201240826 六、發明說明： 【發明所屬之技術領威】 [0001] 本發明涉及一種被覆件及其製造方法。 [先前技術] [0002] 真空鍍膜工藝在工業領域有著廣泛的應用，其中，TiN薄 膜鍍覆在刀具或模具表面能大幅提高刀具和模具的使用 壽命。然而，隨著金屬切削加工朝高切削速度、高進於 速度、高可靠性、長壽命、高精度和良好的切削控制性 ^ 方面發展，對表面被覆件的性能提出了更高的要求。傳 統的單一TiN被覆件在硬度、韌性等方面已經不能滿足要 求。 [〇〇〇3] ZrN薄膜由於其硬度與韌性均優於TiN薄膜而受到人們的 廣泛關注。但單一的ZrN薄膜在硬度、抗氧化性等方面幾 乎已經沒有提高的空間，报難滿足現代工業的需求。又 知，CrN係一種硬質薄骐材料，可作為超硬工具材料及表 面保護材料。但由於CrN本身的硬度並不算很高（約 〇 18GPa) ’使其在刀具或模具上的應用受到了限制，另外 ’上述ZrN或CrN硬質薄犋的抗氧化性效果不佳，鍍覆於 刀具或模具表面不能起到良好的抗氧化作用，容易導致 薄膜的失效。 【發明内容】 _4] #於此’有必要提供—種既具有高硬度又具有較佳抗氧 化性能的被覆件。 _5]另外，錢供-種上述被覆件的製造方法。 100112576 表單編號A0101 第3頁/共16頁 1002020948-0 201240826 [0006] 一種被覆件’包括硬質基體，依次形成於該硬質基體上 的過渡層、複合硬質層和抗氧化層，所述過渡層為鉻層 ’所述複合硬質層包括依次形成於過渡層上的氮化鉻層 '氮化铪和氮化鉬層，所述抗氧化層為氧化鋁層。 [00(Γ7]—種被覆件的製造方法，包括以下步驟： [0008] 提供一硬質基體； [0009] 於該硬質基體的表面磁控滅射絡層； [0010] 於該絡層上磁控錢射氮化鉻層； [0011] 於該氮化絡層上磁控濺射氮化給層； [0012] 於該氮化鉻層上磁控濺射氮化鉬層； [0013] 於該氮化钥層上磁控濺射氧化銘層。 [0014] 所述鉻層對複合硬質廣中的氮化鉻層起到附著作用，其 可很好地把硬質基體和複合硬質層更牢固地結合到一起 。與此同時所述複合硬質層中依次形成的氮化鉻層、氮 化铪與氮化鉬層的結合可使複合硬質層更穩固，主要係 因為氮化鉻層對鉻層有較強的附著力，同時作為外層的 氮化銓和氮化鉬都具有與硬質基體較相近的熱膨脹係數 ，因此介面處内應力小’從而使得外層的氮化铪和氮化 鉬層與氮化鉻層的結合力更強、韌性更高，且位於氮化 鉻和氮化鉬之間的氮化铪層的熱穩定性和化學穩定性都 要優於其他的硬質材料，所以，依次濺射的氮化鉻和氮 化铃層可顯著提高被覆件的硬度和膜層耐脫落性。最後 ，在該複合硬質層磁控濺射氧化鋁層’其可以給上述的 1002020948-0 100112576 表單編號Α0101 第4頁/共16頁 201240826 複合硬質層帶來更好的抗氧化性能，從而延長了產品的 使用壽命。 【實施方式】 [0015] 請參閱圖1，本發明一較佳實施例的被覆件10包括一硬質 基體11，及依次形成於該硬質基體11上的過渡層13、複 合硬質層15及抗氧化層17。 [0016] 該過渡層13為鉻層。 [0017] 該複合硬質層15包括依次形成於硬質基體11上的氮化鉻 〇 層151、氮化铪層153和氮化鉬層155。該氮化鉻層151、 氮化铪層153和氮化#目層155可通過磁控濺射的方式形成 [0018] 該抗氧化層17為氧化鋁層。 [0019] 本實施例中，該複合硬質層15的厚度為4〜8#m。 [0020] 該硬質基體11的材質可以為高速鋼、不銹鋼等硬質金屬 〇 [0021] 本實施例中的被覆件10可為各類切削刀具、精密量具或 模具。 [0022] 製作所述被覆件10的方法主要包括如下步驟： [0023] 提供硬質基體11。 [0024] 對該硬質基體11進行前處理。 [0025] 將所述硬質基體11放入盛裝有乙醇或丙酮溶液的超聲波 清洗器中進行清洗，以除去硬質基體11表面的雜質和油 100112576 表單編號A0101 第5頁/共16頁 1002020948-0 201240826 污。清洗完畢後烘乾備用。 [0026] 對經上述處理後的硬質基體11的表面進行氬氣電漿清洗 ，進一步去除硬質基體11表面的油污，以改善硬質基體 11表面與後續塗層的結合力。 [0027] 提供一鍍膜機100，鍍膜機100包括一鍍膜室20及一用於 對該鍍膜室20抽真空的真空泵30，該鍍膜室20内設有轉 架（未圖示），在該鍍膜室20側壁上各安裝鉻靶22、铪 靶23、鉬靶24、鋁靶25。轉架帶動鋁或鋁合金基體11沿 圓形的軌跡21公轉，且鋁或鋁合金基體11在沿軌跡21公 轉時亦自轉。 [0028] 該電漿清洗的具體操作及工藝參數可為：對該鍍膜室20 進行抽真空處理至真空度為8. 0xl0 — 3Pa，以 300~500sccm (標準狀態毫升/分鐘）的流量向鍍膜室20 内通入純度為99. 999%的氬氣（工作氣體），於硬質基體 11上施加-300〜-800V的偏壓，在所述鍍膜室20中形成高 頻電壓，使所述氬氣電漿化而產生氬氣電漿對硬質基體 11的表面進行物理轟擊，而達到對硬質基體11表面清洗 的目的。所述氬氣電漿清洗的時間為3〜lOmin。 [0029] 在對硬質基體11進行電漿清洗後，於該硬質基體11上形 成所述過渡層13。形成該過渡層13的具體操作及工藝參 數如下：以氬氣為工作氣體，調節氬氣流量為 100〜300sccm，於硬質基體11上施加-50 — 200V的偏壓 ，設置偏壓的佔空比為30%~80%，並加熱鍍膜室20至 100〜150°C，以鉻靶22為靶材，設置其功率為8〜13kw， 100112576 表單編號A0101 第6頁/共16頁 1002020948-0 201240826 沉積過渡層13。該過渡層為一鉻層。沉積該過渡層13的 時間為1 0~30min。 [0030] Ο [0031] 於該過渡層13上形成複合硬質層15。首先形成所述複合 硬質層1 5中的氮化鉻層151。形成該氮化鉻層1 51的具體 操作及工藝參數如下：以氬氣為工作氣體，調節氬氣流 量為100~300sccm，通入流量為10〜70sccm的反應氣體 氮氣，於硬質基體11上施加-50~_200V的偏壓，設置偏 壓的佔空比為30%~80%，並加熱鍍膜室20至1〇〇〜150°C •，開啟鉻靶22，設置其功率為l~3kw，沉積氮化鉻層151 。沉積該氮化絡層1 51的時間為10~30min。 Ο [0032] 於該氮化鉻層151上形成氮化铪層153 ’具體操作及工藝 參數如下：以氬氣為工作氣體，向所述鍍膜室20中通入 流量為1〇~70sccm的反應氣體氮氣’以給勒>23為乾材’ 設置鈐靶23的功率為卜4KW，施加於硬質基體11的偏壓 為-100〜-300V，設置偏壓的佔空比為30%〜80%，氮氣流 量為10~70sccm，濺射溫度為100~200°C，沉積所述氮 化鈐層153。沉積該氮化鉛層153的時間為60〜90miη。 於該氮化鈐層153上形成氮化鉬層155 ’具體操作及工藝 參數如下：以氬氣為工作氣體，設置氬氣流量為 100~200sccm，保持氮氣流量為100〜200sccm，對硬質 基體11施加-50〜-100V的偏壓，設置偏壓的佔空比為 30%~50%，並加熱鍍膜室至100~150°C ;開啟鉬靶24， 設置其功率為8〜13kw，沉積該氮化鉬層155。