Trunk pistons; Plungers
- F16J1/10—Connection to driving members
- F16J1/14—Connection to driving members with connecting-rods, i.e. pivotal connections
- F16J1/16—Connection to driving members with connecting-rods, i.e. pivotal connections with gudgeon-pin; Gudgeon-pins
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- General Engineering & Computer Science (AREA)
- Combustion & Propulsion (AREA)
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- Physical Vapour Deposition (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
- Lubricants (AREA)
- Chemical Vapour Deposition (AREA)
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Abstract
本發明係關於一種具有非晶形碳塗層(含有至少70原子%碳,不包含氫)且意欲藉由滑動與配對零件結合之機械零件,該配對零件之表面硬度至多為該塗層的三分之二,其中該塗層具有使用輪廓測定法量測至多為0.050微米的Ra粗糙度,及藉由原子力顯微鏡量測,具有至少0.004微米及至多0.009微米之微粗糙度。此使較軟之配對零件以及塗層的磨損減至最小。
Description
本發明係關於意欲在重負荷下相對於由較軟材料製成之組件滑動之機械組件的處理。其尤其係關於(但不具排他性)燃燒引擎中之活塞銷的處理,使該等組件接受硬的非晶形碳塗層(有時稱為「DLC型」且亦稱為「碳-鑽石(carbon-diamond);此等概念明確說明於下文)且相對於相當軟的材料諸如青銅、或甚至鋁合金(該銷所穿過之套筒、或承接該銷之活塞本體)摩擦。然而,更一般而言,本發明係關於在涉及已知可能導致顯著磨損之負荷及速度條件的摩擦應用中,通常為金屬之機械組件意欲藉由滑動與另一較軟組件結合的情形。
熟悉技藝人士知曉活塞銷特定言之經非晶形碳塗層的處理。施用此類型塗層的優點係防止活塞銷熔執(seizing)於通常由青銅或鋁製成之配對組件上。
就此而言,可參考DE 10 2011 102 209、WO 2009/144076或I.Etsion、G.Halperin及E.Becher於Wear 261(2006)785-791頁公開之標題為「各種表面處理對活塞銷耐刮擦性的效應(The effect of various surface treatments on piston pin scuffing resistance)」的文件;該
文件可見於以下網址:[http://www.technion.ac.il/~merei02/public/2_The%20effect%20of%20various%20surface%20treatments%20on%20pistor%20pin.pdf]
