TWI496903B - Coating, articles coated with the coating, and method for manufacturing the articles - Google Patents
Coating, articles coated with the coating, and method for manufacturing the articles Download PDFInfo
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Description
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。 The present invention relates to a coating, a coated article 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.
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、高進給速度、高可靠性、長壽命、高精度和良好的切削控制性方面發展,對表面塗層的性能提出了更高的要求。傳統的TiN塗層在硬度、韌性等方面已經不能滿足要求。 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, as metal cutting progresses toward high cutting speeds, high feed rates, high reliability, long life, high precision, and good cutting control, higher demands are placed on the performance of surface coatings. Conventional TiN coatings have been unable to meet the requirements in terms of hardness and toughness.
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、韌性及耐磨性等方面幾乎已經沒有提高的空間,很難滿足現代工業的需求。 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 hardness, toughness and wear resistance, and it is difficult to meet the needs of modern industry.
有鑒於此,提供一種應用具有良好硬度、韌性及耐磨性的塗層的被覆件。 In view of this, there is provided a coated member using a coating having good hardness, toughness and abrasion resistance.
另,還提供一種上述被覆件的製備方法。 Further, a method of preparing the above-mentioned covering member is also provided.
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ZrY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。 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 being a ZrY layer, the coating layer comprising a nano composite layer, the nano composite layer comprising The complex ZrN layer and the complex ZrYN layer, the complex ZrN layer and the complex ZrYN layer are alternately arranged.
一種被覆件的製備方法,包括以下步驟:提供基體;於該基體的表面磁控濺射結合層,該結合層為ZrY層;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。 A method for preparing a coated member, comprising the steps of: providing a substrate; magnetron sputtering a bonding layer on a surface of the substrate, the bonding layer is a ZrY layer; and magnetron sputtering a nano composite layer on the surface of the bonding layer, the nano layer The m composite layer includes a complex ZrN layer and a complex ZrYN layer, and the complex ZrN layer and the complex ZrYN layer are alternately arranged.
在形成所述ZrYN層時,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。 When forming the ZrYN layer, the N atom preferentially forms ZrN grains with the Zr atoms, and the Y atoms are segregated in an independent form on the grain boundaries to form a Y phase, which can inhibit the growth of the ZrN grains, thereby making the ZrYN layer The particle size of the ZrN grains 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 hardness and toughness of the coating and the enhanced bonding between the coating and the substrate can significantly improve the wear resistance of the coating.
10‧‧‧基體 10‧‧‧ base
20‧‧‧結合層 20‧‧‧bonding layer
31‧‧‧奈米複合層 31‧‧‧ nano composite layer
311‧‧‧ZrN層 311‧‧‧ZrN layer
313‧‧‧ZrYN層 313‧‧‧ZrYN layer
33‧‧‧顏色層 33‧‧‧ color layer
40‧‧‧被覆件 40‧‧‧Cladding
圖1為本發明一較佳實施例的塗層的剖視圖;圖2為本發明一較佳實施例的被覆件的剖視圖。 1 is a cross-sectional view of a coating according to a preferred embodiment of the present invention; and FIG. 2 is a cross-sectional view of a covering member in accordance with a preferred embodiment of the present invention.
為了使本發明的目的、技術方案及優點更加清楚明白,以下結合附圖與實施例對本發明進行進一步詳細說明。 The present invention will be further described in detail below with reference to the accompanying drawings and embodiments.
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包括複數氮化鋯(ZrN)層311和複數氮化鋯釔(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。 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 zirconium nitride zirconium (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.
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1~4μm。 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 layer 30 is 1 to 4 μm.
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。 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.
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。 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.
該結合層20為鋯釔(ZrY)層,其厚度為0.05~0.2μm。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。 The bonding layer 20 is a zirconium-germanium (ZrY) layer having a thickness of 0.05 to 0.2 μm. 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.
所述被覆件40的製備方法主要包括如下步驟: The preparation method of the covering member 40 mainly includes the following steps:
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,以除去基體10表面的雜質和油污等。清洗完畢後烘乾備用。 The base body 10 is provided, and the material of the base body 10 can be high speed steel, hard alloy, metal ceramic Porcelain and sintered diamonds. The substrate 10 is placed in an ultrasonic cleaner containing an ethanol and/or acetone solution for vibration cleaning to remove impurities, oil stains, and the like on the surface of the substrate 10. After cleaning, dry and set aside.
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8.0×10-3Pa,以300~600sccm(標準狀態毫升/分鐘)的流量向鍍膜室內通入純度為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3~10min。 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: fixing the substrate 10 to the workpiece holder of the coating chamber of the magnetron sputtering coating machine, and vacuuming the coating chamber to a vacuum of 8.0×10 -3 Pa to 300~ A flow rate of 600 sccm (standard state 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 3 times. ~10min.
