201217085 六、 [0001] [0002] θ [0003] Ο 發明說明： 【發明所屬之技術領域】 本發明涉及一種金屬與陶瓷的連接方法及製得的連接件 ，尤其涉及一種不鏽鋼與氧化锆陶瓷的連接方法及製得 的連接件。 【先前技術】 不鏽鋼於常溫下具有較好的耐腐蝕性能，被廣泛應用於 製造各種工程結構與機械零件。然，當在高溫、腐蝕性 等較為惡劣的環境下使用時，不鏽鋼的耐腐蝕性、耐磨 性、抗沖蝕性、耐高溫性能等已經很難滿足現代生產技 術的進一步需求。而氧化錯陶瓷具有硬度高、高溫抗腐 蝕、耐磨損、抗沖蝕等優點，故，不鏽鋼與氧化錯陶瓷 連接在一起製備成複合結構，對於不鏽鋼於惡劣環境中 應用具有非常重要的意義。 目前，實現不鏽鋼與氧化锆陶瓷的連接主要係於兩者間 添加中間金屬層，於高溫下實現兩者的擴散連接。通常 ，係於陶瓷侧添加活性高的金屬或者膨脹係數小、彈性 模量大的金屬。於陶瓷側添加活性高的金屬，如鈦，雖 然能實現不鏽鋼與氧化銼陶瓷的反應連接，但由於鈦的 熱膨脹係數與陶瓷差異較大，故存在較大的熱應力，從 而使結合力下降。於陶瓷侧添加熱膨脹係數小、彈性模 量大的金屬，如鎳，因該等金屬的活性較低，與陶究的 擴散反應較困難，因此連接難度較高。 【發明内容】 有鑒於此，有必要提供一種易於實現的、可獲得較高連 099136751 表單編號Α0101 第3頁/共14頁 0992064202-0 [0004] 201217085 接強度的不鏽鋼與氧化锆陶瓷的連接方法。 [0005] 另外，還有必要提供一種由上述連接方法製得的連接件 〇 [0006] 一種不鏽鋼與氧化锆陶瓷的連接方法，包括以下步驟： [0007] 提供一待連接的不鏽鋼件、一氧化锯陶瓷件、一鉬箔及 一銅羯； [0008] 對該氧化鍅陶瓷件、不鏽鋼件、鉬箔及銅箔分別進行打 磨及清洗； [0009] 於該氧化鍅陶瓷件表面沉積一鎳金屬層； [0010] 將氧化锆陶瓷件、鉬箔、銅箔及不鏽鋼件放入一連接模 具中，使鉬箔與銅箔夾放於氧化鍅陶瓷件與不鏽鋼件之 間，並且鉬箔與氧化锆陶瓷件相鄰，銅箔與不鏽鋼件相 鄰； [0011] 將連接模具放入一熱壓燒結爐中，於保護氣氛下對工件 進行固相擴散連接； [0012] 待冷卻後取出不鏽鋼與氧化锆陶瓷的連接件。 [0013] 一種不鏽鋼與氧化鍅陶瓷的連接件，該不鏽鋼與氧化锆 陶瓷的連接件包括一不鏽鋼件、一氧化锆陶瓷件及連接 該不鏽鋼件與該氧化锆陶瓷件的連接部，該連接部包括 一第一過渡層、一 #目層、一第二過渡層、一銅層及一第 三過渡層，該第一過渡層位於氧化錯陶瓷件與鉬層之間 ，第一過渡層由鎳鉬金屬間化合物組成，該第二過渡層 位於鉬層與該銅層之間，第二過渡層由鉬銅固熔體及鉬 099136751 表單編號A0101 第4頁/共14頁 0992064202-0 201217085 [0014] Ο 銅金屬間化合物組成，該第三過渡層位於銅層與不鱗鋼 件之間，第三過渡層由銅鐵金屬間化合物及銅鐵固溶體 組成。 相較於習知技術，上述不鏽鋼與氧化锆陶瓷的連接方法 於氧化锆陶瓷件的表面先沉積一鎳金屬層，然後於熱壓 燒結爐中藉由施加銦箔及銅箔作為中間介質層，實現氧 化錯陶瓷件與不鏽鋼件的固相擴散連接。於氧化锆陶究 件一側施加膨脹係數較小的鉬箔作為連接介質，降低了 不鍵鋼與氧化錄陶究間的熱應力，有效防止裂紋產生， 提高了連接強度；沉積於氧化锆陶瓷件表面的鎳金屬層 活性較大，彌補了鉬與氧化锆陶瓷反應滅、不易連接的 缺陷。由該方法製得的不鏽鈿與氧化錄陶瓷的連接件具 有較大的連接強度。 [0015] Ο [0016] 【實施方式】 請參閱圖1，本發明較佳實施例的不 連接方法主要藉由固相擴散來完成， 下步驟： 鏽鋼與氧化锆陶瓷的 该方法主要包括如 ⑴提供待連接的氧化結喊件2G與不鏽鋼糊， 提供㈣40與銅㈣作為連接介質。_ 的厚度均大約為純佳厚度桃U3mm [0017] 50分別進行打磨、清洗，並吹幹 ㈣及銅羯 紙打磨氡聽喊㈣，时切金剛石砂 反化石夕砂紙對不鏽銦体、 099136751 ㈣40及銅㈣進行打磨，使 着鋼件30、 表單編號A0101 第5頁/共丨4頁 、〇陶瓷件20、不鏽鋼 0992064202-1 201217085 件30:銦㈣及銅㈣表面較為平整，再用盛裝有乙醇 的超聲波進行振動清洗5〜15分鐘，⑽去氡化鍅陶究件 2〇、不鏽鋼件3〇、！目落4〇及銅落5〇表面雜質及油污等， 清洗後吹幹備用。以下將氧化㈣兗㈣、不鏽鋼件3〇 、鉬箔4 0及銅箔5 〇統稱為工件。 [0018] [0019] [0020] (3) 於礼化錯陶变件2〇表面沉積一鎳金屬層6〇。該鎳金 屬層60可藉由真空_方式沉積，亦可藉由化學鑛膜的 方式形成’其厚度大約3/zm左右較佳。 (4) 將工件按照氧化鍅陶瓷件20 —鉬箔40 —銅箔50 —不 錄鋼件30的順序放人—連接模具7Q中，使鉬請與銅结 50夾放於氧化鍅陶瓷件2〇與不鏽鋼件3〇之間並且鉬箔 4〇與氧化錯陶究件2〇相鄰，銅落5〇與不鏽鋼件3〇相鄰。 该連接模具70包括上壓頭72、下壓頭74及中模76。該中 模76具有一模腔（圖未示）’用於容置待連接工件。該 上壓頭72與下壓頭74分別從兩側將放置於模腔中的工件 壓緊。5亥連接模具7 〇可為石墨材料製成。 (5)將連接模具7〇放入—熱壓燒結爐1〇〇中，於保護氣 氛下對工件進行固相擴散連接。連接模具7〇放入熱壓燒 結爐1 0 0後對熱壓燒結爐1 〇〇抽真空至2χ 1 〇-3pa~ 8χ 1〇 Pa，然後充入氬氣作為保護氣氛，充入氬氣後熱壓 燒結爐100内壓力可為〇· 2〜〇· 5MPa。於保護氣氛下將熱 壓燒結爐1 0 0升溫，並於如下工藝參數下對工件進行固相 擴散連接·升溫速率為1〇〜5(TC/ min ,連接溫度為 800〜1080 C ’連接溫度保溫時間為1〇〜6〇min，轴向壓 力為liMOOMPa。轴向壓力的具體施加方法為：於溫度 099136751 表單編號A0101 第6頁/共14頁 0992064202-0 201217085 [0021] [0022] Ο [0023] Ο 099136751 到達300。(：時，藉由上麗頭72與下壓頭湘始對工件施加 l〇MPa的轴向壓力，之後慢慢增大軸向壓力，直至溫度為 連接溫度時軸向壓力為最大值。 (6)待冷卻後取出不鏽鋼件3〇與氧化鍅陶瓷件2〇的連接 件。 上述不錄鋼與氧化錯陶究的連接方法於氧化結陶究件2〇 的表面沉積-錄金屬層60，然後於熱壓燒結爐1〇〇中藉由 施加翻㈣與銅糊料中时質層，實魏化錯喊 件20與不鏽鋼件30之固相擴散連接。