由於該等組件之間的接觸壓力逐漸增加,因而需要施用該抗熔執塗層。接觸壓力之增加係為通過慣性降低質量及能量損耗而減小零件尺寸之連續傾向的結果。
熟悉技藝人士一般認為,在一對藉由滑動/摩擦彼此結合的兩個組件中,較軟組件的磨損隨較硬組件的表面粗糙度而減小。因此,在活塞銷之情況中,通常認為青銅或鋁組件之磨損隨經塗佈非晶形碳層之配對組件的粗糙度而減小;結果,為限制青銅或鋁之磨損,特別關注活塞銷在沉積之前的表面光度(surface finish)。然而,使沉積之前的粗糙度減至最小並不足夠且通常必須補充目標在於降低經塗佈零件之粗糙度的最終處理操作;該最終操作可由刷塗(根據熟悉技藝人士知曉之方法)所組成。
然而,應注意,在特定狀況下,青銅及鋁皆不會磨損,反而非晶形碳塗層異常顯著地磨損,儘管該非晶形碳塗層具有顯著硬度。因此,兩種具有相同機械及粗糙度特徵的塗層(就術語的巨觀含義而言,見下文)可以完全不同的方式作用。在一種情況中,可觀察到配對零件(甚軟、或「軟性」材料)之高度磨損及塗層的極小磨損,而在另一情況中,軟性材料之特徵在於最小的磨損結合塗層的高度磨損,並無明顯理由。
可輕易理解為令人滿意地操作系統,兩配對零件之各者必需存在最小磨損,以確保組件的長使用壽命。
因此,需要能夠製造及表徵具有非晶形碳塗層(至少70
原子%碳、或甚至至少90原子%碳,不包括氫)之零件,以確保當與顯著較軟的配對零件(例如小於塗層硬度之2/3)組合時,兩零件在操作中皆未呈現顯著的磨損。
為能夠監測意欲相對較軟材料(即其硬度比塗層小超過1.5倍)摩擦之經塗佈主要由碳組成(超過70原子%碳,不包括氫含量)之非晶形碳之硬且薄之層之零件的磨損,本發明揭示於巨觀標度(習知測量)及於微觀標度(藉由原子力顯微鏡,實際上在小於100平方微米之面積上)的粗糙度條件。
更明確言之,本發明提出一種具有非晶形碳塗層(至少70原子%碳)且意欲與配對零件滑動結合之零件,該配對零件之表面硬度至多為該塗層的三分之二,該塗層具有使用輪廓測定法量測至多等於0.050微米的Ra粗糙度,及藉由原子力顯微鏡量測具有至少等於0.004微米及至多等於0.009微米之微粗糙度。
在此必需明暸Ra粗糙度係待施用塗層之零件的粗糙度。
當明瞭使用兩種不同技術量測,保持在此等粗糙度範圍內導致此一經塗佈零件的適度磨損,而不會導致更為柔軟之配對零件的顯著磨損,不管置於摩擦表面之間之任何潤滑劑的明確特性為何。
為在此兩種粗糙度概念(作為算術平均)之間作區別,在下文將詞語「粗糙度」用於藉由習知方式所測得者,及將表述語「微粗糙度」用於藉由原子力顯微鏡所測得之粗糙度。
習知之粗糙度測量方式受限於通過點尺寸(其通常具有2微米之局部半徑)的解析度。原子力顯微鏡(AFM)中所使用之點小若
干個數量級(其通常具有0.01微米或再更小的局部半徑);因此,AFM之點使其可看到比藉由習知方式所可偵測得者更小的細節。
