201219130 六、發明說明： 【發明所屬之技術領域】 _]本發明涉及一種麵與Μ的連接方法及製得的連接件 ’尤其涉及種與碳化㈣兗的連接方法及製得 的連接件。 【先前技術】 [0002] Ο 不錢鋼於卜下具有較好的耐腐*性能被廣泛應用於 製造各種工程結構與機械科。然，#在高溫、腐純 等的％^兄下使用時，不錢鋼的耐腐射生、耐磨 耐向溫性能等已經很難滿足現代生產技 性、抗沖#性、 術的進—步需求1碳化讀球有硬度高、高溫抗腐 触、耐磨H巾料優點，祕，_鋼與錢♦陶 竞連接在-起製備成複合結構，對於稿鋼於惡劣〜 中應用具有非常重要的意義。 兄 酬目前，實現残喻碳切喊祕衫要係於兩201219130 VI. Description of the Invention: [Technical Field of the Invention] The present invention relates to a method of connecting a face to a crucible and a connector for manufacturing the same, and in particular to a method of joining a carbonized (tetra) crucible and a connector obtained. [Prior Art] [0002] Ο Ο 不 钢 具有 具有 has a good corrosion resistance* performance is widely used in the manufacture of various engineering structures and mechanical departments. However, when used under the high temperature, rot, etc.%^, it is difficult to meet the requirements of modern production techniques, impact resistance, and surgery. - Step demand 1 carbonized reading ball has the advantages of high hardness, high temperature anti-corrosion touch, wear-resistant H towel material, secret, _ steel and money ♦ Tao Jing connection in the preparation of a composite structure, for the manuscript steel in the harsh ~ medium application Very important meaning. Brother pays for the present, realizes the metaphor of carbon and shouts that the secret shirt should be tied to two
添加中間金屬層’於高温下實現兩者的擴散連接。通A ，係於喊侧添加活性高的金屬或者膨脹雜小、彈二 杈量大的金屬。於陶瓷侧添加活性高的金屬如鎳，雖 然能實現不銹鋼與碳化矽陶瓷的反應連接，但由於鎳的 熱膨脹係數與陶瓷差異較大，故存在較大的熱應力y從 而使結合力下降。在陶瓷侧添加熱膨脹係數小、彈性模 量大的金屬’如鉬，因該等金屬的活性較低，與陶曼的 擴散反應較困難，故連接難度較高。 【發明内容】 [0004] 有鑒於此’有必要提供一種易於實現的、可獲得較含連 099138065 表單編號A0101 第3頁/共15頁 201219130 接強度的不銹鋼與碳化矽陶瓷的連接方法。 [0005] 另，還有必要提供一種由上述連接方法製得的連接件。 [0006] 一種不銹鋼與碳化矽陶瓷的連接方法，包括以下步驟： [0007] 提供待連接的不銹鋼件、碳化矽陶瓷件、鉬箔及鎳箔； [0008] 對該碳化矽陶瓷件、不銹鋼件、鉬箔及鎳箔分別進行打 磨與清洗； [0009] 於該碳化矽陶瓷件表面沉積鎳金屬層； [0010] 將碳化矽陶瓷件、鉬箔、鎳箔及不銹鋼件放入連接模具 中，使鉬箔與鎳箔夾放於碳化矽陶瓷件與不銹鋼件之間 ，並且鉬箔與碳化矽陶瓷件上的鎳金屬層相鄰，鎳箔與 不銹鋼件相鄰； [0011] 將連接模具放入熱壓燒結爐中，於保護氣氛下對工件進 行固相擴散連接； [0012] 待冷卻後取出不銹鋼與碳化矽陶瓷的連接件。 [0013] 一種不銹鋼與碳化矽陶瓷的連接件，該不銹鋼與碳化矽 陶瓷的連接件包括不銹鋼件、碳化矽陶瓷件及連接該不 銹鋼件與該碳化矽陶瓷件的連接部，該連接部包括第一 過渡層、鉬層、第二過渡層、銅層及第三過渡層，該第 一過渡層位於碳化矽陶瓷件與鉬層之間，第一過渡層由 錄I目金屬間化合物與錄石夕化合物組成，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銅 金屬間化合物組成，該第三過渡層位於銅層與不銹鋼件 之間，第三過渡層由銅鐵金屬間化合物及銅鐵固熔體組 099138065 表單編號A01O1 第4頁/共15頁 0992066344-0 201219130 成0 [0014] 相較於習知技術，上述不銹鋼與碳化矽陶瓷的連接方去 於碳化矽陶瓷件的表面先沉積一層鎳金屬層，然後於熱 壓燒結爐中藉由施加鉬箔與鎳箔作為中間介質層，叙 汽現 Ο 碳化矽陶瓷件與不銹鋼件的固相擴散連接。於碳化矽陶 瓷件一側施加膨脹係數較小的鉬箔作為連接介質，降低 了不銹鋼與碳化矽陶瓷間的熱應力，有效防止裂紋產生 ’提向了連接強度；沉積在碳化矽陶瓷件表面的鎳金屬 層活性較大’彌補了 19與碳切喊反應慢、不易連接 的缺陷。而施加於獨鋼件—侧的㈣活性較好，與不 錄鋼的_冊’ W與謂鋼_接、_該方法製得 的不錄鋼與碳㈣喊的連接件具有較大的連接強度: 【實施方式】 [0015] 下步驟 Ο [0016] ⑴a 碳化石夕陶瓷件20與不銹鋼件3〇 提供减40與麟5G以連接 娜3Q㈣ .^ 9 η 貝。δ亥鉬箔40與鎳箔50 W.2〜G.5mm，其較佳厚度制.⑷賴 〇 [0017] 099138065 (2)對碳化石夕陶兗件2〇、不錄綱 50分別進行打磨、清洗，並吹幹、，，自4◦與錄箱 紙打磨碳糾«件2G，用碳切砂=金剛石砂 鋼馆4〇與錢50進朴磨 ·鋼件30、 件30、_〇與錄箱5。表面較二:陶:件2°、不錄鋼 表單編號A0101 第5頁/共π頁 I，再用盛裝有乙醇 0992066344-0 201219130 的超聲波進彳τ振動清洗5〜15分鐘，以除去碳切陶究件 20、不錄辦件3〇、翻箱4〇與錄络5〇表面雜質及油亏等 清洗後吹幹備f以下將碳化㈣究㈣、不錄鋼件3〇 、鉬箔40與鎳箔5〇統稱為工件。 [0018] [0019] [0020] (3)於碟化砍陶兗件表面沉積-錄金屬層6〇。