於氧化鍅陶竟件2〇 —側施加膨脹係數較小的鉬簿4〇作為連接介質，降低了 不鏽鋼與氧化锆陶兗間的熱應力，有效防止裂紋產生，提向了連接強度；沉積於氡化鍅陶瓷件2〇表面的鎳金屬 層60活性較大，彌補了鉬與氧化锆陶瓷反應慢、不易連 接的缺陷。 圖2所示為由上述連接方法製得的不鏽鋼與氧化鍅陶瓷的 連接件10，包括該氧化锆陶瓷件20、該不鏽鋼件3〇及連 接該不鏽鋼件30與該氧化锆陶瓷件2〇的連接部8〇。兮連 接部80包括一第一過渡層si、一鉬層82、一第二過产層 83、一銅層84及一第三過渡層85。該第一過渡層8丨位於 氧化锆陶瓷件20與鉬層82之間。第一過渡層81主要由錦 銷金屬間化合物組成。該第二過渡層83位於鉬層82與該 鋼層84之間，其為鉑層82與銅層84連接的過渡層。第_ 過渡層83主要由鉬銅固熔體及鉬銅金屬間化合物組成。 該第三過渡層85位於銅層84與不鏽鋼件30之間，其為铜 層84與不鏽鋼件30速接的過渡層。第三過渡層85主要由 表單編號* A0101 第7頁/共14頁 0992064202〜〇 201217085 銅鐵金屬間化合物及銅鐵固熔體組成。所述鉬層82與銅 層84的厚度大約均為0. 08〜0. 45mm，該連接部80的總厚 度大約為0. 2卜1. 1mm。 [0024] 該不鏽鋼與氧化锆陶瓷的連接件10的連接部80緻密均勻 ，無裂縫，無孔隙。經測試，該不鑛鋼與氧化錯陶瓷的 連接件1 0的不鏽鋼/氧化锆陶瓷介面的剪切強度可達 50~80MPa，抗拉強度達60〜lOOMPa。 【圖式簡單說明】 [0025] 圖1為本發明較佳實施例不鏽鋼與氧化锆陶瓷的連接方法 原理圖。 [0026] 圖2為本發明較佳實施例的不鏽鋼與氧化锆陶瓷的連接件 的剖面示意圖。 【主要元件符號說明】 [0027] 不鏽鋼與氧化锆陶瓷的連接件：10 [0028] 氧化錯陶瓷件：20 [0029] 不鏽鋼件：30 [0030] 鉬箔：4 0 [0031] 銅箔：50 [0032] 鎳金屬層：6 0 [0033] 連接模具：70 [0034] 上壓頭：72 [00351 下壓頭：74 099136751 表單編號A0101 第8頁/共14頁 0992064202-0 201217085 [0036] 中模：76 [0037] 連接部：80 [0038] 第一過渡層·’ 81 [0039] 鉬層：82 [0040] 第二過渡層： 83 [0041] 銅層：84 [0042] 第三過渡層： 85 [0043] 熱壓燒結爐： 100 ❹ 0992064202-0 099136751 表單編號A0101 第9頁/共14頁201217085 VI [0001] [0002] θ [0003] 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明Connection method and the obtained connector. [Prior Art] Stainless steel has good corrosion resistance at room temperature and is widely used in the manufacture of various engineering structures and mechanical parts. However, when used in harsh environments such as high temperature and corrosiveness, the corrosion resistance, wear resistance, erosion resistance, and high temperature resistance of stainless steel have been difficult to meet the further needs of modern production technology. The oxidized ceramics have the advantages of high hardness, high temperature corrosion resistance, wear resistance, erosion resistance, etc. Therefore, the combination of stainless steel and oxidized ceramics is a composite structure, which is very important for the application of stainless steel in harsh environments. At present, the connection between stainless steel and zirconia ceramics is mainly based on the addition of an intermediate metal layer between the two to achieve diffusion bonding between the two at high temperatures. Usually, a highly active metal or a metal having a small expansion coefficient and a large elastic modulus is added to the ceramic side. Adding a highly active metal such as titanium to the ceramic side enables the reaction connection between the stainless steel and the yttria ceramic. However, since the thermal expansion coefficient of titanium is largely different from that of the ceramic, there is a large thermal stress, so that the bonding force is lowered. A metal having a small coefficient of thermal expansion and a large modulus of elasticity, such as nickel, is added to the ceramic side. Since