設定經塗佈DLC(碳-鑽石)膜之零件之最大及最小值粗糙度的原則已於WO 2012/073717中提出。該文件推薦一種含4.5原子%至30原子%氫、及介於5奈米及25奈米(即0.005及0.025微米)之間之均方根粗糙度的DLC塗層;然而,最小臨限值的存在絕非期望使DLC層及配對零件之磨損減至最小,反而係經提出來確保足夠程度的摩擦,以產生能使所使用特定潤滑劑中所提供之添加劑產生作用之反應所需的能量(該潤滑劑包含基於鉬之化合物及鋅及硫添加物,且文件中所給的說明目標在於確保形成MoS2)。事實上,該文件建議兩零件應由相當的材料製成,因此其間沒有顯著的硬度差異且其間無法存在由本發明所解決之技術問題。無論如何,該文件並未揭示使用原子力顯微鏡技術量測粗糙度之優點,或更不用提在一方面針對以習知方式(使用輪廓測定法)測得之粗糙度及另一方面針對使用此極特定方法測得之粗糙度設定臨限值的優點。若僅使用以習知方式測得之粗糙度(表示為均方根粗糙度而非Ra(作為算術平均)),則必需注意該文件揭示甚低於本發明之最大值(作為算術平均Ra)的最大值,其將極可能與本發明之AFM微粗糙度範圍不相容。換言之,本發明隱含揭示一種使用習知量度的粗糙度範圍,其甚大於該文件中之範圍。
較佳地(但非必定),藉由輪廓測定法測得之該Ra粗糙度值係大於0.020微米、或甚至0.025微米之臨限值。在此必需注意此係塗層之粗糙度,其可能不同於塗佈前的表面粗糙度。
較佳地,藉由輪廓測定法測得之粗糙度至多等於0.046微米及藉由原子力顯微鏡測得之微粗糙度包括介於0.004與0.0075微
米之間;該等小範圍似乎更能確保兩個配對零件的低度磨損。然而,必需注意本發明之目標並不在於識別使兩零件之磨損適度所需且足夠的條件;其目標僅在於提供足以達成此一結果的條件。
根據本發明之較佳特徵,視情況地組合:˙使用稱為ERDA之技術量測,該塗層具有20±5原子%之氫含量,˙在含氫的非晶形碳塗層下方,零件包含一層至多一微米的CrN,˙該塗層在距零件表面至多一微米之至少兩微米的膜中包含鎢摻雜。
本發明亦提出一種藉由摩擦結合的零件對,其包括一前述類型的零件及一表面硬度為該塗層之至多三分之二的配對零件。
舉例來說,該配對零件可由銅合金(諸如青銅)製成;作為一變體,其可由鋁合金(例如AlSn)製成。亦可說此等為錫合金。此一配對零件可僅表面係由該材料製成。
本發明之標的物、特徵及優點當可由以下給定作為非限制性說明的敘述參照附圖而明白,其中:圖1係各種實施例之經塗佈零件的粗糙度與該零件之磨損及青銅配對零件之磨損的關聯圖,及圖2係各種實施例之經塗佈零件的微粗糙度與該零件之磨損及青銅配對零件之磨損的關聯圖。
文件的其餘部分係關於在模擬引擎中之活塞軸(或活塞銷)之操作條件的情形下,意欲與青銅(或鋁)配對零件結合之經塗佈非晶形碳膜之實際上由鋼製成的金屬零件;此可係軸於曲軸上的接合或
軸於活塞本身上的接合。
使用具有CrN塗層的實施例來作比較。
根據通常的方法,使用習知的Ra粗糙度量測來界定所需的必要水平,以限制經塗佈硬層之銷之配對零件(特定言之,青銅或鋁)的磨損。然而,就給定的塗層而言,經塗佈零件的習知表徵並無法確定塗層是否會發生磨損。對於相同的Ra粗糙度(以習知方式測量)及硬度值,兩種表面上相似的塗層可能基於尚待瞭解的理由而在一者上未發生磨損及反之,在另一者上過度磨損(其不可能單純地係歸因於配對零件之硬度間之高度相似性所致的磨蝕)。根據本發明之一態樣,使用原子力顯微鏡(或AFM)技術檢測零件之表面有助於能夠確定經塗佈零件所必需具有之理想表面形態來使兩配對零件之磨損減至最小。
