201215692 六、發明說明： 【發明所屬之技術頜 [0001] 本發明涉及一種塗層、具有該塗層的被覆件及該被覆件 ' 的製備方法，特別涉及一種以真空鍍膜的方式形成的塗 層、具有該塗層的被覆件及該被覆件的製備方法。 C先前技術3 [00〇2]真空鍍膜工藝在工業領域有著廣泛的應用，其中，TiN薄 膜鑛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、高進給 速度、咼可靠性、長壽命、高精度和良好的切削控制性 #面發展’對表面塗層的性餘提出了更高的要求。傳統 的TiN塗層在硬度、勃性等方面已經不能滿足要求。 _3] ZrN薄膜由於其硬度與純均優於τ丨N薄_受到人們的 廣泛關注。但單一的ZrN薄膜在硬度、動性及财磨性等方 面幾乎已經没有提高的空間，很難滿足現代工業的需求 1: I I Γ 」| η.〜=::;: 〇 〇 【發明内容】 :ί二v [0004] #鑒於此’提供一種具有良好硬度、勒性及对磨性的塗 層。 闺賴供上述塗層的被覆件。 [剩還提供1上述«件的製備方法。 [0007] -種塗層該塗層包括奈米複合層，該奈米複合層包括 複數ZrN層和複數ZrYN層，所述複數ZrN層和複數ZrYN層 交替排布。 099134794 表單编號A0101 第3頁/共12頁 0992060743-0 201215692 [0008] 一種被覆件，該被覆件包括基體、形成於該基體的結合 層及形成於該結合層上的塗層，該結合層為Z r Y層，該塗 層包括奈米複合層，該奈米複合層包括複數ZrN層和複數 ZrYN層，所述複數ZrN層和複數ZrYN層交替排布。 [0009] 一種被覆件的製備方法，包括以下步驟： [0010] 提供基體； [0011] 於該基體的表面磁控濺射結合層，該結合層為ZrY層； [0012] 於該結合層的表面磁控濺射奈米複合層，該奈米複合層 包括複數ZrN層和複數ZrYN層，所述複數ZrN層和複數 ZrYN層交替排布。 [0013] 在形成所述ZrYN層時，N原子優先與Zr原子形成ZrN晶粒 ，丫原子則以獨立形式偏聚在晶界上形成Y相，其可抑制 ZrN晶粒的長大，因而使得ZrYN層中的ZrN晶粒的粒徑維 持在奈米級，該奈米級的ZrN晶粒可有效提高所述奈米複 合層的硬度和韌性。更重要的，由於奈米級氮化物ZrN與 ZrYN之間剪切模量的差異，交替沉積的每一ZrN層與每一 ZrYN層之間的位錯運動在二膜層的介面處而停止，位元 錯的塞積可產生硬化現象及抑制膜層的變形，從而使得 所述奈米複合層的硬度及韌性進一步得到顯著的提高。 所述的被覆件在基體與奈米複合層之間設置ZrY結合層， 可有效提高塗層與基體之間的結合力。所述塗層的硬度 、韌性的提高及塗層與基體之間結合力的增強，可顯著 地提高所述塗層的耐磨性。 【實施方式】 099134794 表單編號A0101 第4頁/共12頁 0992060743-0 201215692 [0014] 請參閱圖1，本發明一較佳實施例的塗層30包括奈米複合 層31。該奈米複合層31包括複數氮化锆（ZrN)層311和 複數氮化鍅釔（ZrYN)層313，所述複數ZrN層311和複 數ZrYN層313交替排布。所述複數ZrN層311及複數ZrYN 層313藉由磁控濺射的方法形成。該複數ZrN層311及複 數ZrYN層313的層數分別為20〜50層。 [0015] 每一ZrN層311的厚度為10〜20nm，每一ZrYN層313的厚 度為10~20nm。所述塗層30的總厚度為l~4/zm。 [0016] 可以理解的，所述塗層30還可包括於該奈米複合層31的 表面上鍍覆的顏色層33，以增強該塗層30的美觀性。 ' [0017] 請參閱圖2，本發明一較佳實施例的被覆件40包括基體10 、形成於該基體10的結合層20及形成於該結合層20上的 所述塗層30。該基體10的材質可以為高速鋼、硬質合金 及不銹鋼等。該被覆件40可以為各類切削刀具、精密量 具、模具、3C電子產品外殼及各種建築裝飾件等。 〇 [0018] 該結合層20為鍅釔（ZrY)層，其厚度為0. 05~0. 2/zm。 該結合層20藉由磁控濺射法沉積形成。該結合層20的化 學穩定性與熱膨脹係數介於基體10與塗層30之間，因而 可有效提高塗層30與基體10之間的結合力。所述塗層30 與基體11直接結合的為ZrN層311。 [0019] 所述被覆件40的製備方法主要包括如下步驟： [0020] 提供基體10，該基體10的材質可以為高速鋼、硬質合金 、金屬陶瓷及燒結金剛石等。將基體10放入盛裝有乙醇 及/或丙酮溶液的超聲波清洗器中進行震動清洗，以除去 099134794 表單編號A0101 第5頁/共12頁 0992060743-0 201215692 基體ίο表面的雜質和油污等。清洗完畢後烘乾備用。 [0021] 對經上述處理後的基體10的表面進行電漿清洗，以進一 步去除基體10表面的油污，以及改善基體10表面與後續 塗層的結合力。該電漿清洗的具體操作及工藝參數為： 將基體10固定於磁控濺射鍍膜機的鍍膜室的工件架上， 抽真空該鍍膜室至真空度為8. 0x1 (T3Pa，以 300~600sccm (標準狀態毫升/分鐘）的流量向鍍膜室内 通入純度為99. 999%的氬氣，並施加-300〜-800V的偏壓 於基體10，對基體10表面進行電漿清洗，清洗時間為 3〜1Omin 。 [0022] 在對基體10進行電漿清洗後，於該基體10上形成結合層 20。該結合層20為ZrY層。形成該結合層20的具體操作 方法及工藝參數如下：調節氬氣（工作氣體）流量至 150〜300sccm，加熱該鍍膜室至150〜300°C (即濺射溫 度為150〜300°C)，設置所述工件架的公轉速度為 1. 0~3. Or pm (revolution per minute，轉/分鐘） ;開啟分別安裝於所述鍍膜室兩側的鍅靶及锆釔合金靶 的電源，並設置所述锆靶及鍅釔合金靶的電流均為 20〜100A ;於基體10上施加-100~-300V的偏壓，沉積結 合層20。沉積該結合層20的時間為5~15min。所述锆釔 合金靶中Zr的質量百分含量為70〜90%。 [0023] 形成所述結合層20後，於該結合層20上形成奈米複合層 31。該奈米複合層31由複數ZrN層311和複數ZrYN層313 交替沉積形成。形成所述奈米複合層31的具體操作方法 及工藝參數如下：向鍍膜室中通入流量為10〜200sccm的 099134794 表單編號A0101 第6頁/共12頁 0992060743-0 201215692 [0024] ❹ [0025] [0026] Ο [0027]201215692 VI. Description of the Invention: [Technical Jaw of the Invention] [0001] The present invention relates to a coating, a coated member having the same, and a method of preparing the coated member, and more particularly to a coating formed by vacuum coating A coated member having the coating and a method of preparing the coated member. C Prior Art 3 [00〇2] The vacuum coating process has a wide range of