201224177 六、發明說明： 【發明所屬之技術領域】 剛本發明涉及-種鍍膜件及其製備方&，尤其涉及一種具 有硬質塗層的鍍膜件及該鍍膜件的製備方法。 【先前技術】 [0002] 〇 硬質或超硬塗層一直係國内外研究的重要課題，其主要 應用係作為刀模具的保護改性塗層，以減少刀模具與工 件間的擴散和化學反應，提高刀模具的耐磨性和切削硬 度。該硬質或超硬塗層通常以物理或化學氣相沉積的方 法製成。 [0003] 習知的應用較多的硬質或超硬塗層主要係TiiJ、Tic、 TiAIN、TiCN等塗層。相對來講，TiA1N、TiCN等塗層 在硬度及耐磨性能方面均優於TiN、TiC等塗層。隨著汽 車、航空、航夭、重機等工業的發展，以及數控機床的 迅速普及，高速加工、幹式切削已成為目前切削加工的 發展趨勢，而所述的TiA1N、TiCN塗層也已難以滿足現 代化工業對刀模具更好性能的要求,。 【發明内容】 [0004] 鑒於此，有必要提供一種具有更高硬度及耐磨性能的塗 層的鍍膜件。 [0005] 另外，還有必要提供一種上述鍍膜件的製備方法。 [0006] —種鑛膜件，其包括金屬基體及形成於金屬基體表面的 硬質層，該硬質層為一氮化鉻-氮化矽的複合膜層。 [0007] —種鍍膜件的數備方法’其包括如下步驟： 099143852 表單編號A0101 第3頁/共13頁 0992075907-0 201224177 [0008] 提供一金屬基體；201224177 VI. Description of the Invention: [Technical Field] The present invention relates to a coated member and a preparation thereof, and more particularly to a coated member having a hard coat layer and a method of preparing the coated member. [Prior Art] [0002] Tantalum hard or super-hard coating has been an important topic for research at home and abroad. Its main application is as a protective modified coating for knife molds to reduce the diffusion and chemical reaction between the mold and the workpiece. Improve the wear resistance and cutting hardness of the knife mold. The hard or superhard coating is typically made by physical or chemical vapor deposition. [0003] Conventional hard or super hard coatings are mainly TiiJ, Tic, TiAIN, TiCN and the like. Relatively speaking, TiA1N, TiCN and other coatings are superior to TiN, TiC and other coatings in terms of hardness and wear resistance. With the development of industries such as automobiles, aviation, aviation, heavy machinery, and the rapid spread of CNC machine tools, high-speed machining and dry cutting have become the development trend of cutting processing, and the TiA1N and TiCN coatings have been difficult to meet. Modern industrial requirements for better performance of knife molds. SUMMARY OF THE INVENTION [0004] In view of the above, it is necessary to provide a coated member having a coating having higher hardness and wear resistance. [0005] In addition, it is also necessary to provide a method of preparing the above-mentioned coated member. [0006] A mineral film member comprising a metal substrate and a hard layer formed on a surface of the metal substrate, the hard layer being a composite film layer of chromium nitride-tantalum nitride. [0007] A method for preparing a coated member' includes the following steps: 099143852 Form No. A0101 Page 3 of 13 0992075907-0 201224177 [0008] Providing a metal substrate;