在以下實施例中,將起始相同的活塞銷(在製造公差內)各別塗佈氮化鉻CrN及不同類型之基於非晶形碳之材料的沉積物。目前經常使用頭字語DLC作為所有形式之非晶形碳的同義字;事實上,頭字語DLC(類鑽碳)係指示具有呈現雜化作用之碳原子的碳,諸如於鑽石中,且僅應用於此形式的非晶形碳。在文件的其餘部分中,基於簡單理由,將針對各種形式之非晶形碳使用頭字語DLC之簡稱,無論其係指含氫之非晶形碳、不含氫之非晶形碳(頭字語DLC對其而言似乎完全正確)或摻雜鎢的含氫之非晶形碳。
活塞銷在沉積之前的特徵在於Ra粗糙度測量值為0.025微米及Rpk粗糙度測量值為0.040微米。在此,Rpk粗糙度測量值係在粗糙度測量值之外給出,以對實施例的表徵作補充。如前所述,即將沉積的塗層尤其視該塗層的形成方法而定,可具有相當不同的粗糙度。
在文件的其餘部分中,Hv硬度測量值係對應於與塗層之厚度及硬度一致地調整之10至30毫牛頓(mN)之負荷,以致壓痕深度約為沉積物之厚度的十分之一;因此,硬度測量值未明顯包括基板之硬度。
CrN層係藉由磁控濺鍍所產生,經明確說明此類型之沉積通常產生低於化學計量的層。氮含量為40±5原子%氮。實際上,該CrN沉積物之特徵在於1,800±200Hv之維克氏(Vickers)硬度。設想兩種沉積物厚度(1微米及2微米),因此分別指示為CrN1及CrN2。
習知含氫之非晶形碳沉積物係於氬氛圍中藉由化學氣相沉積(CVD)所產生;較佳地,沉積技術係一種特定形式的CVD(即電漿輔助型CVD或PACVD、或電漿增強型CVD、或PECVD)。此等層之特徵在於3,000±400Hv之硬度,其對應於使用ERDA測量為20±5原子%氫之氫含量。此等層係以2微米之厚度沉積於具有兩種可能厚度的CrN底層上:- 0.8微米之CrN及接著2.0微米之含氫非晶形碳的雙沉積物,此處稱為DLC1,- 1.5微米之CrN及接著2.0微米之含氫非晶形碳的雙沉積物,此處稱為DLC2,作為參考DLC1之變型,利用不同的CrN沉積條件形成另一含氫之非晶形碳沉積物,尤其係藉由提高總氬氣壓力;此沉積物在文件的其餘部分中指示為DLC3。
不含氫之非晶形碳塗層係藉由陰極電弧蒸發沉積技術產生。其硬度經測量為4,500Hv。考慮在單一厚度下,即一微米之厚度下;在文件的其餘部分中將以此方式獲得之塗層指示為DLC4。不含
氫之非晶形碳沉積物DLC(或taC)係藉由PVD技術(石墨陰極電弧蒸發)形成。
最後,摻雜鎢的含氫之非晶形碳沉積物係藉由在含有烴分壓之氛圍中使用碳化鎢靶進行陰極磁控濺鍍而產生。此沉積物之特徵在於1,400Hv之硬度及10原子% W含量(不包括氫)。其可經分析為由經碳覆蓋之WC底層所形成(碳含量逐漸增加直至90%;此處考慮的塗層包含0.6微米厚之WC層(其逐漸地富含碳),總厚度為2.5微米;此塗層在文件的其餘部分中稱為DLC5。
應謹記(見上文)上述硬度為塗層之硬度(儘管其厚度小),而非下層材料的硬度。
非晶形碳塗層顯著地較CrN塗層硬,尤其當其為不含氫時(一般由100%碳形成,如同DLC之情況),摻雜鎢的含氫之非晶形碳塗層為例外;結果,非晶形碳塗層(含氫或不含氫、未摻雜鎢)通常具有較CrN塗層高之耐磨性,尤其係藉由磨蝕。
最後,使此等塗層根據本身已知之方法接受或不接受最終階段之或多或少強烈的刷塗。
刷塗之特徵在於兩個主要值-刷壓力及在刷下方的程數,如下表所示。
該刷塗使其可除去可能在層的沉積操作期間形成的任何突起,其構成可以銼刀方式加劇配對零件之磨損的尖物。此等突起具有極低的機械強度,此意謂其會在最輕的刷塗之後經除去。更強的
刷塗導致拋光沉積物之表面。