applications in the industrial field. Among them, the coating of TiN film on the surface of the tool or mold can greatly improve the service life of the tool and the mold. However, with the high cutting speed, high feed rate, high reliability, long life, high precision and good cutting control of metal cutting, higher requirements are placed on the surface coating. Conventional TiN coatings are no longer sufficient in terms of hardness and boring properties. _3] ZrN film is more popular than τ丨N due to its hardness and purity. However, the single ZrN film has almost no room for improvement in terms of hardness, dynamics, and grindiness, and it is difficult to meet the needs of modern industry. 1: II Γ ”| η.~=::;: 〇〇【Contents】 : ί二v [0004] # In view of this, a coating having good hardness, strength and abrasion resistance is provided. The coating for the above coating is relied upon. [There is also a method of preparing the above 1 piece. A coating comprising a nanocomposite layer comprising a plurality of ZrN layers and a plurality of ZrYN layers, the plurality of ZrN layers and the plurality of ZrYN layers being alternately arranged. 099134794 Form No. A0101 Page 3 of 12 0992060743-0 201215692 [0008] A covering member comprising a base body, a bonding layer formed on the base body, and a coating layer formed on the bonding layer, the bonding layer In the Zr Y layer, the coating comprises a nanocomposite layer comprising a plurality of ZrN layers and a plurality of ZrYN layers, the complex ZrN layer and the plurality of ZrYN layers being alternately arranged. [0009] A method for preparing a coated member, comprising the steps of: [0010] providing a substrate; [0011] magnetron sputtering a bonding layer on a surface of the substrate, the bonding layer being a ZrY layer; [0012] A surface magnetron sputtering nanocomposite layer comprising a complex ZrN layer and a complex ZrYN layer, the complex ZrN layer and the complex ZrYN layer being alternately arranged. [0013] When forming the ZrYN layer, the N atom preferentially forms a ZrN crystal with the Zr atom, and the germanium atom is segregated in an independent form on the grain boundary to form a Y phase, which can inhibit the growth of the ZrN crystal grain, thereby making ZrYN The particle size of the ZrN grains in the layer is maintained at the nanometer level, and the nano-sized ZrN grains can effectively improve the hardness and toughness of the nanocomposite layer. More importantly, due to the difference in shear modulus between the nanoscale nitride ZrN and ZrYN, the dislocation motion between each ZrN layer and each ZrYN layer alternately deposited stops at the interface of the two layers. The plug product of the bit error can cause a hardening phenomenon and suppress deformation of the film layer, so that the hardness and toughness of the nanocomposite layer are further significantly improved. The covering member is provided with a ZrY bonding layer between the substrate and the nano composite layer, which can effectively improve the bonding force between the coating and the substrate. The increase in the hardness and toughness of the coating and the enhanced bonding between the coating and the substrate can significantly