[0009] 採用真空濺鍍法在該金屬基體上濺鍍硬質層，該硬質層 為氮化鉻-氮化矽的複合膜層；濺鍍該硬質層同時開啟鉻 乾彳發乾，以鼠氣為反應氣體，絡乾的電源功率為1_2KW ’矽靶的電源功率為1 ο-12KW。 [〇〇1〇]相較於習知技術，所述的硬質層為氮化鉻-氮化矽的複合 膜層，由於氮化矽的硬度較高，而氮化鉻複合於氮化矽 中可起到位錯運動的效應，因此使得該硬質層具有更高 的硬度及更好的耐磨性。 ....... . 【實施方式】 [0011] 請參閱圖1，本發明一較佳實施方式的鍍膜件1〇包括金屬 ·:; -'.咚，,; 基體11及形成於金屬基體π上的硬質層1:5。 [0012] 金屬基體11的材質可為鋁 '鋁合金、鎂、鎂合金、不銹 鋼、硬質合金等。 [0013] 硬質層15為一氮化鉻（CrN )-氣化石夕( SiN)的複合膜 層’其可以真空滅鑛法形成，如磁揮濺射鍵膜法。該 CrN-SiN的複合膜層中cr的原子百分含量（at.%)為 10-15at. % ’ Si 為30-40at. %，N為45-60at. %。該硬質 層15的厚度為〇. 8_1. 5 /zin。 [0014] 該硬質層15中主要含有SiN相，該SiN相在該硬質層15中 為非晶態結構，其使得硬質層15具有較高的硬度；該硬 質層15中還含有CrN相，該CrN相在該硬質層15中為晶態 結構。CrN晶粒均勻分散或鑲嵌於SiN相中，該鑲嵌的 CrN晶粒可起到位錯運動的效應，可進—步提高硬質層15 099143852 表單編號A0101 第4頁/共13頁 0992075907-0 201224177 [0015] Ο [0016] [0017] [0018] 〇 [0019] [0020] [0021] [0022] 的硬度及耐磨性。 另外，由於物理氣相沉積的膜層在其晶界處通常存在微 小孔洞，該微小孔洞很容易成為腐蝕性介質侵入的“通 道”，而腐蝕基底。因此，當金屬基體11的材質為耐腐 蝕性能較差的鋁、鋁合金、鎂或鎂合金時，所述的鑲嵌 於SiN相中的CrN晶粒成為腐蝕性介質侵入硬質層15的“ 通道”中的阻礙物而阻擋腐蝕性介質的進入，從而還提 高了金屬基體11的耐腐蝕性能。 可以理解的，可在金屬基體11與硬質層15之間設置一過 渡層13，以提高硬質層15於金屬基體11的附著力。該過 渡層13可為一金屬絡層。 所述的鍍膜件10可為交通運輸、航空，航天，重機等領 域所需要用到的任意的刀模具。 本發明一較佳實施方式的鍍膜件10的製備方法包括如下 步驟： 提供一金屬基體11，並對該金屬基體11進行前處理。該 前處理可包括以下步驟： 依次用去離子水及無水乙醇對金屬基體11表面進行擦拭 〇 將金屬基體11放入盛裝有丙酮溶液的超聲波清洗器中進 行超聲波清洗，以除去金屬基體11表面的雜質和油污等 0 對經超聲波清洗後的金屬基體11的表面進行電漿清洗， 099143852 表單編號A0101 第5頁/共13頁 0992075907-0 201224177 以進一步去除金屬基體11表面的癖污，以及改善金屬基 體11表面與後續鍍層的結合力。 [0023] 請參閱圖2，將金屬基體11放入一真空濺鍍機20的鍍膜室 21中，裝入鉻靶23及矽靶25，抽真空該鍍膜室21至本底 真空度為8.0\103?8，然後通入流量為150-3003(：(；111( 標準毫升每分）的工作氣體氬氣（純度為99. 999%)，對 金屬基體11施加-300 — 500V的偏壓，使鍍膜室21中產生 高頻電壓，使所述氬氣產生氬氣電漿對金屬基體11的表 面進行物理轟擊，而達到對金屬基體11表面電漿清洗的 目的。所述電漿清洗的時間可為5-10分鐘。 [0024] 所述電漿清洗完成後，在所述鍍膜室21中以真空濺鍍法 ，如磁控濺射鍍膜法，在金屬基體11的表面濺鍍過渡層 13。濺鍍該過渡層13時，使所述鍍膜室21的溫度在 20-1 20°C之間（即濺鍍溫度為20-1 20°C )，保持上述氬 氣的流量不變，調節金屬基體11的偏壓至-15 0〜-500V， 開啟鉻靶23的電源，於金屬基體11的表面沉積過渡層13 。所述鉻靶23由直流電源控制，其功率為1-2KW。該過渡 層13為金屬鉻層，其厚度在200-400nm之間。沉積該過 渡層13的時間可為20-30分鐘。 [0025] 沉積所述過渡層13後，繼續以磁控濺射鍍膜法在過渡層 13的表面濺鍍硬質層15。濺鍍該硬質層15時，同時開啟 鉻靶23及矽靶25，保持鉻靶23的電源功率、金屬基體11 的偏壓、以及氬氣的流量不變，通入流量為40-60sccm 的反應氣體氮氣，並保持氮氣的分壓比為20-40%，沉積 所述硬質層15。沉積該硬質層15的時間可為60-8 0分鐘 099143852 表單編號A0101 第6頁/共13頁 0992075907-0 201224177 。所述矽靶25由射頻電源控制，其功率為1〇_12KW。該 硬質層15為CrN-SiN的複合膜層，其厚度為m ο [0026] 在沉積所述硬質層15的過程中，由於矽靶25的功率遠大 於鉻靶23的功率，因此硬質層15中主要形成SiN相，在此 條件下該SiN相無法獲得足夠的能量結晶，故為非晶態結 構。且由於鉻靶23與矽靶25同時濺射（或共濺射），並 產生的電漿團在金屬基體11表面附近可充分離化，使得 Ο 生成的CrN晶粒在SiN相中的分敏均勻，對硬質層a的硬 度及耐磨性能起到更奸ir提升作用〇 [0027] 以下結合具體實施例對鍍膜件1 (Γ的製備方法友鍍膜件工〇 進行說明： [0028] 實施例1 [0029] 電漿清洗：氬氣流量為280sccm，金屬基體11的偏壓為一 300V，電漿清洗的時間為9分鐘； 〇 [0030] 濺鍍過渡層13 :氬氣流量表MOsccm，金屬基體11的偏 壓為-450V，鉻靶23的功率為1. 8KW，濺鍍溫度為100°C ，濺鍍時間為28分鐘，過渡層13的厚度為370nm ; [0031] 濺锻硬質層15 :氬氣流量為280sccm，氮氣流量為 55sccm，金屬基體11的偏壓為-450V，鉻靶23的功率為 1. 8KW，矽靶25的功率為12KW，濺鍍溫度為100°C，濺鍍 時間為75分鐘，硬質層15的厚度為1.3/im，硬質層15中 Cr的原子百分含量為，Si為40at·% ’ N為46at.% 099143852 ο 表單編號Α0101 第7頁/共13頁 0992075907-0 201224177 [0032] 實施例2 [0033] 電紫清洗：氬氣流量為230sccm，金屬基體11的偏壓為-480V ’電漿清洗的時間為7分鐘； [0034] 錢鍍過渡層13 :氬氣流量為23〇sccm，金屬基體11的偏 壓為-2 30V，鉻靶23的功率為1. 5KW，濺鍍溫度為7(TC， 漱鍍時間為25分鐘，過渡層13的厚度為280nm ; [0035] 錢鑛硬質層15 :氬氣流量為23〇sccm，氮氣流量為 50sccm，金屬基體11的偏壓為-230V，鉻靶23的功率為 1. 5KW，矽靶2δ的功率為llKf，濺鍍溫度為7〇t：，濺鍍 時間為70分鐘’硬質層1 5的厚度為1. 1以，硬質層15中 Cr的原子百分含量為i3at. %，Si為37at. %，N為50at. % o . ' [0036] 實施例3 [0〇37]電漿清洗：氬氣流量為160sccm，金屬基犛11的偏壓為-400V，電漿清洗的時間為6分鐘； [0038] 濺鍍過渡層13 :氬氣流量為i6〇sccm，金屬基體丨丨的偏 壓為-160V，鉻靶23的功率為1. 2KW，濺鍍溫度為3(TC， 賤鍍時間為22分鐘，過渡層13的厚度為220nm ; [0039] 減錄硬質層15 :氬氣流量為160sccm，氮氣流量為 42sccm ’金屬基體11的偏壓為-160V，鉻靶23的功率為 1. 2KW，矽靶25的功率為10KW，濺鍍溫度為3(TC，濺鍍 時間為65分鐘’硬質層15的厚度為0.9/ζιη，硬質層15中 Cr的原子百分含量為i3at·% ’ Si為38at.