使所有此等零件經歷利用輪廓測定法的粗糙度表徵、以及使用稱為原子力顯微鏡(AFM)之技術、取5 x 5微米影像之微粗糙度測量。換言之,使各種零件經歷使用粗糙度計(以十分之一微米之標度)之巨觀(習知)粗糙度測量及利用AFM(以數十奈米之標度)之奈米測量;如前所述,將此粗糙度稱為「微粗糙度」以使其與巨觀粗糙度作區別。
最後使所有零件就摩擦項目來表徵,目標在於量化經塗佈零件之磨損及由在此定為軟性(即其硬度至多為相關塗層的三分之二)之金屬製成之配對零件的磨損。
在以下實施例中,軟性金屬係直徑10毫米的青銅圓柱體,其0.3微米之Ra係實際零件的代表。於交叉軸組態中進行摩擦測試。在平行於活塞銷上之條紋的方向中產生相對移動,且使接觸點於青銅銷在10毫米衝程上的產生線上移動。施加的負荷為11.6牛頓。在由偏心系統所賦予之交替移動中的平均滑動速度為100毫米/秒。在測試之前,用一滴SAE5W30油潤濕接點。將系統加熱至110℃。
於9,000個測試循環後,藉由測量摩擦區之尺寸來表徵磨損。對於青銅銷,測量係橫跨摩擦標記的寬度進行。對於經塗佈零件,磨損係於摩擦方向測量。應注意在青銅上之起始接觸寬度為320微米;結果,在青銅上320微米至340微米左右的摩擦標記尺寸指示青銅的低度或零磨損。類似地,在摩擦方向中在經塗佈銷上之起始接觸區域的尺寸為240微米;因此,至多260微米之尺寸指示塗層的低度磨損。必需注意,由於塗層顯著地較配對零件硬,因此其磨損不可能係由磨蝕所產生。
下表使塗層之各種特性相關聯。磨損測量值可對應於較下文所述之起始測量值低的值,特定言之係歸因於測量不確定性(事實上,試樣係其粗糙度及幾何形狀不如用來計算接觸尺寸之特性般理想的圓柱體;實際的幾何形狀及實際的表面形態可能具有起始區域(其理論上為橢圓形)可能稍小於240微米的效應)。
此等結果亦展示於圖1中之圖上(使用具有2微米半徑之觸角之粗糙度計的Ra粗糙度測量值)及圖2中之圖上(使用AFM之微粗糙度,簡單標示為μ Ra):
- 方形顯示青銅零件相對於DLC塗層之以微米計的磨損(左手邊的標度),- 菱形顯示DLC塗層之磨損(右手邊的標度),- 三角形顯示青銅零件相對於CrN塗層之磨損(左手邊的標度),及- 十字形顯示CrN塗層之磨損(右手邊的標度)。
可認定兩粗糙度測量標度未提供完全相同的資訊:巨觀粗糙度主要係由在沉積塗層之前機器加工零件所產生,而微粗糙度主要係表徵塗層之生長,前述機器加工的影響較小。
圖1中之圖顯示自先前技術獲知之結果,即當以習知方式測量時,青銅的磨損係與配對零件的粗糙度相關。經塗佈零件之粗糙度的減少自然導致較軟之配對零件的磨損減少。
然而,該圖1中之圖顯示,與可能的認定相反,DLC塗層可能發生顯著磨損,儘管事實為其性質未預知其易磨損(其較青銅零件硬)。再者,塗層的磨損與其粗糙度無關。就CrN塗層而言,觀察到磨損似乎與塗層的粗糙度無關,而就DLC塗層而言,咸信甚至可觀察到負關聯,即粗糙度愈低,磨損愈大。
可對圖2中之圖作出類似的評論,明確說明為青銅零件之磨損幾乎與AFM粗糙度成比例(x軸在極低AFM粗糙度值下之平均截距)。就經塗佈非晶形碳之零件的磨損而言,當該AFM粗糙度超過0.0050微米左右之值時,此似乎仍然合理(就CrN塗層而言,在所有情況中磨損皆保持為低度)。
換言之,此等粗糙度及微粗糙度測量值突顯在經塗佈零件之粗糙度及微粗糙度與其相對然而較不硬(或更軟)之配對零件的磨損之間存在反比關係,因看來係最光滑的非晶形碳層顯現最大的磨損。
