201229271 六、發明說明： 【發明所屬之技術領域】 [0001] 本發明涉及一種被覆件及其製造方法。 [先前技術] [0002] 碳纖維由於其具有低密度、高強度、高模量、低熱膨脹 係數、耐腐蝕、易編織加工以及較好的熱、電性能等優 良特性被廣泛用於航天航空、建築及電子元器件製造等 領域。然，碳纖維的抗氧化性能較差，且與金屬、X八201229271 VI. Description of the Invention: [Technical Field of the Invention] [0001] The present invention relates to a covering member and a method of manufacturing the same. [Prior Art] [0002] Carbon fiber is widely used in aerospace, construction due to its low density, high strength, high modulus, low coefficient of thermal expansion, corrosion resistance, easy weaving, and good thermal and electrical properties. And the field of electronic components manufacturing. However, the carbon fiber has poor oxidation resistance and is compatible with metal and X8.
物複合材料的潤濕性不佳，大大限制了碳纖維材料2 述領域的應用。 ... '。.....：.......The poor wettability of the composite material greatly limits the application of the carbon fiber material. ... '. .....:.......
[0003] 習知技術利用化學氣相沉積技術（cvp)將碳纖維 與ZrB2相結合形成Cf/ZrB2a合材料，該種Cf/ZrB(2 ) 材料具有優良的機械性能及勃性，然其高溫抗斤合 差。 匕性較 _4]貴金屬鉉（Ir) '辕點2443〇c，因飽和蒸氣壓低、& 率低而具有優良的高溫抗乳化性能，係唯-在16:滲透 上的空氣中仍具♦彳良好機械性能的金屬。由於t 銀塗層之間職性較差，沉積於碳纖崎料上的=維與 經高溫處理後會產生大量裂紋，因此所述銀塗層二塗層 抗氧化性及抗熱震性能較差。 的兩溫 【發明内容】 _5]鑒於此，提供-氆有效解決上述問題的被覆件。 _]料，還提供1上述被覆件的製造方法。 圃—種被覆件，包#基體、依次形成於該基體上的路渗入 100100110 表單編號A0101 第3頁/共12頁 201229271 層、鉻層及銥層，該基體材質為碳纖維/ZrB2複合材料。 [0008] 一種被覆件的製造方法，包括以下步驟： [0009] 提供基體，該基體材質為碳纖維/ZrB2複合材料； [0010] 以鉻靶為靶材，於所述基體表面磁控濺射鉻層，濺射溫 度為100〜200°C，濺射時間為150〜250min ;在磁控濺射 該鉻層的過程中，該鉻層與基體介面處的金屬鉻向基體 擴散，於基體與鉻層之間形成鉻滲入層； [0011] 以銥靶為靶材，於所述鉻層上磁控濺射形成銥層。 [0012] 所述鉻層的形成可提高所述銥層與基體之間的結合力， 使被覆件經高溫處理後銥層不易剝落或裂紋，如此可提 高所述銥層的高溫抗氧化性能。此外，藉由上述製造方 法形成的銥層幾乎無針孔、具有良好的緻密性，如此可 進一步提高所述銥層的抗氧化性。 [0013] 所述銥層還具有良好的抗熱震性能，主要有如下兩方面 的原因：一方面，由於所述鉻層從由靠近該基體至遠離 該基體的方向呈梯度過渡，沒有成分和力學性能的突變 :另一方面，所述銥層與鉻層之間過渡較好，沒有成分 和力學性能的突變。 [0014] 故，所述被覆件具有良好的高溫抗氧化性及抗熱震性。 【實施方式】 [0015] 請參閱圖1，本發明一較佳實施例的被覆件10包括基體11 、依次形成於該基體11上的鉻滲入層13、鉻層15及銥層 17。該被覆件10可為渦輪葉片、喷嘴等航天航空機械零 100100110 表單編號A0101 第4頁/共12頁 1002000192-0 201229271 [0016] [0017] Ο [0018] [0019] [0020] Ο [0021] 100100110 4件’亦可為建築、電子及汽車等交通工具的零部件。 該基體11的材質為碳纖維/ZrB2複合材料。 所述路層15及銥層17均可藉由磁控濺射鍍膜法形成。所 述路層15的厚度為2~3. 5 ym。所述銥層π的厚度為 2〜3. 。 所述鉻滲入層13係在所述鉻層15的形成過程中，鉻層15 與基體11介面處的金屬鉻向基體Π内擴散而形成。所述 路滲入層13包括碳纖維（Cf )、2^2陶瓷相、Cr金屬相 及Cr-C相。 ...: . .. ..... . 本發明一較佳實施例的製造所述被覆件1 〇的方法主要包 括如下步驟： Λ ,¾ 提供基體11，該基體11的材質為碳纖維/ZrB2複合材料。 請參閱圖2，提供一真空鍍膜機1〇〇，將所述基體11置於 該真空鍍膜機1〇〇内進行電漿清洗’以進一步去除基體11 表面的油污，以及改善基體11表面與後續塗層的結合力 Ο ' !! i 該鍍膜機100包括一鍍膜室20及與鍍膜室20相連接的一真 空泵30，真空泵30用以對鍵膜室20抽真空。該鑛膜室20 内設有轉架（未圖示）、二第一靶材22及二第二靶材23 。轉架帶動基體11沿圓形軌跡21運行，且基體11在沿軌 跡21運行時亦自轉。二第一靶材22與二第二靶材23關於 軌跡21的中心對稱設置，且二第一靶材22相對地設置在 軌跡21的内外侧，二第二乾材23相對地設置在軌跡21的 内外側。每-第-輕材22及每一第二乾材23的兩端均設 表單編號A0101 第5真/共12買 ^02000192-0 201229271 有氟源通道24 ’氣體經該氣源通道24進入所述嫉膜室20 中。當基體11穿過二第一乾材22之間時，將锻上第一乾 材22表面濺射出的粒子，當基體丨丨穿過二第二靶材23之 間時，將鑛上第二乾材2 3表面濺射出的粒子。本實例中 ，所述第一靶材22為鉻靶，所述第二靶材23為銥靶。 [0022] [0023] [0024] [0025] 该電漿清洗的具體操作及工藝參數為：如圖2所示，基體 11安裝於鍍膜室20内，真空泵30對所述鍍膜室2〇進行抽 真空處理至真空度為& 〇xl〇-3Pa，然後以3〇〇〜500sccm (標準狀態毫升/分鐘）的流量向鍍勝室2〇内通入純度為 99.999%的氬氣，並施加-5〇0~-8〇肝的偏壓於基體11， 對基體11表面進行電漿清洗，清洗時間為5〜15min。 在對基體11進行電漿清洗後，於該基體u上形成鉻層丄5 。