the activity of the metals is low, the diffusion reaction with the ceramics is difficult, and thus the connection is difficult. SUMMARY OF THE INVENTION In view of the above, it is necessary to provide a method for connecting stainless steel and zirconia ceramics which is easy to implement and which can obtain higher connection 099136751 Form No. 1010101 Page 3/14 Page 0992064202-0 [0004] 201217085 . [0005] In addition, it is also necessary to provide a connector 制 [0006] a method of joining stainless steel and zirconia ceramics, comprising the following steps: [0007] providing a stainless steel piece to be connected, oxidizing Saw ceramic parts, a molybdenum foil and a copper crucible; [0008] grinding and cleaning the yttria ceramic parts, stainless steel parts, molybdenum foils and copper foils respectively; [0009] depositing a nickel metal on the surface of the yttria ceramic parts [0010] The zirconia ceramic piece, the molybdenum foil, the copper foil and the stainless steel piece are placed in a joint mold, and the molybdenum foil and the copper foil are sandwiched between the yttria ceramic part and the stainless steel piece, and the molybdenum foil is oxidized The zirconium ceramic pieces are adjacent to each other, and the copper foil is adjacent to the stainless steel piece; [0011] the connecting mold is placed in a hot press sintering furnace, and the workpiece is subjected to solid phase diffusion bonding under a protective atmosphere; [0012] the stainless steel is taken out after being cooled Connector for zirconia ceramics. [0013] A connecting piece of stainless steel and cerium oxide ceramic, the connecting piece of the stainless steel and the zirconia ceramic comprises a stainless steel piece, a zirconia ceramic piece and a connecting portion connecting the stainless steel piece and the zirconia ceramic piece, the connecting part The first transition layer is disposed between the oxidized ceramic part and the molybdenum layer, and the first transition layer is composed of nickel. The first transition layer is disposed between the oxidized ceramic part and the molybdenum layer. a molybdenum intermetallic compound, the second transition layer is located between the molybdenum layer and the copper layer, the second transition layer is composed of a molybdenum copper solid solution and molybdenum 099136751 Form No. A0101 Page 4 / 14 pages 0992064202-0 201217085 [0014 Ο Copper intermetallic compound composition, the third transition layer is located between the copper layer and the non-scale steel member, and the third transition layer is composed of a copper-iron intermetallic compound and a copper-iron solid solution. Compared with the prior art, the above method for joining stainless steel and zirconia ceramics first deposits a nickel