沉積氮化 翻層155的時間為40~70min。 100112576 表單編號A0101 第7頁/共16頁 1002020948-0 201240826 []所述鉻層13對複合硬質層15起到增強附著的作用。複合 硬貝層15中作為最外層的氮化銷155具有與氮化給層153 較相近的熱膨脹係數，因此介面處内應力小，從而使得 /〜、氮化姶層153的結合力更強 '韌性更高，且氮化铪 153層與氮化鉬1 55的熱穩定性和化學穩定性都要優於其 他的硬質材料’所以，依次麟的氮化鉻151、氮化給 153和氮化鉬155層可顯著提高被覆件1〇的硬度。 [0034] 於”亥複合硬質層15上形成抗氧化層17，其具體操作及工 藝參數如下：以氬氣為工作氣體，設置氬氣流量為 〜2〇〇sccin，以氧氣為反應氣體，設置氧氣流量為 150〜2〇〇sccin，對硬質基體11施加-5〇~-i〇〇v的偏壓， 設置偏壓的佔空比為30%〜50% ’並加熱鍍膜室至1〇〇〜15〇 C ’開啟|g乾25 ’设置其功率為8〜13kw，沉積氧化铭層 17。>儿積氧化紹層1 7的時間為3 0 ~ 6 0 m i η。控制氧化紹層 17的厚度為0. 5〜1. 0 /zm。 [0035] 被覆件1〇在加工使用時表面溫度會升高，通過在被覆件 10外表面披覆一層化學性能非常穩定的氧化鋁膜層17， 可以保護披覆件10上的硬質塗層不因使用而加劇氧化， 因此可以提高被覆件10的使用溫度，延長了被覆件1〇的 使用壽命。 [0036] 以下結合具體實施例對被覆件10的製備方法及被覆件10 進行說明： [0037] 實施例1 [0038] 電漿清洗：氬氣流量為280sccm，硬質基體11的偏壓為- 100112576 表單編號A0101 第8頁/共16頁 1002020948-0 201240826 300V，電漿清洗的時間為9分鐘； [0039] 濺鍍過渡層13 :通入氬氣lOOsccm，於硬質基體11上施 加的偏壓為-50V，開啟鉻靶22，設置其功率為8kw，沉 積時間為1 0 m i η。 [0040] 藏鍍氣化鉻層151 :氬氣流量為lOOsccm，氮氣流量為 lOsccm，開啟鉻靶22，設置其功率為lkw，對硬質基體 11施加的偏壓為-100V，沉積20分鐘； [0041] 滅鑛氮化铪層153 :氬氣流量為10Osccm，氮氣流量為 lOsccm，開啟铪靶23，在硬質基體11上施加-100V的偏 壓，沉積60分鐘。 [0042] 濺鍍氮化鉬層1 55 :氬氣流量為1 OOsccm，設置氮氣 40sccm，開啟鉬靶24，在硬質基體11上施加-200V的偏 壓，沉積40分鐘。 [0043] 滅錄抗氧化層17 :氛氣流量為150sccm，氧氣流量為 75sccm，開啟鋁靶25，在硬質基體11上施加-100V的偏 壓，沉積時間為50min，在硬質基體11上施加-50V的偏 壓，沉積時間為30min。 [0044] 實施例2 [0045] 電漿清洗：氬氣流量為280sccm，硬質基體11的偏壓為-300V，電漿清洗的時間為9分鐘； [0046] 濺鍍過渡層13 :通入氬氣lOOsccm，於硬質基體11上施 加的偏壓-100V，開啟鉻靶22，設置其功率為10kw，沉 積時間為2 0 m i η。 100112576 表單編號 Α0101 第 9 頁/共 16 頁 1002020948-0 201240826 [0047] 滅鑛氮化鉻層151 :通入氬氣lOOsccm，氮氣流量為 40sccm，開啟鉻把22，設置其功率為2kw，設置硬質基 體11的偏壓為-150V，沉積25分鐘； [0048] 濺鍍氮化給層1 53 :氬氣流量為1 OOsccm，設置氮氣 40sccm，開啟铪靶23，在硬質基體11上施加-200V的偏 壓，沉積7 0分鐘。 [0049] 減:鍍說化鉬層1 55 :氬氣流量為1 OOsccm，設置氮氣 40sccm，開啟鉬靶24，在硬質基體11上施加-200V的偏 壓，沉積50分鐘。 [0050] 抗氧化層1 7 :氬氣流量為1 50sccm，氧氣流量為75sccm ，開啟鋁靶25，在硬質基體11上施加-100V的偏壓，沉 積時間為5 0 m i η。 [0051] 實施例3 [0052] 電漿清洗：氬氣流量為280sccm，硬質基體11的偏壓為-300V，電漿清洗的時間為9分鐘； [0053] 濺鍍過渡層13 :氬氣流量為lOOsccm，於硬質基體11上 施加的偏壓為-100V，開啟鉻靶22，設置其功率為13kw ，沉積時間為30min。 [0054] 濺鏟氮化鉻層1 51 :氬氣流量為1 OOsccm，氮氣流量為 70sccm ’開啟鉻乾22，設置其功率為3kw，設置硬質基 體11的偏壓為-300V，沉積30分鐘； [0055] 滅;鑛氮化給層153 :氬氣流量為1 OOsccm，氮氣流量為 70sccm，開啟铪靶23，在硬質基體11上施加-300V的偏 100112576 表單編號A0101 第10頁/共16頁 1002020948-0 201240826 壓，沉積90分鐘。 [0056] 濺鍍氮化鉬層155 :氬氣流量為lOOsccm，設置氮氣 40sccm，開啟钥祀24，在硬質基體11上施加_200V的偏 壓，沉積70分鐘。 [0057] 抗氧化層17 :氬氣流量為15〇sccm，氧氣流量為75sccm ，開啟鋁靶25，在硬質基體11上施加-150V的偏壓’沉 積時間為6 0 m i η。 [0058] 被覆件10的性能測試 〇 [0059] ( 1 )硬度測試，具體測試方法如下： [0060] 採用MVK-H11型維氏硬度計，在載荷為0. 025kg力的作用 下，測試被覆件10的維氏硬度。 [0061] 結果表明，由本發明實施例1至3所製造的被覆件10的維 氏硬度分別為621HV、630HV及634HV。可見，該被覆件 10具有較高的硬度。 Q [0062] (2)高溫抗氧化測試，具體測試方法如下： [0063] 採用的測試儀器為管式熱處理爐，測試條件為：升溫速 率為10°C/min，熱處理溫度為800°C，保溫時間為l〇h。 [0064] 測試結果顯示，由本發明實施例1至3所製備的被覆件1〇 經800°C熱處理1 Oh後均未見氧化、脫落等不良。 【圖式簡單說明】 [0065] 圖1係本發明較佳實施例的被覆件的剖視圖； [0066] 圖2係本發明較佳實施例的被覆件的俯視示意圖。 