更明確言之,對於含氫之非晶形碳層(DLC1至DLC3):˙當刷塗塗層時,青銅配對零件的磨損幾乎不會減少(甚至可注意到在測量不確定性內,在實施例3及6之間沒有明顯差異),˙當刷塗提升時(見DLC1),該青銅配對零件之磨損並未減少(或甚至增加),˙當進行刷塗時,塗層之Ra粗糙度減小,但增加刷塗時間並不一定會對該減小具有有利效應,˙反之,當進行刷塗時,塗層之AFM微粗糙度減小,及當增加刷
塗時間時進一步減小,且對於DLC1(具有最薄的CrN底層)觀察到最小的微粗糙度,˙刷塗不會導致塗層(DLC2、DLC3)的磨損減少;但於DLC1上注意到有輕微的減少,增加刷塗時間甚至具有促進磨損的效應,˙除了就已經歷延長刷塗的DLC1而言外,塗層的磨損仍維持適度(低於260微米),˙增加CrN底層對青銅零件之磨損並無有利效應;相對地,僅具有僅僅0.8微米之底層厚度的DLC1塗層於未經刷塗或輕度刷塗狀態中顯示適度磨損,˙增加塗層沉積期間之氬氣壓力並無可見的正面效應(比較DLC2與DLC3)。
就不含氫之DLC(DLC4)而言:˙刷塗塗層似乎係維持青銅配對零件的合理磨損程度所必需,但不利於塗層的磨損,˙可認為適度刷塗能夠導致可接受的折衷。
最後,就含有鎢的DLC(DLC5)而言:˙刷塗似乎對青銅配對零件之磨損具有正面效應,但該磨損即使在不存在該刷塗時仍保持適度,˙反之,刷塗對配對零件的正面效應似乎不利於塗層的磨損。
可注意到刷塗的效能係記述於活塞銷製造者之說明書中來消除塗層中之生長缺陷的操作;然而,由於其相當低的密度(除了不含氫的非晶形碳沉積物外,其視製造技術的明確特徵而定,可能具有相當大量的生長缺陷),似乎懷疑該等缺陷可能會對上述磨損現象具有顯著影響。
可注意到實施例1及7至9係遵從熟悉技藝人士已知之情況的例子,即對於最粗糙的經塗佈試樣(具有大於0.050±0.001微米之Ra粗糙度)注意到青銅配對零件之顯著磨損,但在粗糙度與磨損之間不存在真正的比例(實施例1較實施例7粗糙但導致較少磨損;粗糙度並非唯一的相關參數)。必需注意於此等實施例中記錄之AFM微粗糙度係在所記錄的最高值之間(大於0.0090)。
就實施例5、6、10及12而言,可注意到其係對應於高塗層磨損值。此結果對於熟悉技藝人士而言似乎係驚人的,因為在該等零件上之塗層就機械或化學特性而言與其較粗糙的同型層並無不同。雖然塗層較青銅配對零件(顯著較軟)硬得多,但觀察到高磨損。粗糙度的AFM檢測顯示在數平方微米之標度上,此等層與其他層的區別在於特別低的Ra(低於0.004微米)。
可注意到實施例11係對應於僅僅大於所給臨限值之青銅零件的磨損,且可視為邊界。
此導致當非晶形碳塗層(至少70原子%碳)具有至多等於0.050微米之Ra粗糙度結合大於0.004微米但小於0.009微米之AFM Ra微粗糙度時,獲得塗層及青銅配對零件(儘管其較塗層顯著地柔軟)之低磨損之組合的考量。
只有滿足上述雙重條件的實施例才能導致相互摩擦之兩零件的低度磨損。
當塗層之粗糙度如下時,磨損看來較低:
- 當以習知方式測量時,至多等於0.046微米
- 且當藉由AFM測量時,包括介於0.004與0.0075微米之間。
值得強調以此方式識別之良好實施例係對應於利用含
