201217560 六、發明說明： 【發明所屬之技術領域】 [0001] 本發明涉及一種锻膜件及該鍍膜件的製備方法。 【先前技術】 [0002] 有害細菌的傳播和感染嚴重威脅著人類的健康，尤其近 年來SARS病毒、禽流感等的傳播和感染，使抗菌材料在 曰常生活中的應用迅速發展起來。將抗菌金屬（Cu、Zn、 Ag等）塗覆於基材上形成抗菌鍍膜件在目前市場上有著廣 泛的應用。該抗菌鍵膜件的殺菌機理為：锻膜件在使用 過程中，抗菌金屬塗層會緩慢轉放出金屬離子WCu2+、 Zn2+，當微量的具有殺菌性的金屬離子與細满等微生物 接觸時，該金屬離子依靠庫倫力與帶有負電荷的微生物 牢固吸附，金屬離子穿透細胞壁與細菌體内蛋白質上的 巯基、氨基發生反應’使蛋白質活性破壞，使細胞喪失 分裂增殖能力而死亡，從而達到殺菌的目的。 酬3]然該類金屬抗菌塗層厚度通常比較缚，且表面硬度較低 容易磨知’從而降低了金屬抗:牵丨塗層的抗菌持久性。 【發明内容】 [0004] 有鑒於此，有必要提供一種抗菌效果較為持久的鍍膜件 〇 [0005] 另外，還有必要提供一種上述鍍臈件的製備方法。 [0006] 一種鍵膜件’其包括基材、形成於基材表面的打底層， 該打底層為Cr層，該鍍膜件還包括形成於打底層表面的 複數CrN層和複數Cu-Ti合金層，該複數CrN層和複數Cu. 099136032 表單編號A0101 第4頁/共12頁 0992062997-0 201217560201217560 VI. Description of the Invention: [Technical Field of the Invention] [0001] The present invention relates to a forged film member and a method of preparing the coated member. [Prior Art] [0002] The spread and infection of harmful bacteria is a serious threat to human health. Especially in recent years, the spread and infection of SARS virus, avian flu, etc., have rapidly developed the application of antibacterial materials in normal life. The application of antibacterial metals (Cu, Zn, Ag, etc.) on substrates to form antibacterial coated parts has a wide range of applications on the market. The sterilization mechanism of the antibacterial membrane member is: during the use of the forged membrane member, the antibacterial metal coating will slowly transfer the metal ions WCu2+, Zn2+, when a trace amount of bactericidal metal ions are in contact with microorganisms such as fine particles, Metal ions rely on Coulomb force and negatively charged microorganisms to firmly adsorb. Metal ions penetrate the cell wall and react with the sulfhydryl groups and amino groups on the proteins in the bacteria' to destroy the protein activity and cause the cells to lose their ability to divide and proliferate and die. the goal of. Remuneration 3] Although the thickness of such metal antibacterial coatings is usually relatively limited, and the surface hardness is low, it is easy to wear, thus reducing the metal resistance: antibacterial durability of the traction coating. SUMMARY OF THE INVENTION [0004] In view of the above, it is necessary to provide a coating member having a relatively long-lasting antibacterial effect. [0005] In addition, it is also necessary to provide a method for preparing the above-described rhodium-plated member. [0006] A key film member includes a substrate, a primer layer formed on a surface of the substrate, the primer layer is a Cr layer, and the coating member further includes a plurality of CrN layers and a plurality of Cu-Ti alloy layers formed on the surface of the primer layer. , the plural CrN layer and the plural Cu. 099136032 Form number A0101 Page 4 / Total 12 pages 0992062997-0 201217560