100112576 表單編號A0101 第11頁/共16頁 1002020948-0 201240826 【主要元件符號說明】 [0067] 被覆件：10 [0068] 硬質基體：11 [0069] 過渡層：13 [0070] 複合硬質層：15 [0071] 氮化鉻層：151 [0072] 氮化給層：153 [0073] 氮化銘層：1 5 5 [0074] 抗氧化層：17 [0075] 鍍膜機：100 [0076] 真空泵：30 [0077] 軌跡：21 [0078] 鉻靶：22 [0079] 铪靶：23 [0080] 鉬乾：24 [0081] 鋁靶：25 [0082] 鍍膜室：20 100112576 表單編號A0101 第12頁/共16頁 10020209_48-0201240826 VI. Description of the Invention: [Technical Leadership of Invention] [0001] The present invention relates to a covering member and a method of manufacturing the same. [Prior Art] [0002] The vacuum coating process has a wide range of applications in the industrial field, in which the TiN film is coated on the surface of the tool or the mold to greatly improve the service life of the tool and the mold. However, as metal cutting progresses toward high cutting speeds, high speeds, high reliability, long life, high precision, and good cutting control, higher demands are placed on the performance of surface coverings. Conventional single TiN coatings have been unable to meet the requirements in terms of hardness and toughness. [〇〇〇3] ZrN films have attracted much attention due to their hardness and toughness being superior to those of TiN films. However, the single ZrN film has almost no room for improvement in terms of hardness and oxidation resistance, and it is difficult to meet the needs of modern industry. It is also known that CrN is a hard and thin material that can be used as a superhard tool material and a surface protection material. However, since the hardness of CrN itself is not very high (about 18GPa), its application on tools or molds is limited. In addition, the above ZrN or CrN hard thinner has poor oxidation resistance and is coated on The surface of the tool or mold does not have a good anti-oxidation effect, which easily leads to failure of the film. SUMMARY OF THE INVENTION It is necessary to provide a covering member having both high hardness and preferable oxidation resistance. _5] In addition, money is supplied to a method of manufacturing the above-mentioned covering member. 100112576 Form No. A0101 Page 3 of 16 1002020948-0 201240826 [0006] A covering member includes a hard substrate, a transition layer, a composite hard layer and an oxidation resistant layer sequentially formed on the hard substrate, the transition layer being The chromium layer 'the composite hard layer includes a chromium nitride layer 'tantalum nitride and a molybdenum nitride layer sequentially formed on the transition layer, and the oxidation resistant layer is an aluminum oxide layer. [00 (7) - a method of manufacturing a coated member, comprising the steps of: [0008] providing a hard substrate; [0009] magnetically destroying the emissive layer on the surface of the hard substrate; [0010] magnetically on the layer Controlling the carbon chrome layer; [0011] magnetron sputtering nitriding the layer on the nitride layer; [0012] magnetron sputtering the molybdenum nitride layer on the chromium nitride layer; The magnetized sputtering layer oxidizes the inscription layer on the nitriding layer. [0014] The chrome layer plays a role in the composite hard and wide chromium nitride layer, which can better strengthen the hard substrate and the composite hard layer. At the same time, the combination of the chromium nitride layer, the