形成該鉻層15的具體操作及工藝參數如下：以氬氣為 工作氣體，s周郎氩氣流量為2〇〜i5〇sccm，於基體11上施 加-100〜-300V的偏壓，並加熱鍍膜室2〇至1〇〇〜2〇〇艽（ 即鍍膜溫度為100〜200t：) ;開啟已安裝於該鍍膜機内的 第一靶材22的電源，設置其功參馬2〜5kw，沉積鉻層15 。沉積該鉻層15的時間為I50~250min。 在形成所述鉻層15的過程中，由於鉻金屬與碳纖維/zrB2 複合材料之間具有良好的潤濕性，所述鉻層丨5與基體u 介面處的金屬鉻向基體Π内擴散，形成包括碳纖維 )、ZrB^瓷相、Cr金屬相及Cr-C相的鉻滲入層13。該 絡滲入層13提高了鉻層15與基體11之間的結合力。 於该鉻層15上形成銀層17，形成所述錶層17的具體操作 100100110 表單編號A0101 第6頁/共12頁 1002000192-0 201229271 及工藝參數如下：關閉所述第一靶材22的電源，保持所 述氬氣的流量、施加於基體Π的偏壓及鍍膜溫度不變， 開啟已安裝於所述鍍膜室20内第二靶材23的電源，設置 其功率為2〜5kw，於所述鉻層1 5上沉積銥層1 7。沉積該 銘層17的時間為15〇〜250min。 [0026] 在磁控濺射所述形成鉉層17的過程中，鈒金屬將擴散至 所述鉻層15的表層内，如此使銥層17與鉻層15之間過渡 較好，沒有成分和力學性能的突變。 [0027] 本發明較佳實施例被覆件10的製造方法，先於基體11上 磁控濺射形成鉻層15，再於所述鉻層15上播成銥層17。 所述鉻層15的形成可提高所述銥層1 7與基體11之間的結 合力，使被覆件10經高溫處理後銥層17不易剝落或裂紋 ’如此可提高所述銥層17的高溫抗氧化性能。此外，藉 由上述製造方法形成的銥層17幾乎無針孔、具有良好的 緻密性，如此可進一步提高所述銥層17的抗氧化性。 [0028] 所述銀層17還具有良好的抗熱震性能|主要有如下兩方 面的原因：一方面，由於所述絡層15由靠近該基體^至 遠離該基體11的方向呈梯度過渡，沒有成分和力學性能 的突變；另一方面’所述銥層17與鉻層15之間過渡較好 ，沒有成分和力學性能的突變。 [0_故’所述被覆件1Q具有良好的高溫抗氧化性及抗熱震性 【圖式簡單說明】 卿]_1為本發錢佳實關的被覆件的剖視圖； 100100110 表單編號A0101 第7頁/共12頁 1002000192-0 201229271 [0031] 圖2為製造圖1中鍍膜件所用真空鍍膜機的示意圖。 【主要元件符號說明】 [0032] 被覆件：10 [0033] 基體：11 [0034] 鉻滲入層：13 [0035] 鉻層：15 [0036] 錶層：1 7 [0037] 鍍膜機：100 [0038] 鍍膜室：20 [0039] 真空泵：30 [0040] 軌跡：21 [0041] 第一靶材：22 [0042] 第二靶材：23 [0043] 氣源通道：24 100100110 表單編號A0101 第8頁/共12頁 1002000192-0[0003] The prior art utilizes chemical vapor deposition (cvp) to combine carbon fibers with ZrB2 to form a Cf/ZrB2a composite material. The Cf/ZrB(2) material has excellent mechanical properties and bounciness, but its high temperature resistance. The pound is poor.匕4 〇 2 _ _ _ _ _ 2 〇 2 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇金属 Good mechanical properties of the metal. Due to the poor service between the t-silver coatings, a large amount of cracks are generated after the high-temperature treatment of the carbon-coated coatings, so the silver coating has poor oxidation resistance and thermal shock resistance. Two Temperatures [Summary Contents] _5] In view of this, a cover member that effectively solves the above problems is provided. Further, a method for producing the above-mentioned covering member is also provided.圃------------------------------------------------------------------------------------------------------ [0008] A method for manufacturing a coated member, comprising the following steps: [0009] providing a substrate, the substrate material is a carbon fiber / ZrB2 composite material; [0010] using a chromium target as a target, magnetron sputtering chromium on the surface of the substrate The layer has a sputtering temperature of 100 to 200 ° C and a sputtering time of 150 to 250 min. During the magnetron sputtering of the chromium layer, the chromium layer and the metal chromium at the interface of the substrate diffuse to the substrate, and the substrate and the chromium A chromium infiltrated layer is formed between the layers; [0011] a germanium target is used as a target, and a germanium layer is formed by magnetron sputtering on the chromium layer. [0012] The