%，N為49at.% 099143852 表單編號A0101 第8頁/共13頁 0992075907-0 201224177 [0040] ❹ [0041] [0042] [0043] [0044] 〇 [0045] [0046] [0047] [0048] [0049] [0050] 相較於習知技術，所述鍍膜件10的製備方法以共濺射的 方式，藉由控制鉻靶23及矽靶25的濺射功率，使SiN相形 成為非晶態結構及主要的相，提高了硬質層15的硬度， 同時使CrN晶粒均勻分散於SiN相中，產生位錯運動效應 ，進一步提高了硬質層15的硬度及耐磨性。且所述硬質 層15還具有防腐蝕的功能，可有效的保護金屬基體11免 受侵蝕，延長了鍍膜件10的使用壽命，提高了鍍膜件10 的使用價值。 【圖式簡單說明】 圖1係本發明一較佳實施方式的鍍膜件的剖視示意圖。 圖2係本發明一較佳實施方式的真空濺鍍機的示意圖。 【主要元件符號說明】 鍍膜件：10 金屬基體：11 過渡層：13 硬質層：15 真空濺鍍機：20 鍍膜室：21 鉻靶：23 矽乾：25 099143852 表單編號A0101 第9頁/共13頁 0992075907-0[0009] a hard layer is sputtered on the metal substrate by vacuum sputtering, the hard layer is a composite film layer of chromium nitride-tantalum nitride; the hard layer is sputtered while the dry chrome is dried, and the mouse is made For the reaction gas, the power supply of the network is 1_2KW. The power supply of the target is 1 ο-12KW. [〇〇1〇] Compared with the prior art, the hard layer is a composite film of chromium nitride-tantalum nitride, and the chromium nitride is composited in tantalum nitride due to the higher hardness of tantalum nitride. It can play the role of dislocation motion, thus making the hard layer have higher hardness and better wear resistance. [0011] Referring to FIG. 1, a coated member 1 of a preferred embodiment of the present invention includes a metal:: -'.咚,;; a substrate 11 and a metal formed thereon The hard layer on the substrate π is 1:5. [0012] The material of the metal base 11 may be aluminum 'aluminum alloy, magnesium, magnesium alloy, stainless steel, hard alloy, or the like. [0013] The hard layer 15 is a chromium nitride (CrN)-gas hydride (SiN) composite film layer which can be formed by a vacuum ore mining method such as a magnetic sputtering sputtering film method. The atomic percentage (at.%) of cr in the composite film layer of CrN-SiN is 10-15 at. % ' Si is 30-40 at. %, and N is 45-60 at. %. The thickness of the hard layer 15 is _1. 8_1. 5 /zin. [0014] The hard layer 15 mainly contains a SiN phase, and the SiN phase has an amorphous structure in the hard layer 15, which makes the hard layer 15 have a high hardness; the hard layer 15 further contains a CrN phase, The CrN phase has a crystalline structure in the hard layer 15. The CrN grains are uniformly dispersed or embedded in the SiN phase, and the embedded CrN grains can play the role of dislocation motion, and the hard layer can be further improved. 15 099143852 Form No. A0101 Page 4 / Total 13 Page 0992075907-0 201224177 [ 0015] 硬度 [0016] [0018] [0020] [0022] [0022] hardness and wear resistance. In addition, since the physical vapor deposited film layer usually has micropores at its grain boundaries, the microscopic holes easily become "channels" for the intrusion of corrosive media and corrode the substrate. Therefore, when the material of the metal substrate 11 is aluminum, aluminum alloy, magnesium or magnesium alloy having poor corrosion resistance, the