tantalum nitride and the molybdenum nitride layer formed in the composite hard layer simultaneously makes the composite hard layer more stable, mainly because the chromium nitride layer is opposite to the chromium layer. It has strong adhesion, and both the tantalum nitride and the molybdenum nitride as the outer layer have a thermal expansion coefficient similar to that of the hard matrix, so the internal stress at the interface is small', so that the outer layer of tantalum nitride and molybdenum nitride layer and nitrogen The chrome layer has stronger bonding strength and higher toughness, and is located in the tantalum nitride layer between chromium nitride and molybdenum nitride. The stability and chemical stability are superior to those of other hard materials. Therefore, the successively sputtered chromium nitride and nitride ring layers can significantly improve the hardness of the coated part and the peeling resistance of the film. Finally, in the composite hard layer Magnetron Sputtered Alumina Layer 'It can give the above 1002020948-0 100112576 Form No. Α0101 Page 4 / Total 16 Page 201240826 The composite hard layer brings better oxidation resistance and thus prolongs the service life of the product. [0015] Referring to FIG. 1, a covering member 10 according to a preferred embodiment of the present invention includes a rigid substrate 11, and a transition layer 13, a composite hard layer 15, and an oxidation resistant layer 17 sequentially formed on the hard substrate 11. [0016] The transition layer 13 is a chromium layer. [0017] The composite hard layer 15 includes a chrome nitride layer 151, a tantalum nitride layer 153, and a molybdenum nitride layer 155 which are sequentially formed on the hard substrate 11. The chromium layer 151, the tantalum nitride layer 153, and the nitride layer 155 may be formed by magnetron sputtering. [0018] The oxidation resistant layer 17 is an aluminum oxide layer. [0019] In this embodiment, the composite hard material The thickness of the layer 15 is 4 to 8 #m. [0020] The hard base The material of 11 may be a hard metal such as high speed steel or stainless steel. [0021] The covering member 10 in this embodiment may be various types of cutting tools, precision measuring tools or molds. [0022] The method for manufacturing the covering member 10 mainly includes the following Step: [0023] A hard substrate 11 is provided. [0024] The hard substrate 11 is pretreated. [0025] The hard substrate 11 is placed in an ultrasonic cleaner containing an ethanol or acetone solution for cleaning to remove the hard material. Impurities and oil on the surface of the substrate 11 100112576 Form No. A0101 Page 5 of 16 Page 1002020948-0 201240826 Stained. After cleaning, dry and set aside. The surface of the hard substrate 11 subjected to the above treatment is subjected to argon plasma cleaning to further remove the oil stain on the surface of the hard substrate 11 to improve the bonding force between the surface of the hard substrate 11 and the subsequent coating. [0027] A