該鎳金 屬層60可藉由真空鍍膜方式，如騎形成，亦可藉由化 學艘膜的U形成’其厚度大㈣2〜…，3〜4^較佳 (4)將工件按照碳化矽陶瓷件2〇—鉬箔4〇―鎳箔π —不 錄鋼件3G的順較人—連接模具7()巾，使㈣4Q與錄羯 50夾放於碳化矽陶瓷件2〇與不銹鋼件3〇之間並且鉬箔 40與碳化矽陶瓷件2〇的鎳金屬層60相鄰，鎳箔50與不銹 鋼件30相鄰。該連接模具7〇包括上壓頭72、下壓頭以及 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。該連接模具7〇可以為石墨材料製成 (5)將連接模具70放入一熱壓燒結爐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100後對熱壓燒結爐1〇〇抽真空至2xl〇-3Pa〜8x l(T3Pa，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0. 2~0. 5MPa。於保護氣氛下將熱 壓燒結爐100升溫，並在如下工藝參數下對工件進行固相 擴散連接：溫度到達300°c前升溫速率為20〜4(TC/min， 超過300°C以後升溫速率為60~120°C/min，連接溫度為 099138065 表單編號A0101 第6頁/共15頁 0992066344-0 201219130 [0021] Ο [0022] [0023] Ο [0024] 850〜ll〇(TC，連接溫度保溫時間為15 35min，轴向壓 力為UMOOMPa。軸向壓力的具體施加方法為：在溫度 到達30(TC時，藉由上麼頭72與下廢頭74開始對工件^加 l〇MPa的軸向壓力，之後慢慢增大轴向壓力，直至溫度為 連接溫度時軸向壓力為最大值。 於上述溫度及壓力作用下，各卫件接觸介面之間充分地 相互擴散；於連接溫度的保溫時間控制在15 35分鐘範圍 内時:各接觸介面間形成的擴散過渡層厚度對應的連接 強度最大；保溫時間過長時，不利於節約能源而如果 保溫時間過短，則讀之_散不充分，難以形成明顯 ' ；： ：' . ：'： ：；' L . (6)待冷卻後取出不銹鋼件3〇與碳化矽陶^件別的連接 件。 上述不錢鋼與碳切喊的連接方法於碳切陶究件別 的表面沉積—錄金屬層6 0，然後於熱壓燒結爐1 〇 〇中藉由 施加鉬㈣_⑽作為中間介㈣’實現碳切陶曼 件20與不_件3〇的@相錄連接。於碳切陶究件^ 一側施加膨脹係數較小的钥辖4〇作為連接介質降低了 不銹鋼與碳化矽陶瓷間的熱應力，有效防止裂紋產生， 提高了連接強度；沉積於碳化石夕陶曼件2〇表面的錄金屬 層60活性較大’彌補了飽與碳化石夕陶:是反應慢、不易連 接的缺陷。而施加在不銹鋼件3〇 一側的鎳箔5〇活性較好 ，與不銹鋼的固熔性好，易於與不銹鋼件30連接。 圖2所示為由上述連接方法製得的残哺碳切陶曼的 099138065 表單編號A0101 第7 1/共15頁 0992066344-0 201219130 連接件10，包括該碳化矽陶瓷件20、該不銹鋼件30及連 接該不銹鋼件3 0與該碳化矽陶瓷件2 0的連接部8 0。該連 接部80包括一第一過渡層81、一鉬層82、一第二過渡層 83、一鎳層84及一第三過渡層85。 [0025] 該第一過渡層81位於碳化矽陶瓷件20與鉬層82之間。第 一過渡層81主要由鎳鉬金屬間化合物與鎳矽化合物組成 。第一過渡層81由所述鑛覆於碳化石夕陶竟件20上的錄金 屬層60與鉬層82與碳化矽陶瓷件20中的矽元素反應而得 ，由於鎳金屬層60厚度較小，在連接過程中與翻層82與 碳化矽陶瓷件20中的矽元素完全反應掉。 [0026] 該第二過渡層83位於鉬層82與該鎳層84之間，其為鉬層 82與鎳層84連接的過渡層。第二過渡層83主要由鉬鎳固 熔體及鉬鎳金屬間化合物組成。 [0027] 該第三過渡層85位於鎳層84與不銹鋼件30之間，其為鎳 層84與不銹鋼件30連接的過渡層。第三過渡層85主要由 鎳鐵金屬間化合物及鎳鐵固熔體組成。 [0028] 所述鉬層82與鎳層84的厚度大約均為0. 08〜0. 45mm，該 連接部8 0的總厚度大約為0. 21〜1. lmm。 [0029] 該不銹鋼與碳化矽陶瓷的連接件10的連接部80緻密均勻 ，無裂缝，無孔隙。經測試，該不銹鋼與碳化矽陶瓷的 連接件1 0的不銹鋼/碳化矽陶瓷介面的剪切強度可達 50〜80MPa，抗拉強度達60~100MPa。 【圖式簡單說明】 [0030] 圖1為本發明較佳實施例不銹鋼與碳化矽陶瓷的連接方法 099138065 表單編號A0101 第8頁/共15頁 0992066344-0 201219130 [0031] 原理圖。 圖2為本發明較佳實施例的不銹鋼與碳化矽陶瓷的連接件 的剖面示意圖。 [0032] 【主要元件符號說明】 不銹鋼與碳化矽陶瓷的連接件：10 [0033] 碳化矽陶瓷件：20 [0034] 不銹鋼件：30 [0035] ❹ [0036] 鉬箔：40 鎳箔：50 [0037] 鎳金屬層：60 [0038] 連接模具：70 [0039] 上壓頭：72 [0040] 下壓頭：74 £ [0041] 中模：76 [0042] 連接部：80 [0043] 第一過渡層：81 [0044] 鉬層：82 [0045] 第二過渡層：83 [0046] 鎳層：84 [0047] 第三過渡層：85 099138065 表單編號A0101 第9頁/共15頁 0992066344-0 201219130 100 [0048] 熱壓燒結爐 099138065The addition of the intermediate metal layer ' achieves a diffusion bond between the two at high temperatures. Pass A, which is a metal with high activity or a small amount of expansion and a large amount of carbon. Adding a highly active metal such as nickel to the ceramic side enables the reaction connection between the stainless steel and the tantalum carbide ceramic. However, since the thermal expansion coefficient of nickel is largely different from that of the ceramic, a large thermal stress y is present to lower the bonding force. A metal such as molybdenum having a small coefficient of thermal expansion and a large modulus of elasticity is added to the ceramic side. Since the activity of the metals is low, the diffusion reaction with Tauman is difficult, so that the connection is