Ti合金層交替排布。 [0007] —種鍍膜件的製備方法，其包括如下步驟： [0008] 提供一基材； [0009] 在該基材的表面形成打底層，該打底層為Cr層； [0010] 在該打底層的表面形成CrN層； [0011] 在該CrN層的表面形成Cu-Ti合金層； [0012] 重複交替形成CrN層和Cu-Ti合金層以形成最外層為CrN 層的鍍膜件。 [0013] 本發明所述鍍膜件在基材表面交替濺鍍CrN層和Cu-Ti合 金層，CrN層形成為疏鬆多孔的結構，而使Cu-Ti合金層 的部分嵌入到該CrN層中，對Cu-Ti合金層中Cu離子的快 速溶出起到阻礙作用，從而可緩釋Cu金屬離子的溶出， 使Cu-Ti合金層具有長效的抗菌效果；同時Cu-Ti合金層 中的Ti與空氣中的氧氣接觸可生成具有抗菌效果的Ti〇2 ，可強化Cu-Ti合金層的抗菌效果。 【實施方式】 [0014] 請參閱圖1，本發明一較佳實施方式的鍍膜件100包括基 材10、形成於基材10表面的打底層20，形成於打底層20 表面的複數CrN層30和複數Cu-Ti合金層40，該複數CrN 層30和複數Cu-Ti合金層40交替排布，其中與所述打底 層20直接相結合的為CrN層30，最外層為CrN層30。所述 複數CrN層30和複數Cu-Ti合金層40的總厚度可為1〜8" m。本實施例中，所述複數CrN層30和複數Cu-Ti合金詹 099136032 表單編號A0101 第5頁/共12頁 0992062997-0 201217560 40的層數可分別為5〜20層。 [0015] 該基材10的材質可為不銹鋼或含Cr的合金。 [0016] 該打底層2 0可以磁控濺射的方式形成。該打底層為一 Cr 層。該打底層20的厚度可為100〜200nm。 [0017] 該複數CrN層30可以磁控濺射的方式形成。所述每一 CrN 層30的厚度可為50〜lOOnm。濺鍍該CrN層30時採用較低 的沉積溫度和沉積偏壓，使CrN層30具有更好的疏鬆多孔 的結構，可使所述Cu-Ti合金層40的部分嵌入到該CrN層 30中。 [0018] 該複數Cu-Ti合金層40可以磁控濺射的方式形成。所述每 一Cu-Ti合金層40的厚度可為200〜300nm。在每一Cu-Ti 合金層 40 與相鄰的每一 CrN層 30 的介面處， 有部分 Cu-Ti合金層40拔入到CrN層30中，從而對Cu-Ti合金層40 起到固持的作用，並可緩釋Cu金屬離子的溶出，使Cu-Ti 合金層40具有長效的抗菌效果。 [0019] 本發明一較佳實施方式的鍍膜件100的製備方法，其包括 如下步驟： [0020] 提供一基材10，該基材10的材質可為不銹鋼或含Cr的合 金。 [0021] 對該基材10進行表面預處理。該表面預處理可包括常規 的對基材10進行拋光、無水乙醇超聲波清洗及烘乾等步 驟。 [0022] 對經上述處理後的基材10的表面進行氬氣電漿清洗，以 099136032 表單編號A0101 第6頁/共12頁 0992062997-0 201217560 [0023] Ο [0024] ❹ 099136032 進一步去除基材10表面殘留的雜質，以及改善基材1〇表 面與後續鍍層的結合力。具體操作及工藝參數為：將基 材10放入一磁控濺射鍍膜機（圖未示）的鍍臈室内，將該 鑛膜室抽真空至3x10 5torr，然後向鍍膜室内通入流量 為100〜300sccin(標準狀態毫升/分鐘）的氬氣（純度為 99. 999%)，並施加-200〜-800V的偏壓於基材1 〇，對基 材10表面進行氬氣電漿清洗，清洗時間為3〜。 採用磁控濺射法在經氬氣電漿清洗後的基材1〇的表面濺 鍍一打底層20 ’該打底層20可為一鉻層。濺鍍該打底層 20在所述磁控濺射鍍膜機中進行。使用金屬鉻靶，所述 鉻靶採用直流磁控電源。濺鍍時，開啟鉻靶，通入工作 氣體氬氣，氬氣流量可為1〇〇〜300sccm，對基材10施加 -50〜-150V的偏壓，鍍膜室的溫度可為80〜150°C，鍍 膜時間可為5〜lOmin。該打底層20的庠度可為1〇〇〜 200nm。 繼續採用磁控濺射法在所述打底層20的表面濺鍵一CrN層 30。使用金屬鉻靶，所述鉻靶採用直流磁控電源。濺鍍 時’開啟鉻靶’通入反應氣體氮氣，氮氣流量可為1〇〜 20sccm ’通入工作氣體氬氣，氬氣流量可為2〇〜5〇sccm ’對基材10施加直流偏壓，直流偏壓大小可為-50〜- 150V，基材10的溫度可為70〜130°C，鍍膜時間可為2〜 3min。該CrN層30的厚度可為50〜l〇〇nm。濺鍍該CrN層 30採用較低的沉積溫度和較低的沉積偏壓，可使CrN層30 達到較好的疏鬆多孔的結構。 繼續採用磁控濺射法在所述CrN層30的表面濺鍍一Cu-Ti 第7黃/共12真 表單編號A0101 0992062997-0 [0025] 201217560 合金層40。使用銅鈦合金靶，所述銅鈦合金靶中銅的質 量百分含量為80%〜90%，所述銅鈦合金靶採用射頻磁控 電源。濺鍍時，開啟銅鈦合金靶，通入工作氣體氬氣， 氬氣流量可為20〜50sccm，對基材施加编合脈衝偏壓， 搞合脈衝偏壓大小可為-180〜- 350V，脈衝頻率為ΙΟΚΗζ ，脈衝寬度為20;zs，基材10的溫度可為70〜130°C，鍍 膜時間可為2〜3min。該Cu-Ti合金層40的厚度可為200 〜300nm。 [0026] 參照上述步驟，重複交替濺鍍CrN層30和Cu-Ti合金層40 ，且最外層為CrN層30。交替濺鍍的次數總共可為5〜20 次。所述複數CrN層30和複數Cu-Ti合金層40的總厚度可 為1〜8 /z m。 [0027] 所述鍍膜件100在基材10表面交替濺鍍有CrN層30和Cu-Ti 合金層 40 ， CrN 層 30 形成為疏鬆多孔的結構 ，可使 Cu-Ti 合金層 40 的 部分嵌入到該 CrN 層 30 中 ，對Cu-Ti 合金層 40中Cu離子的快速溶出起到阻礙作用，從而可緩釋Cu金 屬離子的溶出，使Cu-Ti合金層40具有長效的抗菌效果； 另外Cu-Ti合金層40中的Ti與空氣中的氧氣接觸可生成 具有抗菌效果的Ti〇2，可強化Cu-Ti合金層40的抗菌效 果；同時CrN層30具有良好的耐磨性、耐腐蝕性能以及色 澤美觀等特點，因而在整個膜層的最外層鍍上CrN層30有 助於提升鍍膜件100的耐磨性及美觀性，可延長鍍膜件 1 0 0的使用壽命。 【圖式簡單說明】 [0028] 圖1為本發明一較佳實施例鍍膜件的剖視圖。 