coating machine 100 is provided. The coating machine 100 includes a coating chamber 20 and a vacuum pump 30 for evacuating the coating chamber 20. The coating chamber 20 is provided with a rotating frame (not shown). A chromium target 22, a target 23, a molybdenum target 24, and an aluminum target 25 are attached to the side walls of the chamber 20. The turret drives the aluminum or aluminum alloy substrate 11 to revolve along a circular trajectory 21, and the aluminum or aluminum alloy substrate 11 also rotates as it revolves along the trajectory 21. [0028] The specific operation and process parameters of the plasma cleaning may be: vacuuming the coating chamber 20 to a vacuum of 8. 0xl0 - 3Pa, with a flow rate of 300 ~ 500sccm (standard state ML / min) An argon gas (working gas) having a purity of 99.999% is introduced into the chamber 20, and a bias voltage of -300 to -800 V is applied to the hard substrate 11, and a high-frequency voltage is formed in the coating chamber 20 to cause the argon. The surface of the hard substrate 11 is physically bombarded by gas-electric slurrying to produce an argon plasma, thereby achieving the purpose of cleaning the surface of the hard substrate 11. The argon plasma cleaning time is 3 to 10 min. [0029] After the hard substrate 11 is plasma-cleaned, the transition layer 13 is formed on the hard substrate 11. The specific operation and process parameters for forming the transition layer 13 are as follows: argon gas is used as a working gas, the argon gas flow rate is adjusted to 100 to 300 sccm, and a bias voltage of -50 to 200 V is applied to the hard substrate 11 to set a duty ratio of the bias voltage. 30%~80%, and heating the coating chamber 20 to 100~150 °C, with the target of chrome target 22, set its power to 8~13kw, 100112576 Form No. A0101 Page 6 / Total 16 Page 1002020948-0 201240826 A transition layer 13 is deposited. The transition layer is a chrome layer. The time for depositing the transition layer 13 is 10 to 30 minutes. [0030] A composite hard layer 15 is formed on the transition layer 13. First, a chromium nitride layer 151 in the composite hard layer 15 is formed. The specific operation and process parameters for forming the chromium nitride layer 151 are as follows: argon gas is used as a working gas, the argon gas flow rate is adjusted to 100-300 sccm, and a reaction gas nitrogen gas having a flow rate of 10 to 70 sccm is introduced to be applied to the hard substrate 11. -50~_200V bias, set the duty cycle of the bias voltage to 30%~80%, and heat the coating chamber 20 to 1〇〇~150°C. • Turn on the chrome target 22 and set its power to l~3kw. A chromium nitride layer 151 is deposited. The time for depositing the nitride layer 1 51 is 10 to 30 minutes. Ο [0032] Forming a tantalum nitride layer 153 on the chromium nitride layer 151. The specific operation and process parameters are as follows: argon gas is used as a working gas, and a flow rate of 1 〇 to 70 sccm is introduced into the coating chamber 20. The gas nitrogen gas has a power of 