improve the abrasion resistance of the coating. [Embodiment] 099134794 Form No. A0101 Page 4 of 12 0992060743-0 201215692 [0014] Referring to FIG. 1, a coating 30 according to a preferred embodiment of the present invention includes a nanocomposite layer 31. The nanocomposite layer 31 includes a complex zirconium nitride (ZrN) layer 311 and a complex tantalum nitride (ZrYN) layer 313, and the complex ZrN layer 311 and the complex ZrYN layer 313 are alternately arranged. The complex ZrN layer 311 and the complex ZrYN layer 313 are formed by a magnetron sputtering method. The number of layers of the complex ZrN layer 311 and the complex ZrYN layer 313 is 20 to 50 layers, respectively. [0015] Each ZrN layer 311 has a thickness of 10 to 20 nm, and each ZrYN layer 313 has a thickness of 10 to 20 nm. The total thickness of the coating 30 is from 1 to 4/zm. [0016] It will be appreciated that the coating 30 may also include a color layer 33 plated on the surface of the nanocomposite layer 31 to enhance the aesthetics of the coating 30. Referring to FIG. 2, a covering member 40 according to a preferred embodiment of the present invention includes a base 10, a bonding layer 20 formed on the substrate 10, and the coating layer 30 formed on the bonding layer 20. The material of the base 10 may be high speed steel, hard alloy, stainless steel or the like. The covering member 40 can be various types of cutting tools, precision measuring tools, molds, 3C electronic product casings, and various architectural decorative parts. 5至0. 2/zm。 The thickness of the layer is 0. 05~0. 2/zm. The bonding layer 20 is formed by magnetron sputtering deposition. The chemical stability and thermal expansion coefficient of the bonding layer 20 is between the substrate 10 and the coating layer 30, so that the bonding force between the coating layer 30 and the substrate 10 can be effectively improved. The coating 30 directly bonded to the substrate 11 is a ZrN layer 311. [0019] The method for preparing the covering member 40 mainly includes the following steps: [0020] A substrate 10 is provided, and the material of the substrate 10 may be high speed steel, cemented carbide, cermet, sintered diamond or the like. The substrate 10 is placed in an ultrasonic cleaner containing an ethanol and/or acetone solution for vibration cleaning to remove 099134794 Form No. A0101 Page 5 of 12 0992060743-0 201215692 Substrate ίο Surface impurities and oil stains, etc. After cleaning, dry and set aside. [0021] The surface of the substrate 10 subjected to the above treatment is subjected to plasma cleaning to further remove the oil stain on the surface of the substrate 10, and to improve the bonding force between the surface of the substrate 10 and the subsequent coating. The specific operation and process parameters of the plasma cleaning are as follows: The substrate 10 is fixed on the workpiece holder of the coating chamber of the magnetron sputtering coating machine, and the vacuum chamber is evacuated to a vacuum of 8. 