difficult. SUMMARY OF THE INVENTION [0004] In view of the above, it is necessary to provide an easy-to-implement method for connecting stainless steel and tantalum carbide ceramics having a connection strength of 099138065 Form No. A0101, Page 3 of 15 201219130. [0005] In addition, it is also necessary to provide a connector made by the above connection method. [0006] A method for joining stainless steel and tantalum carbide ceramics, comprising the steps of: [0007] providing a stainless steel piece to be joined, a tantalum carbide ceramic piece, a molybdenum foil, and a nickel foil; [0008] the tantalum carbide ceramic piece, the stainless steel piece Molybdenum foil and nickel foil are respectively polished and cleaned; [0009] depositing a nickel metal layer on the surface of the tantalum carbide ceramic member; [0010] placing the tantalum carbide ceramic member, the molybdenum foil, the nickel foil and the stainless steel into the joint mold, The molybdenum foil and the nickel foil are sandwiched between the tantalum carbide ceramic piece and the stainless steel piece, and the molybdenum foil is adjacent to the nickel metal layer on the tantalum carbide ceramic piece, and the nickel foil is adjacent to the stainless steel piece; [0011] the connecting die is placed In the hot press sintering furnace, the workpiece is subjected to solid phase diffusion bonding under a protective atmosphere; [0012] After cooling, the joint of the stainless steel and the tantalum carbide ceramic is taken out. [0013] A joint of stainless steel and tantalum carbide ceramic, the joint of the stainless steel and the tantalum carbide ceramic comprises a stainless steel piece, a tantalum carbide ceramic piece and a connection portion connecting the stainless steel piece and the tantalum carbide ceramic piece, the connection part comprises a transition layer, a molybdenum layer, a second transition layer, a copper layer and a third transition layer, the first transition layer is located between the tantalum carbide ceramic piece and the molybdenum layer, and the first transition layer is recorded by the inter-metal compound and the recorded stone a compound composition, the second transition layer is located between the molybdenum layer and the copper layer, and the second transition layer is composed of a molybdenum-copper solid solution and a molybdenum-copper intermetallic compound, the third transition layer being located between the copper layer and the stainless steel member , the third transition layer consists of copper-iron intermetallic compound and copper-iron solid solution group 099138065 Form No. A01O1 Page 4 / Total 15 Page 0992066344-0 201219130 into 0 [0014] Compared with the prior art, the above stainless steel and tantalum carbide The ceramic connection is to deposit a layer of nickel metal on the surface of the tantalum carbide ceramic part, and then apply the molybdenum foil and the nickel foil as an intermediate medium layer in the hot press sintering furnace. The solid phase diffusion bonding of steel. Applying