metal layer on the surface of the zirconia ceramic member, and then applies an indium foil and a copper foil as an intermediate medium layer in the hot press sintering furnace. A solid phase diffusion connection between the oxidized ceramic part and the stainless steel piece is achieved. On the side of the zirconia ceramics, a molybdenum foil with a small expansion coefficient is applied as a connecting medium, which reduces the thermal stress between the unbonded steel and the oxide-recorded ceramics, effectively prevents cracks and improves the joint strength; and deposits on the zirconia ceramics. The nickel metal layer on the surface of the piece has a large activity, which makes up for the defect that the molybdenum and the zirconia ceramic react and disappear. The joint of the stainless steel and the oxide-recorded ceramic obtained by the method has a large joint strength. [0015] [Embodiment] Referring to FIG. 1, the non-connection method of the preferred embodiment of the present invention is mainly completed by solid phase diffusion, and the following steps: the method of rust steel and zirconia ceramic mainly includes (1) Providing an oxidized squeegee 2G and a stainless steel paste to be connected, and providing (4) 40 and copper (4) as a connection medium. The thickness of _ is about pure thickness peach U3mm [0017] 50 respectively polished, cleaned, and blown dry (four) and copper crepe paper polished 氡 shouted (four), when cut diamond sand counter-stone sandpaper against stainless indium, 099136751 (4) 40 and copper (4) for grinding, making steel parts 30, form number A0101 page 5 / total 4 pages, enamel ceramic parts 20, stainless steel 0992064202-1 201217085 pieces 30: indium (four) and copper (four) surface is relatively flat, and then used to dress Ultrasonic cleaning with ethanol for 5 to 15 minutes, (10) 2 〇 鍅 鍅 鍅 鍅 究 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 Surface impurities and oil stains, etc., are cleaned and dried. Hereinafter, the oxidized (four) bismuth (four), the stainless steel member 3 〇, the molybdenum foil 40, and the copper foil 5 are collectively referred to as a workpiece. [0020] [0020] (3) depositing a nickel metal layer 6〇 on the surface of the liturgical ceramic member. The nickel metal layer 60 may be deposited by a vacuum method or may be formed by a chemical ore film having a thickness of about 3/zm or so. (4) The workpiece is placed in the order of the yttria ceramic member 20 - the molybdenum foil 40 - the copper foil 50 - the unrecorded steel member 30 - in the mold 7Q, so that the molybdenum and the copper joint 50 are sandwiched between the yttrium oxide ceramic members 2 Between the crucible and the stainless steel piece 3并且 and the molybdenum foil 4〇 is adjacent to the oxidized wrong ceramic piece 2〇, the copper drop 5〇 is adjacent to the stainless steel piece 3〇. The joint mold 70 includes an upper ram 72, a lower ram 74, and a middle mold 76. The middle mold 76 has a cavity (not shown) for accommodating the workpiece to be joined. The upper ram 72 and the lower ram 74 respectively press the workpiece placed in the cavity from both sides. 