formation of the chrome layer can improve the bonding force between the enamel layer and the substrate, and the ruthenium layer is not easily peeled off or cracked after the high temperature treatment of the coated member, so that the high temperature oxidation resistance of the ruthenium layer can be improved. Further, the tantalum layer formed by the above-described production method has almost no pinholes and has good compactness, so that the oxidation resistance of the tantalum layer can be further improved. [0013] The ruthenium layer also has good thermal shock resistance, mainly for the following two reasons: on the one hand, since the chrome layer has a gradient transition from a direction close to the substrate to away from the substrate, there is no composition and Mutations in mechanical properties: On the other hand, the transition between the ruthenium layer and the chrome layer is better, with no mutations in composition and mechanical properties. [0014] Therefore, the coated member has good high temperature oxidation resistance and thermal shock resistance. [Embodiment] Referring to Fig. 1, a covering member 10 according to a preferred embodiment of the present invention includes a base 11, a chromium infiltrated layer 13, a chrome layer 15, and a ruthenium layer 17 which are sequentially formed on the base 11. The covering member 10 can be an aerospace machine such as a turbine blade or a nozzle. No. 100100110 Form No. A0101 Page 4 / Total 12 Page 1002000192-0 201229271 [0017] [0018] [0020] [0020] [0021] 100100110 4 pieces 'can also be parts of transportation such as construction, electronics and automobiles. The material of the base 11 is a carbon fiber/ZrB2 composite material. The road layer 15 and the ruthenium layer 17 can be formed by a magnetron sputtering coating method. The thickness of the road layer 15 is 2~3. 5 ym. The thickness of the 铱 layer π is 2~3. The chromium infiltration layer 13 is formed during the formation of the chromium layer 15, and the metal chromium at the interface between the chromium layer 15 and the substrate 11 is diffused into the matrix crucible. The road infiltration layer 13 includes a carbon fiber (Cf), a 2^2 ceramic phase, a Cr metal phase, and a Cr-C phase. The method for manufacturing the covering member 1 according to a preferred embodiment of the present invention mainly comprises the following steps: Λ, 3⁄4 providing a base body 11 made of carbon fiber/ ZrB2 composite. Referring to FIG. 2, a vacuum coating machine 1 is provided, and the substrate 11 is placed in the vacuum coating machine for plasma cleaning to further remove oil stain on the surface of the substrate 11, and to improve the surface of the substrate 11 and subsequent The bonding force of the coating Ο '!! i The coating machine 100 includes a coating chamber 20 and a vacuum pump 30 connected to the coating chamber 20, and the vacuum pump 30 is used to evacuate the key film chamber 20. A rotating frame (not shown), two