a molybdenum foil with a small expansion coefficient as a connecting medium on the side of the tantalum carbide ceramic member reduces the thermal stress between the stainless steel and the tantalum carbide ceramic, and effectively prevents the crack from being generated, which is deposited on the surface of the tantalum carbide ceramic part. The nickel metal layer is more active' to make up for the shortcomings of 19 and carbon shouting slow response and difficult to connect. However, it is applied to the single-steel part—the side (4) has better activity, and the unrecorded steel is not connected to the steel, and the steel is not connected to the steel, and the non-recorded steel produced by the method has a large connection with the carbon (four) shouting connector. Strength: [Embodiment] [0015] Next step Ο [0016] (1) a carbonized stone ceramic piece 20 and stainless steel piece 3 〇 provide 40 minus 5G to connect Na 3Q (4). ^ 9 η shell. δ海钼箔40 and nickel foil 50 W.2~G.5mm, its preferred thickness system. (4) Lai 〇 [0017] 099138065 (2) Polishing carbonized stone 兖 兖 兖 2 2 2 2 2 2 2 2 , cleaning, and drying,, from 4 ◦ with the box paper grinding carbon correction « pieces 2G, with carbon cutting sand = diamond sand steel museum 4 〇 with money 50 into the wood mill steel parts 30, pieces 30, _ 〇 With the box 5. Surface comparison: Pottery: 2°, no steel form No. A0101, page 5 / total π page I, and then ultrasonically cleaned with ultrasonic wave 0992066344-0 201219130 for 5~15 minutes to remove carbon cut Ceramics 20, do not record 3 〇, turn the box 4 〇 and record 5 〇 surface impurities and oil loss, etc. After cleaning, blow dry, prepare the following f carbonization (four) (four), do not record steel parts 3 〇, molybdenum foil 40 It is called a workpiece with a nickel foil. [0020] [0020] (3) deposition on the surface of the dish-cut ceramics - recording metal layer 6 〇. The nickel metal layer 60 can be formed by a vacuum coating method, such as riding, or by forming a U of a chemical film. The thickness thereof is large (four) 2 to..., 3 to 4^ preferably (4). 2 〇 - molybdenum foil 4 〇 - nickel foil π - non-recording steel 3G compliant - connect the mold 7 () towel, so that (4) 4Q and recording 羯 50 placed in the 碳 矽 ceramic parts 2 〇 and stainless steel parts 3 〇 The molybdenum foil 40 is adjacent to the nickel metal layer 60 of the tantalum carbide ceramic member 2, and the nickel foil 50 is adjacent to the stainless steel member 30. The joining mold 7A includes an upper pressing head 72, a lower pressing head, 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 press the workpiece placed in the cavity from both sides, respectively. The joining mold 7 can be made of a graphite material. (5) The joining mold 70 is placed in a hot press sintering furnace 1 to perform solid phase diffusion bonding of the workpiece under a protective atmosphere. After the mold 7 is placed in the hot press sintering furnace 100, the hot press sintering furnace is evacuated to 2xl 〇 -3 Pa 〜 8 x l (T3Pa, then argon gas is charged as a protective atmosphere, and argon gas is charged and then hot pressed and sintered. The pressure in the furnace 100 can be 0. 