099136032 表單編號A0101 第8頁/共12頁 0992062997-0 201217560 【主要元件符號說明】 [0029] 鍍膜件：100 [0030] 基材：10 [0031] 打底層：20 [0032] CrN層：30 [0033] Cu_Ti 合金層：40The Ti alloy layers are alternately arranged. [0007] A method for preparing a coated member, comprising the steps of: [0008] providing a substrate; [0009] forming a primer layer on a surface of the substrate, the primer layer being a Cr layer; A surface of the underlayer forms a CrN layer; [0011] a Cu-Ti alloy layer is formed on the surface of the CrN layer; [0012] The CrN layer and the Cu-Ti alloy layer are alternately formed to form a plated member having the outermost layer of the CrN layer. [0013] The coated member of the present invention alternately sputters a CrN layer and a Cu-Ti alloy layer on the surface of the substrate, and the CrN layer is formed into a loose porous structure, and a part of the Cu-Ti alloy layer is embedded in the CrN layer. It can hinder the rapid dissolution of Cu ions in the Cu-Ti alloy layer, so as to release the dissolution of Cu metal ions and make the Cu-Ti alloy layer have a long-lasting antibacterial effect. At the same time, Ti in the Cu-Ti alloy layer Contact with oxygen in the air produces Ti〇2 with an antibacterial effect, which enhances the antibacterial effect of the Cu-Ti alloy layer. [0014] Referring to FIG. 1, a coated article 100 according to a preferred embodiment of the present invention includes a substrate 10, a primer layer 20 formed on the surface of the substrate 10, and a plurality of CrN layers 30 formed on the surface of the primer layer 20. And a plurality of Cu-Ti alloy layers 40, the plurality of CrN layers 30 and the plurality of Cu-Ti alloy layers 40 are alternately arranged, wherein the primer layer 20 is directly bonded to the CrN layer 30, and the outermost layer is the CrN layer 30. The total thickness of the plurality of CrN layers 30 and the plurality of Cu-Ti alloy layers 40 may be 1 to 8 " m. In this embodiment, the plurality of CrN layers 30 and the plurality of Cu-Ti alloys Zhan 099136032 Form No. A0101 Page 5 / Total 12 pages 0992062997-0 201217560 40 layers can be 5 to 20 layers, respectively. [0015] The material of the substrate 10 may be stainless steel or an alloy containing Cr. [0016] The underlayer 20 can be formed by magnetron sputtering. The underlayer is a Cr layer. The underlayer 20 may have a thickness of 100 to 200 nm. [0017] The plurality of CrN layers 30 may be formed by magnetron sputtering. Each of the CrN layers 30 may have a thickness of 50 to 100 nm. When the CrN layer 30 is sputtered, a lower deposition temperature and a deposition bias are used, so that the CrN layer 30 has a better porous structure, and a portion of the Cu-Ti alloy layer 40 can be embedded in the CrN layer 30. . [0018] The plurality of Cu-Ti alloy layers 40 may be formed by magnetron sputtering. Each of the Cu-Ti alloy layers 40 may have a thickness of 200 to 300 nm. At the interface of each Cu-Ti alloy layer 40 and each adjacent CrN layer 30, a portion of the