first targets 22, and two second targets 23 are provided in the film chamber 20. The turret drives the base body 11 to run along the circular path 21, and the base body 11 also rotates as it travels along the trajectory 21. The two first targets 22 and the two second targets 23 are symmetrically disposed with respect to the center of the trajectory 21, and the two first targets 22 are oppositely disposed on the inner and outer sides of the trajectory 21, and the second second dry materials 23 are oppositely disposed on the trajectory 21. Inside and outside. Each of the -th-light material 22 and each of the second dry material 23 has a form number A0101 on both ends thereof. 5th true/common 12 buy^02000192-0 201229271 Fluoride source passage 24' gas enters through the gas source passage 24 Said in the diaphragm chamber 20. When the substrate 11 passes between the two first dry materials 22, the particles sputtered on the surface of the first dry material 22 will be forged, and when the substrate is passed between the two second targets 23, the second will be placed on the mine. The particles sputtered on the surface of the dry material 2 3 . In the present example, the first target 22 is a chromium target and the second target 23 is a target. [0025] [0024] [0025] The specific operation and process parameters of the plasma cleaning are: as shown in FIG. 2, the substrate 11 is installed in the coating chamber 20, and the vacuum pump 30 pumps the coating chamber 2 Vacuum treatment to a vacuum of & 〇xl〇-3Pa, and then a argon gas having a purity of 99.999% is introduced into the plating chamber 2〇 at a flow rate of 3 〇〇 to 500 sccm (standard state ML/min), and - 5〇0~-8〇 The liver is biased to the substrate 11, and the surface of the substrate 11 is plasma-cleaned for 5 to 15 minutes. After the substrate 11 is plasma-cleaned, a chromium layer 丄5 is formed on the substrate u. The specific operation and process parameters for forming the chrome layer 15 are as follows: argon gas is used as the working gas, sirro argon gas flow rate is 2 〇 to i5 〇 sccm, and a bias voltage of -100 〜 300 V is applied to the substrate 11 and heated. The coating chamber is 2〇 to 1〇〇~2〇〇艽 (that is, the coating temperature is 100~200t:); the power of the first target 22 already installed in the coating machine is turned on, and the power of the horse is set to 2~5kw, deposition Chrome layer 15 . The time for depositing the chromium layer 15 is from I50 to 250 min. In the process of forming the chromium layer 15, due to good wettability between the chromium metal and the carbon fiber/zrB2 composite material, the chromium layer 5 and the metal chromium at the interface of the substrate u diffuse into the matrix crucible to form A chromium infiltrated layer 13 comprising a carbon fiber), a ZrB^ceramic phase, a Cr metal phase, and a Cr-C phase. The infiltrated layer 13 increases the bonding force between the chromium layer 15 and the substrate 11. A silver layer 17 is formed on the