2~0. 5MPa. The hot press sintering furnace 100 is heated under a protective atmosphere, and the workpiece is subjected to solid phase diffusion connection under the following process parameters: the temperature rise rate is 20 before the temperature reaches 300 °c. ~4(TC/min, after 300°C, the heating rate is 60~120°C/min, the connection temperature is 099138065 Form No. A0101 Page 6/15 pages 0992066344-0 201219130 [0021] Ο [0022] [0023 Ο [0024] 850~ll〇(TC, connection temperature holding time is 15 35min, axial pressure is UMOOMPa. The specific application method of axial pressure is: when the temperature reaches 30 (TC, by the upper head 72 The lower waste head 74 starts to apply an axial pressure of 10 MPa to the workpiece, and then slowly increases the axial pressure until the temperature is the maximum temperature at the connection temperature. Under the above temperature and pressure, the guards The interface between the contact interfaces is fully interdiffused; the holding time at the connection temperature is controlled at 15 35 minutes. Internal time: the thickness of the diffusion transition layer formed between each contact interface is the largest; when the holding time is too long, it is not conducive to saving energy. If the holding time is too short, the reading is not sufficient, and it is difficult to form obvious ';: :' . :': :;' L . (6) After cooling, take out the joints of stainless steel parts 3〇 and tantalum carbide pottery. The above-mentioned connection method of carbon steel and carbon shouting is in carbon cutting ceramics Other surface deposition—recording the metal layer 60, and then applying the molybdenum (4)_(10) as the intermediate medium (4) in the hot press sintering furnace 1 to realize the @相录 connection of the carbon cut ceramic member 20 and the non-piece 3〇. On the side of the carbon-cut ceramics, a key with a small expansion coefficient is applied as a connecting medium to reduce the thermal stress between the stainless steel and the tantalum carbide ceramics, effectively preventing cracks and improving the joint strength; depositing on the carbonized stone The metal layer 60 on the surface of the 2 member of the man-made member has a large activity, which makes up for the deficiency of carbonization and ceramsite: it is a reaction that is slow in reaction and difficult to connect. The nickel foil 5 applied to the side of the stainless steel member has better activity. Good solid solution with stainless steel, easy to be stainless Figure 30 shows the connection of the carbon-cut Tauman made by the above-mentioned joining method. 