0x1 (T3Pa, 300~600sccm) The flow rate of the standard body ML/min was introduced into the coating chamber to an argon gas having a purity of 99.999%, and a bias of -300 to -800 V was applied to the substrate 10, and the surface of the substrate 10 was plasma-cleaned for a cleaning time of 3~1Omin. [0022] After the plasma cleaning of the substrate 10, a bonding layer 20 is formed on the substrate 10. The bonding layer 20 is a ZrY layer. The specific operation method and process parameters for forming the bonding layer 20 are as follows: 0~3。 The argon gas (working gas) flow rate to 150~300sccm, the coating chamber is heated to 150~300 ° C (ie, the sputtering temperature is 150~300 ° C), the revolving speed of the workpiece holder is set to 1. 0~3. Or pm (revolution per minute, rpm); turn on the power supply of the yttrium target and the zirconium-niobium alloy target respectively installed on both sides of the coating chamber, and set the current of the zirconium target and the yttrium alloy target to 20~ 100A; a bonding layer 20 is deposited by applying a bias of -100 to -300 V on the substrate 10. The time for the bonding layer 20 is 5 to 15 minutes, and the mass percentage of Zr in the zirconium-niobium alloy target is 70 to 90%. [0023] After the bonding layer 20 is formed, the nano layer is formed on the bonding layer 20. The rice composite layer 31. The nano composite layer 31 is formed by alternately depositing a plurality of ZrN layers 311 and a plurality of ZrYN layers 313. The specific operation method and process parameters for forming the nanocomposite layer 31 are as follows: the flow rate into the coating chamber is 099134794 of 10~200sccm Form No. A0101 Page 6 of 12 0992060743-0 201215692 [0024] ❹ [0025] [0026] Ο [0027]
純度為99. 999%的氮氣，以沉積所述奈米複合層31。沉 積該奈米複合層31時，交替開啟分別安裝於所述磁控濺 射鍍膜機的鍅釔合金靶及鍅靶，以於結合層20上交替沉 積複數ZrN層311和複數ZrYN層313。沉積該奈米複合層 31的時間為60~120min。 關閉負偏壓、鍅釔合金靶及鍅靶電源，停止通入氬氣及 氮氣，待所述奈米複合層31冷卻後，向鍍膜内通入空氣 ，打開鍍膜室門，取出鍍覆有結合層20及奈米複合層31 的基體10。 可以理解的，製備所述被覆件40的方法還可包括在該奈 米複合層31的表面鍍覆顏色層33，以增強被覆件40的美 觀性。 在形成ZrYN層313時，由於Y與Zr不能形成固溶體，且Y 不易與氮氣反應，沉積過程中氮氣中的N原子優先與Zr原 子形成ZrN晶粒，Y原子則以獨立形式偏聚在晶界上形成Y 相，其可抑制ZrN晶粒的長大，因而使得ZrYN層313中的 ZrN晶粒的粒徑維持在奈米級，該奈米級的ZrN晶粒可顯 著地提高所述奈米複合層31的硬度和韌性。更重要的為 ，由於奈米級氮化物ZrN與ZrYN之間剪切模量的差異，交 替沉積的每一ZrN層311與每一ZrYN層313之間的位錯運 動在二膜層的介面處而停止，位元錯的塞積可產生硬化 現象及抑制膜層的變形，從而使得所述奈米複合層31的 硬度及韌性進一步得到顯著的提高。 所述之被覆件40在基體10與奈米複合層31之間設置ZrY 099134794 表單編號A0101 第7頁/共12頁 0992060743-0 201215692 結合層20，由於該結合層20的化學穩定性與熱膨脹係數 介於基體10與奈米複合層31之間，因而可有效提高奈米 複合層31與基體10之間的結合力。所述奈米複合層31的 硬度、韌性的提高及奈米複合層31與基體10之間結合力 的增強，可顯著地提高所述塗層30的耐磨性。 [0028] 此外，所述塗層30在磨損過程中，塗層30表層的Y可與膜 層外界的0、S等元素結合，形成含有對應的氧化物或/和 硫化物的膜層，該膜層緻密且硬度較高，在工作過程中 對所述被覆件40起到較好的保護作用，間接地提高了被 覆件40的硬度及耐磨性。 【圖式簡單說明】 [0029] 圖1為本發明一較佳實施例的塗層的剖視圖； [0030] 圖2為本發明一較佳實施例的被覆件的剖視圖。 【主要元件符號說明】 [0031] 基體：10 [0032] 結合層：20 [0033] 奈米複合層：31 [0034] ZrN層：311 [0035] ZrYN層：313 [0036] 顏色層：3 3 [0037] 被覆件：40 099134794 表單編號A0101 第8頁/共12頁 0992060743-0Nitrogen gas having a purity of 99.999% was deposited to deposit the nanocomposite layer 31. When the nanocomposite layer 31 is deposited, the tantalum alloy target and the tantalum target respectively mounted on the magnetron sputtering coater are alternately opened to alternately deposit a plurality of ZrN layers 311 and a plurality of ZrYN layers 313 on the bonding layer 20. The time for depositing the nanocomposite layer 31 is 60 to 120 min. The negative bias voltage, the bismuth alloy target and the target power supply are turned off, and