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℃(即濺射溫度為150~300℃),設置所述工件架的公轉速度為1.0~3.0rpm(revolution per minute,轉/分鐘);開啟分別安裝於所述鍍膜室兩側的鋯靶及鋯釔合金靶的電源,並設置所述鋯靶及鋯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。所述鋯釔合金靶中Zr的質量百分含量為70~90%。 After the substrate 10 is subjected to plasma cleaning, 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: adjusting the flow rate of the argon gas (working gas) to 150 to 300 sccm, and heating the coating chamber to 150 to 300 ° C (ie, the sputtering temperature is 150 to 300 ° C). The revolution speed of the workpiece holder is 1.0 to 3.0 rpm (revolution per minute); the power supply of the zirconium target and the zirconium-niobium alloy target respectively mounted on both sides of the coating chamber is opened, and the zirconium target and zirconium are disposed. The current of the tantalum alloy target is 20 to 100 A; a bonding layer of 20 is deposited by applying a bias of -100 to -300 V on the substrate 10. The time for depositing the bonding layer 20 is 5 to 15 minutes. The mass percentage of Zr in the zirconium-niobium alloy target is 70-90%.
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鋯釔合金靶及鋯靶,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。 After the bonding layer 20 is formed, a nanocomposite layer 31 is formed on the bonding layer 20. The nanocomposite 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: nitrogen gas having a flow rate of 10 to 200 sccm and having a purity of 99.999% is introduced into the coating chamber to deposit the nanocomposite layer 31. When the nanocomposite layer 31 is deposited, it is alternately opened and installed separately in the office. The zirconium-niobium alloy target and the zirconium target of the magnetron sputtering coating machine are used 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.
關閉負偏壓、鋯釔合金靶及鋯靶電源,停止通入氬氣及氮氣,待所述奈米複合層31冷卻後,向鍍膜內通入空氣,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。 The negative bias voltage, the zirconium-niobium alloy target and the zirconium target power source are turned off, and the argon gas and the nitrogen gas are stopped. After the nano-composite 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.
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。 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.
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。 When the 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 the Zr atom during the deposition process, and the Y atom is segregated in an independent form. A Y phase is formed on the grain boundary, which can suppress the growth of ZrN crystal grains, thereby maintaining the particle size of the ZrN crystal grains in the ZrYN layer 313 at the nanometer level, and the nano-sized ZrN crystal grains can remarkably improve the Nai 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.
所述之被覆件40在基體10與奈米複合層31之間設置ZrY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。 The covering member 40 is provided with a ZrY bonding layer 20 between the substrate 10 and the nanocomposite layer 31. Since the chemical stability and the coefficient of thermal expansion of the bonding layer 20 are between the substrate 10 and the nanocomposite layer 31, The bonding force between the nanocomposite layer 31 and the substrate 10 is 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.
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O、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。 In addition, during the abrasion process of the coating layer 30, the surface layer Y of the coating layer 30 may be combined with elements such as O and S outside the film layer to form a film layer containing a corresponding oxide or/and sulfide, and the film layer is dense. Moreover, the hardness is high, and the covering member 40 is better protected during the working process, and the hardness and wear resistance of the covering member 40 are indirectly improved.
綜上所述,本發明符合發明專利要件,爰依法提出專利申請。惟,以上所述者僅為本發明之較佳實施方式,舉凡熟悉本案技藝之人士,於爰依本發明精神所作之等效修飾或變化,皆應涵蓋於以下之申請專利範圍內。 In summary, the present invention complies with the requirements of the invention patent and submits a patent application according to law. The above description is only the preferred embodiment of the present invention, and equivalent modifications or variations made by those skilled in the art will be covered by the following claims.
10‧‧‧基體 10‧‧‧ base
20‧‧‧結合層 20‧‧‧bonding layer
31‧‧‧奈米複合層 31‧‧‧ nano composite layer
311‧‧‧ZrN層 311‧‧‧ZrN layer
313‧‧‧ZrYN層 313‧‧‧ZrYN layer
33‧‧‧顏色層 33‧‧‧ color layer
40‧‧‧被覆件 40‧‧‧Cladding
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US20060147728A1 (en) * | 2004-05-03 | 2006-07-06 | Yaogen Shen | Multi-layered superhard nanocomposite coatings |
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US20060147728A1 (en) * | 2004-05-03 | 2006-07-06 | Yaogen Shen | Multi-layered superhard nanocomposite coatings |
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