4 kW for the target material 23, a bias voltage of -100 to -300 V applied to the hard substrate 11, and a duty ratio of 30% to 80 for the bias voltage. %, the nitrogen flow rate is 10 to 70 sccm, and the sputtering temperature is 100 to 200 ° C, and the tantalum nitride layer 153 is deposited. The time for depositing the lead nitride layer 153 is 60 to 90 μη. The molybdenum nitride layer 155 is formed on the tantalum nitride layer 153. The specific operation and process parameters are as follows: argon gas is used as the working gas, the argon gas flow rate is set to 100-200 sccm, and the nitrogen gas flow rate is 100-200 sccm, and the hard substrate 11 is applied. Apply a bias voltage of -50 to -100V, set the duty cycle of the bias voltage to 30% to 50%, and heat the coating chamber to 100~150 °C; turn on the molybdenum target 24, set its power to 8~13kw, deposit the Molybdenum nitride layer 155. The time for depositing the nitride layer 155 is 40 to 70 minutes. 100112576 Form No. A0101 Page 7 of 16 1002020948-0 201240826 [The chromium layer 13 acts to enhance the adhesion of the composite hard layer 15. The nitriding pin 155 as the outermost layer in the composite hard shell layer 15 has a thermal expansion coefficient close to that of the nitriding layer 153, so that the internal stress at the interface is small, so that the bonding force of the Mn layer 153 is stronger. The toughness is higher, and the thermal stability and chemical stability of 153 layers of tantalum nitride and molybdenum nitride 1 55 are superior to those of other hard materials. Therefore, the chromium nitride 151, nitriding 153 and nitriding of the lining The layer of molybdenum 155 can significantly increase the hardness of the coated member. [0034] An anti-oxidation layer 17 is formed on the "Hay composite hard layer 15," and the specific operation and process parameters are as follows: argon gas is used as a working gas, and an argon gas flow rate of ~2 〇〇sccin is set, and oxygen is used as a reaction gas. The oxygen flow rate is 150~2〇〇sccin, the bias voltage of -5〇~-i〇〇v is applied to the hard substrate 11, the duty ratio of the bias is set to 30%~50%' and the coating chamber is heated to 1〇〇. ~15〇C 'Open|g dry 25' set its power to 8~13kw, deposit oxidation layer 17. The time of oxidation of the layer is 3 0 ~ 60 0 η. Control oxidation layer 17 The thickness of the coating member is 0. 5~1. 0 / zm. [0035] The surface temperature of the coated member 1 is increased during processing, and the outer surface of the coated member 10 is covered with a layer of alumite film 17 which is very stable in chemical properties. The hard coating on the covering member 10 can be protected from oxidation due to use, so that the use temperature of the covering member 10 can be increased, and the service life of the covering member 1〇 can be prolonged. [0036] The following is a combination of the specific embodiments. The preparation method of 10 and the covering member 10 are described: [0037] Example 1 [0038] Plasma cleaning: argon