CrN crystal grains embedded in the SiN phase become a "channel" in which the corrosive medium intrudes into the hard layer 15. The obstruction blocks the entry of corrosive media, thereby also improving the corrosion resistance of the metal substrate 11. It can be understood that a transition layer 13 can be provided between the metal substrate 11 and the hard layer 15 to improve the adhesion of the hard layer 15 to the metal substrate 11. The transition layer 13 can be a metal layer. The coating member 10 can be any knife mold required for transportation, aviation, aerospace, heavy machinery and the like. A method of fabricating a coated member 10 according to a preferred embodiment of the present invention includes the steps of: providing a metal substrate 11 and pretreating the metal substrate 11. The pretreatment may include the following steps: sequentially wiping the surface of the metal substrate 11 with deionized water and absolute ethanol, and placing the metal substrate 11 in an ultrasonic cleaner containing an acetone solution for ultrasonic cleaning to remove the surface of the metal substrate 11. Impurities, oil stains, etc. 0 Plasma cleaning of the surface of the ultrasonically cleaned metal substrate 11, 099143852 Form No. A0101 Page 5 of 13 0992075907-0 201224177 To further remove the stain on the surface of the metal substrate 11, and to improve the metal The bonding force between the surface of the substrate 11 and the subsequent plating layer. Referring to FIG. 2, the metal substrate 11 is placed in the coating chamber 21 of a vacuum sputtering machine 20, and the chromium target 23 and the target 25 are loaded, and the coating chamber 21 is evacuated to a background vacuum of 8.0. 103?8, then a flow rate of 150-3003 (: (; 111 (standard milliliters per minute) of working gas argon (purity of 99.999%) is applied, and a bias voltage of -300 - 500V is applied to the metal substrate 11, A high-frequency voltage is generated in the coating chamber 21, and the argon gas generates an argon plasma to physically bombard the surface of the metal substrate 11 to achieve the purpose of cleaning the surface of the metal substrate 11. The plasma cleaning time [0024] After the plasma cleaning is completed, the transition layer 13 is sputtered on the surface of the metal substrate 11 by vacuum sputtering, such as magnetron sputtering coating, in the coating chamber 21. When the transition layer 13 is sputtered, the temperature of the coating chamber 21 is between 20 and 20 ° C (ie, the sputtering temperature is 20-1 20 ° C), and the flow rate of the argon gas is kept unchanged. The metal substrate 11 is biased to -15 0 to -500 V to turn on the power of the chrome target 23, and a transition layer 13 is deposited on the surface of the metal substrate 11. The chrome target 23 is straight The power supply control has a power of 1-2 KW. The transition layer 13 is a metal chromium layer