Cu-Ti alloy layer 40 is pulled into the CrN layer 30 to hold the Cu-Ti alloy layer 40. The action and the slow release of Cu metal ions are eluted, so that the Cu-Ti alloy layer 40 has a long-lasting antibacterial effect. A method for preparing a coated member 100 according to a preferred embodiment of the present invention includes the following steps: [0020] A substrate 10 is provided, which may be made of stainless steel or a Cr-containing alloy. [0021] The substrate 10 is subjected to surface pretreatment. The surface pretreatment may include conventional steps of polishing the substrate 10, ultrasonic cleaning with anhydrous ethanol, and drying. [0022] The surface of the substrate 10 after the above treatment is subjected to argon plasma cleaning to 099136032 Form No. A0101 Page 6 / Total 12 Page 0992062997-0 201217560 [0023] Ο [0024] ❹ 099136032 Further removal of the substrate 10 residual impurities on the surface, as well as improving the bonding force between the substrate 1 surface and the subsequent plating layer. The specific operation and process parameters are as follows: the substrate 10 is placed in a rhodium plating chamber of a magnetron sputtering coating machine (not shown), and the membrane chamber is evacuated to 3×10 5 torr, and then the flow rate into the coating chamber is 100. Argon gas (purity of 99.999%) of ~300sccin (standard state ML/min), and applying a bias of -200 to -800V to the substrate 1 〇, argon plasma cleaning of the surface of the substrate 10, cleaning The time is 3~. The surface of the substrate 1 after the argon plasma cleaning is sputtered by a magnetron sputtering method. The underlayer 20' may be a chromium layer. Sputtering the underlayer 20 is carried out in the magnetron sputtering coater. A metallic chromium target is used, which uses a DC magnetron power supply. During sputtering, the chromium target is turned on, and the working gas argon gas is introduced. The flow rate of the argon gas may be 1 〇〇 300 300 cm, and the substrate 10 is biased by -50 to -150 V, and the temperature of the coating chamber may be 80 to 150 °. C, the coating time can be 5~10 min. The thickness of the underlayer 20 can be from 1 〇〇 to 200 nm. A CrN layer 30 is sputter-bonded to the surface of the underlayer 20 by magnetron sputtering. A metallic chromium target is used, which uses a DC magnetron power supply. When sputtering, 'turn on the chromium target', the reaction gas is introduced into the nitrogen gas. The flow rate of nitrogen gas can be 1〇~20sccm. 