099138065 Form No. A0101 No. 7 1 / Page 15 0992066344-0 201219130 Connector 10, including the tantalum carbide member 20, The stainless steel member 30 and the connecting portion 80 connecting the stainless steel member 30 and the tantalum carbide ceramic member 20. The connecting portion 80 includes a first transition layer 81, a molybdenum layer 82, a second transition layer 83, and a A nickel layer 84 and a third transition layer 85. [0025] The first transition layer 81 is located between the tantalum carbide ceramic member 20 and the molybdenum layer 82. The first transition layer 81 is mainly composed of a nickel-molybdenum intermetallic compound and a nickel ruthenium compound. The first transition layer 81 is obtained by reacting the metal layer 60 coated on the carbonized stone ceremonial member 20 with the lanthanum element in the molybdenum layer 82 and the tantalum carbide ceramic member 20, since the thickness of the nickel metal layer 60 is small. During the joining process, the layer 82 is completely reacted with the tantalum element in the tantalum carbide ceramic member 20. The second transition layer 83 is located between the molybdenum layer 82 and the nickel layer 84, which is a transition layer between the molybdenum layer 82 and the nickel layer 84. The second transition layer 83 is mainly composed of a molybdenum-nickel solid solution and a molybdenum-nickel intermetallic compound. [0027] The third transition layer 85 is located between the nickel layer 84 and the stainless steel member 30, which is a transition layer in which the nickel layer 84 is joined to the stainless steel member 30. The third transition layer 85 is mainly composed of a nickel-iron intermetallic compound and a nickel-iron solid solution. l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l [0029] The connecting portion 80 of the connecting member 10 of the stainless steel and the tantalum carbide ceramic is dense and uniform without cracks and voids. It has been tested that the stainless steel/cerium carbide ceramic interface of the stainless steel and tantalum carbide ceramic joint 10 has a shear strength of 50 to 80 MPa and a tensile strength of 60 to 100 MPa. BRIEF DESCRIPTION OF THE DRAWINGS [0030] FIG. 1 is a connection method of a stainless steel and a tantalum carbide ceramic according to a preferred embodiment of the present invention. 099138065 Form No. A0101 Page 8 of 15 0992066344-0 201219130 [0031] Schematic. Figure 2 is a cross-sectional view showing a joint of a stainless steel and a tantalum carbide ceramic according to a preferred embodiment of the present invention. [Description of main component symbols] Connector of stainless steel and tantalum carbide ceramics: 10 [0033] Tantalum carbide ceramic parts: 20 [0034] Stainless steel parts: 30 [0035] ❹ [0036] Molybdenum foil: 40 Nickel foil: 50 [0037] Nickel metal layer: 60 [0038] Connecting mold: 70 [0039] Upper pressing head: 72 [0040] Lower pressing head: 74 £ [0041] Medium mold: 76 [0042] Connection portion: 80 [0043] A transition layer: 81 [0044] Molybdenum layer: 82 [0045] Second transition layer: 83 [0046] Nickel layer: 84 [0047] Third transition layer: 85 099138065 Form number A0101 Page 9 / Total 15 page 0992066344- 0 201219130 100 [0048] Hot pressing sintering furnace 099138065
表單編號A0HU 第10頁/共15頁 0992066344-0Form No. A0HU Page 10 of 15 0992066344-0