5 Hai connection mold 7 〇 can be made of graphite material. (5) The connecting mold 7 is placed in a hot-pressing sintering furnace 1 to perform solid-phase diffusion bonding of the workpiece under a protective atmosphere. After connecting the mold 7〇 into the hot press sintering furnace 100, vacuum the hot press sintering furnace 1 to 2χ 1 〇-3pa~ 8χ 1〇Pa, then fill with argon as a protective atmosphere, and then fill with argon gas. The pressure in the hot press sintering furnace 100 may be 〇·2~〇·5 MPa. The hot-pressing sintering furnace was heated in a protective atmosphere at a temperature of 100 °, and the workpiece was subjected to solid phase diffusion bonding under the following process parameters. The heating rate was 1 〇 5 (TC/min, and the connection temperature was 800 to 1080 C 'connection temperature). The holding time is 1〇~6〇min, and the axial pressure is liMOOMPa. The specific application method of axial pressure is: at temperature 099136751 Form No. A0101 Page 6 / Total 14 Page 0992064202-0 201217085 [0021] [0022] Ο [ 0023] Ο 099136751 Arrives at 300. (: When the upper head 72 and the lower head start to apply an axial pressure of 10 MPa to the workpiece, then slowly increase the axial pressure until the temperature is the connection temperature. The pressure is the maximum value. (6) After cooling, remove the joint between the stainless steel piece 3〇 and the yttria ceramic part 2。. The above-mentioned method of connecting the non-recorded steel and the oxidized ceramic is on the surface of the oxidized ceramic piece 2〇 Depositing and recording the metal layer 60, and then in the hot press sintering furnace 1 by applying a turn (4) to the solid phase layer in the copper paste, the solid phase diffusion joint of the real Weihua component 20 and the stainless steel member 30 is oxidized.鍅陶竟件2〇—The side of the molybdenum book with a small expansion coefficient is applied as a joint The medium is connected to reduce the thermal stress between the stainless steel and the zirconia pottery, effectively preventing the crack from being generated and improving the joint strength; the nickel metal layer 60 deposited on the surface of the tantalum crucible ceramic member has a large activity, which makes up for the molybdenum and The zirconia ceramic has a slow reaction and is difficult to connect. Figure 2 shows the joint 10 of stainless steel and yttria ceramic obtained by the above joining