'The working gas is argon gas. The flow rate of argon gas can be 2〇~5〇sccm'. Apply DC bias to the substrate 10. The DC bias voltage may be -50 to -150V, the substrate 10 may have a temperature of 70 to 130 ° C, and the coating time may be 2 to 3 minutes. The CrN layer 30 may have a thickness of 50 to 1 〇〇 nm. Sputtering the CrN layer 30 with a lower deposition temperature and a lower deposition bias allows the CrN layer 30 to achieve a better porous structure. The surface of the CrN layer 30 is continuously sputtered by a magnetron sputtering method to form a Cu-Ti film 7 yellow/total 12 form number A0101 0992062997-0 [0025] 201217560 alloy layer 40. A copper-titanium alloy target having a mass percentage of copper in the copper-titanium alloy target of 80% to 90% is used, and the copper-titanium alloy target is a radio frequency magnetron power source. During sputtering, the copper-titanium alloy target is turned on, and the working gas argon gas is introduced. The flow rate of the argon gas may be 20 to 50 sccm, and a pulsed bias voltage is applied to the substrate, and the pulse bias voltage may be -180 to 350V. The pulse frequency is ΙΟΚΗζ, the pulse width is 20; zs, the temperature of the substrate 10 can be 70~130 ° C, and the coating time can be 2~3 min. The Cu-Ti alloy layer 40 may have a thickness of 200 to 300 nm. Referring to the above steps, the CrN layer 30 and the Cu-Ti alloy layer 40 are alternately sputter-sputtered, and the outermost layer is the CrN layer 30. The number of alternate sputterings can be 5 to 20 times in total. The total thickness of the plurality of CrN layers 30 and the plurality of Cu-Ti alloy layers 40 may be 1 to 8 /z m. [0027] The coating member 100 alternately sputters a CrN layer 30 and a Cu-Ti alloy layer 40 on the surface of the substrate 10, and the CrN layer 30 is formed into a loose porous structure, and a portion of the Cu-Ti alloy layer 40 can be embedded therein. In the CrN layer 30, the rapid elution of Cu ions in the Cu-Ti alloy layer 40 is hindered, so that the dissolution of Cu metal ions can be sustainedly released, and the Cu-Ti alloy layer 40 has a long-lasting antibacterial effect; The Ti in the Ti alloy layer 40 is in contact with oxygen in the air to form Ti〇2 having an antibacterial effect, which can enhance the antibacterial effect of the Cu-Ti alloy layer 40; and the CrN layer 30 has good wear resistance and corrosion resistance. The color and the appearance of the color, so that the outermost layer of the entire layer of the CrN layer 30 helps to improve the wear resistance and aesthetics of the coated member 100, and can extend the service life of the coated member 100. BRIEF DESCRIPTION OF THE DRAWINGS [0028] FIG. 1 is a cross-sectional view of a coated member according to a preferred embodiment of the present invention. 099136032 Form No. A0101 Page 8 / Total 12 Page 0992062997-0 201217560 [Description of main component symbols] [0029] Coated member: 100 [0030] Substrate: 10 [0031] Underlayer: 20 [0032] CrN layer: 30 [ 0033] Cu_Ti alloy layer: 40
099136032 表單編號A0101 第9頁/共12頁 0992062997-0099136032 Form number A0101 Page 9 of 12 0992062997-0