having a thickness of between 200 and 400 nm. The time for depositing the transition layer 13 may be 20-30 minutes. [0025] depositing the transition layer After 13 , the hard layer 15 is sputtered on the surface of the transition layer 13 by magnetron sputtering. When the hard layer 15 is sputtered, the chromium target 23 and the target 25 are simultaneously turned on to maintain the power and metal of the chromium target 23 . The bias voltage of the substrate 11 and the flow rate of the argon gas are constant, a reaction gas nitrogen gas having a flow rate of 40-60 sccm is introduced, and a partial pressure ratio of nitrogen gas is maintained at 20-40%, and the hard layer 15 is deposited. The hard layer is deposited. The time of 15 can be 60-8 0 minutes 099143852 Form No. A0101 Page 6 / Total 13 page 0992075907-0 201224177. The target 25 is controlled by a radio frequency power source, and its power is 1〇_12KW. The hard layer 15 is CrN. a composite film layer of -SiN having a thickness of m [0026] In the process of depositing the hard layer 15, since the power of the target 25 is much larger than the power of the chromium target 23, a SiN phase is mainly formed in the hard layer 15. Under this condition, the SiN phase cannot obtain sufficient energy to crystallize, so it is an amorphous structure. The chromium target 23 is simultaneously sputtered (or co-sputtered) with the tantalum target 25, and the resulting plasma mass is sufficiently ionized near the surface of the metal substrate 11, so that the partial distribution of the CrN grains formed by the niobium in the SiN phase is uniform. The hardness and wear resistance of the hard layer a are further enhanced. [0027] Hereinafter, the coating member 1 (the preparation method of the coating method) will be described in conjunction with the specific embodiment: [0028] Example 1 [0029] Plasma cleaning: argon gas flow rate is 280 sccm, metal substrate 11 has a bias voltage of 300 V, plasma cleaning time is 9 minutes; 〇 [0030] Sputtering transition layer 13: argon flow meter MOsccm, metal matrix 11 has a bias voltage of -450 V, a chromium target 23 has a power of 1. 8 KW, a sputtering temperature of 100 ° C, a sputtering time of 28 minutes, and a thickness of the transition layer 13 of 370 nm; [0031] a sputtered hard layer 15: The flow rate of argon gas is 280 sccm, the flow rate of nitrogen gas is 55 sccm, the bias voltage of the metal substrate 11 is -450 V, the power of the chromium target 23 is 1. 8 KW, the power of the target 25 is 12 KW, the sputtering temperature is 100 ° C, and the sputtering time is For 75 minutes, the thickness of the hard layer 15 is 1.3 / im, the atomic percentage of Cr in the hard layer 15 is 40, Si is 40 at % ' N is 46 at. % 099143852 ο Form No. 101 0101 Page 7 / Total 13 Page 0992075907-0 201224177 [0032] Example 2 [0033] Electro violet cleaning: argon flow rate is 230 sccm, metal substrate 11 bias is - The volts of the chrome target 23 is 1. 