chrome layer 15, and the specific operation 100100110 of the surface layer 17 is formed. Form No. A0101, page 6 / page 12, 1002000192-0 201229271, and the process parameters are as follows: the power of the first target 22 is turned off. Keeping the flow rate of the argon gas, the bias voltage applied to the substrate 及 and the coating temperature unchanged, and turning on the power source of the second target 23 installed in the coating chamber 20, and setting the power to 2 to 5 kW. A layer of germanium 17 is deposited on the chromium layer 15 . The time for depositing the layer 17 is 15 〇 to 250 min. In the process of magnetron sputtering the formation of the ruthenium layer 17, the ruthenium metal will diffuse into the surface layer of the chrome layer 15, so that the transition between the ruthenium layer 17 and the chrome layer 15 is better, without composition and Mutations in mechanical properties. In the manufacturing method of the coated member 10 of the present invention, the chromium layer 15 is formed by magnetron sputtering on the substrate 11, and the germanium layer 17 is then spread on the chromium layer 15. The formation of the chrome layer 15 can improve the bonding force between the enamel layer 17 and the substrate 11, so that the ruthenium layer 17 is not easily peeled off or cracked after the high temperature treatment of the coated member 10, so that the high temperature of the ruthenium layer 17 can be improved. Antioxidant properties. Further, the tantalum layer 17 formed by the above-described manufacturing method has almost no pinholes and has good compactness, so that the oxidation resistance of the tantalum layer 17 can be further improved. [0028] The silver layer 17 also has good thermal shock resistance performance mainly for the following two reasons: on the one hand, since the complex layer 15 has a gradient transition from the substrate body to the direction away from the substrate body 11, There are no mutations in composition and mechanical properties; on the other hand, the transition between the ruthenium layer 17 and the chrome layer 15 is better, with no mutations in composition and mechanical properties. [0_故' The coated member 1Q has good high temperature oxidation resistance and thermal shock resistance [Simple description of the drawing] Qing]_1 is a cross-sectional view of the coated piece of the money payment Jiajianguan; 100100110 Form No. A0101 No. 7 Page / Total 12 pages 1002000192-0 201229271 [0031] FIG. 2 is a schematic view of a vacuum coater used for manufacturing the coated member of FIG. [Main component symbol description] [0032] Covering member: 10 [0033] Base: 11 [0034] Chromium infiltrated layer: 13 [0035] Chromium layer: 15 [0036] Surface layer: 1 7 [0037] Coating machine: 100 [ 0038] Coating chamber: 20 [0039] Vacuum pump: 30 [0040] Track: 21 [0041] First target: 22 [0042] Second target: 23 [0043] Air source passage: 24 100100110 Form No. A0101 No. 8 Page / Total 12 pages 1002000192-0