method, including the zirconia ceramic member 20, the stainless steel member 3〇 and the stainless steel. The connecting portion 8 of the member 30 and the zirconia ceramic member 2A. The connecting portion 80 includes a first transition layer si, a molybdenum layer 82, a second over-production layer 83, a copper layer 84, and a third transition. a layer 85. The first transition layer 8 is located between the zirconia ceramic member 20 and the molybdenum layer 82. The first transition layer 81 is mainly composed of a rug intermetallic compound. The second transition layer 83 is located at the molybdenum layer 82 and the steel. Between the layers 84, which is a transition layer connecting the platinum layer 82 and the copper layer 84. The first transition layer 83 is mainly composed of a molybdenum-copper solid solution and a molybdenum-copper intermetallic compound. The third transition layer 85 is located on the copper layer 84 and Between the stainless steel members 30, the copper layer 84 is fastened to the stainless steel member 30. The third transition layer 85 is mainly composed of a copper-iron intermetallic compound and a copper-iron solid solution, which is composed of a form number * A0101, page 7 / 14 pages 0992064202 - 〇201217085. The thickness of the molybdenum layer 82 and the copper layer 84 is approximately The total thickness of the connecting portion 80 is about 0.2 b 1. 1 mm. [0024] The connecting portion 80 of the connecting member 10 of the stainless steel and the zirconia ceramic is dense and uniform without cracks. No porosity. After testing, the stainless steel/zirconia ceramic interface of the non-mineral steel and oxidized ceramic joint 10 has a shear strength of 50-80 MPa and a tensile strength of 60-100 MPa. BRIEF DESCRIPTION OF THE DRAWINGS [0025] FIG. 1 is a schematic view showing a method of joining stainless steel and zirconia ceramics according to a preferred embodiment of the present invention. 2 is a cross-sectional view showing a joint of a stainless steel and a zirconia ceramic according to a preferred embodiment of the present invention. [Description of main component symbols] [0027] Connector of stainless steel and zirconia ceramic: 10 [0028] Oxidized ceramic part: 20 [0029] Stainless steel part: 30 [0030] Molybdenum foil: 4 0 [0031] Copper foil: 50 [0032] Nickel metal layer: 6 0 [0033] Connecting mold: 70 [0034] Upper pressing head: 72 [00351 Lower pressing head: 74 099136751 Form No. A0101 Page 8 / Total 14 page 0992064202-0 201217085 [0036] Mode: 76 [0037] Connection: 80 [0038] First transition layer · '81 [0039] Molybdenum layer: 82 [0040] Second transition layer: 83 [0041] Copper layer: 84 [0042] Third transition layer : 85 [0043] Hot pressing furnace: 100 ❹ 0992064202-0 099136751 Form number A0101 Page 9 of 14