氫之非晶形碳(較佳具有包括薄的CrN底層(表觀不超過一微米)之氫含量)或摻雜鎢的含氫之非晶形碳(同樣表觀不超過一微米)之未經刷塗或經輕度刷塗的塗層。就不含氫的非晶形碳而言,適度刷塗似乎可導致滿足上述條件及因此適度的往復磨損。
再者,以上顯示塗層之性質具決定性,如包含硬的基於非晶形碳之層(超過70原子%碳,不包括氫)之實施例1至12會導致與利用CrN塗層所獲得之實施例13至15不同的結論。特定而言,就非晶形碳層而言,當經塗佈零件之粗糙度增加時,CrN沉積物會導致青銅的磨損增加,而在低或極低粗糙度下,CrN層未磨損且不會磨損青銅配對零件。此等結果顯示非晶形碳塗層的磨損現象既非機械性亦非磨蝕性,因此等層比CrN硬或顯著地比配對零件硬超過1.5倍。因此,在極低粗糙度值下非晶形碳層的高度磨損並非熟悉技藝人士已知的常見現象。由於相關塗層主要係由碳組成,因此不希望受限於此解釋,可想像涉及可能為摩擦氧化類型之機制,且因此不受碳層之硬度影響。
僅由耐磨性的觀點來看,相當光滑的CrN層表現所需功能。然而,對於降低摩擦的恆定期望,非晶形碳塗層較CrN為佳,因其容許較低的摩擦係數。以上指出的粗糙度範圍使其可確保合理的磨損程度。
在前表中,可注意到在Ra與μ Ra(AFM)欄位之間有一欄標為RPk;此欄係顯示根據不同的粗糙度測量法獲得的粗糙度。可注意到此另一表徵粗糙度的方式產生類似的結論。
以上結論可擴展至其他材料對;因此,更一般而言,配對零件(具有以上定義的低硬度)可由任何銅合金、或任何鋁合金製成;此尤其可係活塞銷的情況。其可係諸如AlSn的錫合金(尤其使用於特
定的曲軸軸承中或連桿大端上)。應瞭解可能僅該配對零件之表面係由軟性材料製成(且包含由不同材料製成的核心)。
值得強調,知曉待獲得的粗糙度及微粗糙度來調整沉積條件,係在熟悉技藝人士之範疇內。熟悉技藝人士可改變沉積物及甚至PVD底層之形態來獲得一系列的操作參數;PVD層一般係以柱狀結構生長,其尺寸隨厚度增加,其會影響粗糙度。
Claims (10)
- 一種具有非晶形碳塗層(含有至少70原子%碳,不包含氫)且意欲藉由滑動與配對零件結合之機械零件,該配對零件之表面硬度至多為該塗層的三分之二,該塗層具有使用輪廓測定法量測至多等於0.050微米的Ra粗糙度,及藉由原子力顯微鏡量測,具有至少等於0.004微米及至多0.009微米之微粗糙度。
- 如申請專利範圍第1項之零件,其使用輪廓測定法測得之粗糙度至多等於0.046微米及其使用原子力顯微鏡測得之微粗糙度包括介於0.004與0.0075微米之間。
- 如申請專利範圍第1或2項之零件,其使用輪廓測定法測得之粗糙度係大於0.025微米。
- 如申請專利範圍第1至3項中任一項之零件,使用稱為ERDA之技術量測,該塗層具有20±5原子%氫之氫含量。
- 如申請專利範圍第1至4項中任一項之零件,其在含氫的該非晶形碳塗層下方包含一層至多一微米的CrN。
- 如申請專利範圍第1至4項中任一項之零件,其在距該零件之表面至多一微米處之至少兩微米的膜中包含鎢摻雜。
- 一種藉由摩擦結合的零件對,其包括一申請專利範圍第1至6項中任一項之零件及一表面硬度為該塗層之至多三分之二的配對零件。
- 如申請專利範圍第7項之零件對,其中,該配對零件係銅合金。
- 如申請專利範圍第7項之零件對,其中,該配對零件係鋁合金。
- 如申請專利範圍第7項之零件對,其中,該配對零件係錫合金。
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