gas The flow rate is 280 sccm, the bias of the hard substrate 11 is -100112576 Form No. A0101 Page 8 / Total 16 pages 1002020948-0 201240826 300V, plasma cleaning time is 9 minutes; [0039] Sputtering transition layer 13: argon is introduced The gas lOOsccm is applied with a bias voltage of -50 V on the hard substrate 11, and the chromium target 22 is turned on, and the power is set to 8 kw, and the deposition time is 10 μm. [0040] The vaporized chromium layer 151 is deposited: the flow rate of the argon gas is lOOsccm, the nitrogen flow rate is lOsccm, the chromium target 22 is turned on, the power is set to lkw, the bias voltage applied to the hard substrate 11 is -100 V, and deposition is performed for 20 minutes; [0041] The cerium nitride layer 153: the argon flow rate is 10 Osccm The nitrogen flow rate is 10 sccm, the crucible target 23 is opened, a bias of -100 V is applied to the hard substrate 11, and deposition is performed for 60 minutes. [0042] Sputtering molybdenum nitride layer 1 55: argon gas flow rate is 100 sec, nitrogen gas is set to 40 sccm, The molybdenum target 24 was turned on, and a bias of -200 V was applied to the hard substrate 11 for 40 minutes. [0043] The anti-oxidation layer 17 was destroyed: the flow rate of the atmosphere was 150 sccm, the flow rate of oxygen was 75 sccm, and the aluminum target 25 was opened on the hard substrate. Apply a bias of -100V on the 11 and a deposition time of 50 min on a hard substrate A bias voltage of -50 V was applied to the deposition time of 30 min. [0044] Example 2 [0045] Plasma cleaning: argon gas flow rate was 280 sccm, hard substrate 11 bias was -300 V, and plasma cleaning time was 9 [0046] Sputtering transition layer 13: argon gas of 100 sccm was applied, and a bias voltage of -100 V was applied to the hard substrate 11, and the chromium target 22 was turned on, and the power was set to 10 kw, and the deposition time was 20 μm. 100112576 Form No. 1010101 Page 9 of 16 1002020948-0 201240826 [0047] Mine Chromium Nitride Layer 151: Pass argon gas 100sccm, nitrogen flow rate is 40sccm, turn on chrome handle 22, set its power to 2kw, set hard The substrate 11 has a bias voltage of -150 V and is deposited for 25 minutes. [0048] Sputtering nitriding layer 1 53 : Argon gas flow rate is 100 sec, nitrogen gas is set to 40 sccm, yttrium target 23 is opened, and -200 V is applied to the hard substrate 11. Bias, deposited for 70 minutes. [0049] Subtraction: Molybdenum plating layer 1 55: Argon gas flow rate was 100 sec, nitrogen gas was set to 40 sccm, molybdenum target 24 was opened, and a bias voltage of -200 V was applied to the hard substrate 11 to deposit for 50 minutes. [0050] The oxidation resistant layer 17: an argon gas flow rate of 150 sccm and an oxygen flow rate of 75 sccm, the aluminum target 25 was opened, and a bias voltage of -100 V was applied to the hard substrate 11, and the deposition time was 5 0 m i η. Example 3 [0052] Plasma cleaning: argon gas flow rate was 280 sccm, hard substrate 11 bias was -300 V, plasma cleaning