5KW, splashed. The volts of the metal substrate 11 is -2 30V, the power of the chrome target 23 is 1. 5KW, splashing The plating temperature is 7 (TC, the plating time is 25 minutes, and the thickness of the transition layer 13 is 280 nm; [0035] the hard ore layer 15: the argon flow rate is 23 〇sccm, the nitrogen flow rate is 50 sccm, and the bias of the metal substrate 11 The power of the hard layer 15 is 1. 1 ,, the thickness of the hard layer 15 is 1. 以, the sputtering temperature is 〇Kf, the sputtering temperature is 7 〇t:, the sputtering time is 70 minutes. The atomic percentage of Cr in the hard layer 15 is i3 at. %, Si is 37 at. %, and N is 50 at. % o . ' [0036] Example 3 [0〇37] Plasma cleaning: argon flow rate is 160 sccm, The metal base 11 has a bias voltage of -400 V and a plasma cleaning time of 6 minutes; [0038] Sputtering transition layer 13: argon flow rate is i6 〇 sccm, metal substrate 丨丨 bias is -160 V, chrome target twenty three The power is 1. 2KW, the sputtering temperature is 3 (TC, the plating time is 22 minutes, the thickness of the transition layer 13 is 220 nm; [0039] the hard layer 15 is reduced: the argon flow rate is 160 sccm, and the nitrogen flow rate is 42 sccm ' The metal substrate 11 has a bias of -160 V, the chrome target 23 has a power of 1. 2 KW, the target 25 has a power of 10 KW, and the sputtering temperature is 3 (TC, the sputtering time is 65 minutes. The thickness of the hard layer 15 is 0.9. /ζιη, the atomic percentage of Cr in the hard layer 15 is i3at·% 'Si is 38at.%, N is 49at.% 099143852 Form No. A0101 Page 8/Total 13 Page 0992075907-0 201224177 [0040] ❹ [0041 [0049] [0050] [0050] [0050] [0050] [0050] Compared to the prior art, the coating member 10 is prepared by co-sputtering By controlling the sputtering power of the chromium target 23 and the target 25, the SiN phase is formed into an amorphous structure and a main phase, the hardness of the hard layer 15 is improved, and the CrN grains are uniformly dispersed in the SiN phase, resulting in uniform generation. The dislocation motion effect further improves the hardness and wear resistance of the hard layer 15. Moreover, the hard layer 15 also has an anti-corrosion function, which can effectively protect the metal substrate 11 from corrosion, prolong the service life of the coated member 10, and improve the use value of the coated member 10. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a cross-sectional view showing a coated member according to a preferred embodiment of the present invention. 2 is a schematic view of a vacuum sputtering machine in accordance with a preferred embodiment of the present invention. [Main component symbol description] Coated parts: 10 Metal substrate: 11 Transition layer: 13 Hard layer: 15 Vacuum sputtering machine: 20 Coating chamber: 21 Chromium target: 23 Dry: 25 099143852 Form No. A0101 Page 9 of 13 Page 0992075907-0