the argon gas and the nitrogen gas are stopped. After the nanocomposite layer 31 is cooled, air is introduced into the coating film, the coating chamber door is opened, and the plating is combined and removed. The layer 20 and the substrate 10 of the nanocomposite layer 31. It is to be understood that the method of preparing the covering member 40 may further include plating the color layer 33 on the surface of the nanocomposite layer 31 to enhance the aesthetics of the covering member 40. When ZrYN layer 313 is formed, since Y and Zr cannot form a solid solution, and Y is not easily reacted with nitrogen, the N atom in the nitrogen preferentially forms ZrN grains with Zr atoms during deposition, and the Y atoms are segregated in an independent form. A Y phase is formed on the grain boundary, which suppresses the growth of the ZrN crystal grain, thereby maintaining the particle size of the ZrN crystal grain in the ZrYN layer 313 at the nanometer level, and the nano-sized ZrN crystal grain can remarkably improve the Nye The hardness and toughness of the rice composite layer 31. More importantly, due to the difference in shear modulus between the nanoscale nitride ZrN and ZrYN, the dislocation motion between each ZrN layer 311 and each ZrYN layer 313 alternately deposited is at the interface of the two layers. On the other hand, the plugging of the bit error can cause a hardening phenomenon and suppress deformation of the film layer, so that the hardness and toughness of the nanocomposite layer 31 are further remarkably improved. The covering member 40 is disposed between the base 10 and the nanocomposite layer 31. ZrY 099134794 Form No. A0101 Page 7 / Total 12 Page 0992060743-0 201215692 Bonding layer 20 due to chemical stability and thermal expansion coefficient of the bonding layer 20 Between the substrate 10 and the nanocomposite layer 31, the bonding force between the nanocomposite layer 31 and the substrate 10 can be effectively improved. The improvement in hardness and toughness of the nanocomposite layer 31 and the enhancement of the bonding force between the nanocomposite layer 31 and the substrate 10 can remarkably improve the wear resistance of the coating layer 30. [0028] In addition, during the abrasion process of the coating layer 30, the Y of the surface layer of the coating layer 30 may be combined with elements such as 0, S and the like outside the film layer to form a film layer containing the corresponding oxide or/and sulfide. The film layer is dense and has high hardness, and the coating member 40 is better protected during the working process, and the hardness and wear resistance of the covering member 40 are indirectly improved. BRIEF DESCRIPTION OF THE DRAWINGS [0029] FIG. 1 is a cross-sectional view of a coating according to a preferred embodiment of the present invention; [0030] FIG. 2 is a cross-sectional view of a covering member in accordance with a preferred embodiment of the present invention. [Main component symbol description] [0031] Base: 10 [0032] Bonding layer: 20 [0033] Nano composite layer: 31 [0034] ZrN layer: 311 [0035] ZrYN layer: 313 [0036] Color layer: 3 3 [0037] Covering: 40 099134794 Form No. A0101 Page 8 / Total 12 Page 0992060743-0