time was 9 minutes; [0053] Sputtering transition layer 13: argon flow rate For lOOsccm, the bias voltage applied to the hard substrate 11 was -100 V, the chromium target 22 was turned on, the power was set to 13 kw, and the deposition time was 30 min. [0054] Splash slag chromium nitride layer 1 51: argon flow rate of 100 sec, nitrogen flow rate of 70sccm 'open chrome dry 22, set its power is 3kw, set the hard substrate 11 bias is -300V, deposition for 30 minutes; [0055] annihilation; mineral nitriding layer 153: argon gas flow rate is 100 sec, nitrogen gas flow rate is 70 sccm, opening yttrium target 23, applying -300 V biasing on hard substrate 11 100112576 Form No. A0101 Page 10 of 16 1002020948-0 201240826 Pressure, deposition for 90 minutes. [0056] The molybdenum nitride layer 155 was sputtered: a flow rate of argon gas was 100 sccm, nitrogen gas was set to 40 sccm, the key 祀 24 was opened, and a bias of _200 V was applied to the hard substrate 11 to deposit for 70 minutes. [0057] The oxidation resistant layer 17: an argon gas flow rate of 15 〇sccm, an oxygen flow rate of 75 sccm, opening of the aluminum target 25, and applying a bias voltage of -150 V on the hard substrate 11 was a deposition time of 60 μm. [0058] The performance test of the covering member 10 [0059] (1) hardness test, the specific test method is as follows: [0060] using MVK-H11 type Vickers hardness tester, under the effect of a load of 0. 025kg, test coating Vickers hardness of piece 10. The results showed that the Vickers 10 manufactured by the inventive Examples 1 to 3 had Vickers hardness of 621 HV, 630 HV, and 634 HV, respectively. It can be seen that the covering member 10 has a high hardness. Q [0062] (2) High-temperature oxidation test, the specific test method is as follows: [0063] The test instrument used is a tube heat treatment furnace, the test conditions are: heating rate is 10 ° C / min, heat treatment temperature is 800 ° C, The holding time is l〇h. [0064] The test results showed that the coated member 1 prepared in Examples 1 to 3 of the present invention showed no defects such as oxidation and shedding after heat treatment at 800 ° C for 1 Oh. BRIEF DESCRIPTION OF THE DRAWINGS [0065] FIG. 1 is a cross-sectional view of a coated member in accordance with a preferred embodiment of the present invention; [0066] FIG. 2 is a top plan view of a coated member in accordance with a preferred embodiment of the present invention. 100112576 Form No. A0101 Page 11 of 16 1002020948-0 201240826 [Description of main component symbols] [0067] Covering member: 10 [0068] Hard substrate: 11 [0069] Transition layer: 13 [0070] Composite hard layer: 15 [0071] Chromium nitride layer: 151 [0072] Nitrided donor layer: 153 [0073] Nitride inscribed layer: 1 5 5 [0074] Antioxidant layer: 17 [0075] Coating machine: 100 [0076] Vacuum pump: 30 Track: 21 [0078] Chromium target: 22 [0079] 铪 target: 23 [0080] Molybdenum dry: 24 [0081] Aluminum target: 25 [0082] Coating chamber: 20 100112576 Form No. A0101 Page 12 / Total 16 pages 10020209_48-0