201226205 六、發明說明： 【發明所屬之技術領威】 [0001] 本發明涉及一種金屬與陶瓷之複合件及其製造方法，尤 其涉及一種錫青銅與碳化矽陶瓷複合件及其製造方法。 [先前技術3 [0002] 錫青銅在常溫下具有較好之耐腐蝕性能，被廣泛應用於 製造各種工程結構和機械零件。然而，在高溫、腐蝕性 等較為惡.劣之故境下’踢青銅之财腐钱性、财磨性、抗 沖蝕性、耐高溫性能等已經很難滿足現代生產技術之進 一步需求。而碳化矽陶驚具有硬度高高溫抗腐蝕、耐 磨知 '抗沖触等優點β因此.，錫青銅和破作妙陶究連接 在一起製備成複合結構，對於錫青銅在:惡劣環境中應用 具有非常重要之意義。 〃'ί [0003] 目前，實現錫青銅與碳化矽陶瓷之連搔i要係在兩者間 添加中間單層或多層金屬層，在€溫下實現兩者之擴散 連接。採用單層金屬層難於形成熱膨脹係數之階梯弋變 化，在降低熱應力上作用有限，錫青鋼與碳化矽陶瓷 結合力欠佳。而目前採用之多層金屬層更注重中之 層之活性和相互間之反應，未能充分考慮到熱膨 要形成階梯式變換，不能大幅降低熱應力。 、 【發明内容】 [0004] 有鑒於此，有必要提供一種易於實現之、可獲得較一連 接強度之錫青鋼與碳化石夕陶瓷複合件。 [0005] 另外，還有必要提供一種製造上述複合件之製造方去 099145093 表單編號A0101 第3頁/共13頁 201226205 [0006] 一種錫青銅與碳化矽陶瓷複合件，談主 兗複合件包括-錫青銅件、1 炭化砂陶^、兔化石夕陶 青銅件與㈣化卵究件之連接# 〗連接該錫 、 日’该連接層包括—篦 一過渡層、一鋁層、一第二過渡屉、 第 m —錄層及一莖：T、風 渡層，該第-减層餘碳切”件純層= 一過渡層主要由鋁碳化合物及矽鉋化人 弟 過渡層位於鋁層與該鎳層之間，、、勿、且成，δ亥第二 化合物及㈣S1溶體組成，該第 、層主要由在呂鎳 青銅件之間，第三過渡層主要 物組成。 體及鎳銅化合 [0007] 種锡青銅與碳化矽陶瓷複合件之製造方 步驟： ’ 包括以 下 [0008] [0009] 提供一錫㈣、〜㈣、-料及-㈣; :和該::衝件，銅件、〜分別 進行打 [0010] [0011] [0012] =切陶究件、及錫青銅件放入 具中，使_和_夹放在碳切陶 =接板 鄰； ㈣切岐件《，㈣與錫青铜件相 在保護氣氛下進行固 將連接模具放入—厭 熱壓燒結爐中 相擴散連接； 待冷卻後取碳切㈣複合件。 上述锡青銅與碳切㈣複合件之製造方法在熱麼燒結 099145093 表單編號A0I01 第4頁/共13頁 0992077814-0 [0013] 201226205201226205 VI. Description of the Invention: [Technical Leadership of Invention] [0001] The present invention relates to a composite of metal and ceramics and a method of manufacturing the same, and more particularly to a tin bronze and tantalum carbide ceramic composite and a method of manufacturing the same. [Prior Art 3 [0002] Tin bronze has good corrosion resistance at room temperature and is widely used in the manufacture of various engineering structures and mechanical parts. However, it is difficult to meet the further needs of modern production technology by playing the green money, the grindiness, the erosion resistance and the high temperature resistance of high-temperature, corrosive and other inferior circumstances. The carbonized bismuth ceramic has the advantages of high hardness, high temperature, corrosion resistance, wear resistance, and anti-shocking. Therefore, tin bronze and broken ceramics are connected together to prepare a composite structure for tin bronze in: harsh environment. Very important. 〃'ί [0003] At present, the realization of the connection between tin bronze and tantalum carbide ceramics is to add an intermediate single layer or multiple layers of metal between the two to achieve the diffusion connection between the two. The use of a single layer of metal layer is difficult to form a step change in the thermal expansion coefficient, and has a limited effect on reducing thermal stress. The bonding strength between tin-green steel and tantalum carbide ceramics is poor. However, the multi-layer metal layer currently used pays more attention to the activity of the middle layer and the reaction between them. The thermal expansion is not fully considered to form a stepwise transformation, and the thermal stress cannot be greatly reduced. SUMMARY OF THE INVENTION [0004] In view of the above, it is necessary to provide a tin-cyan steel and carbon carbide ceramic composite member which is easy to realize and which can obtain a relatively high strength. [0005] In addition, it is also necessary to provide a manufacturing method for manufacturing the above composite member to 099145093 Form No. A0101 Page 3 / Total 13 pages 201226205 [0006] A tin bronze and tantalum carbide ceramic composite member, the main composite member includes - Tin bronze pieces, 1 carbonized sand pottery ^, rabbit fossil eve pottery bronze pieces and (four) ovulation parts connection # 〗 Connect the tin, day 'the connection layer includes - 篦 a transition layer, an aluminum layer, a second transition Drawer, m-recording layer and one stem: T, wind-crossing layer, the first-reduced layer carbon cut "pure layer" = a transition layer mainly composed of aluminum carbon compound and 矽 化 人 人 位于 位于 位于The nickel layer is composed of a second compound and a (4) S1 solution, and the first layer is mainly composed of a main layer of the third transition layer between the Lu-nickel bronze pieces and the nickel-copper. [0007] The manufacturing steps of the tin-copper and tantalum-cerium composite parts: 'Including the following [0008] [0009] Providing a tin (four), ~ (four), - material and - (four); and::: punching, copper parts , ~ separately play [0010] [0011] [0012] = cut ceramic pieces, and tin bronze pieces into the set, Place the _ and _ clips on the carbon cut pot = joint plate; (4) cut the piece ", (4) and the tin bronze piece in a protective atmosphere to solidify the joint mold into the - anisotropic pressure sintering furnace phase diffusion connection; After cooling, the carbon cut (four) composite piece is taken. The manufacturing method of the above-mentioned tin bronze and carbon cut (four) composite parts is hot sintered 099145093 Form No. A0I01 Page 4 / Total 13 Page 0992077814-0 [0013] 201226205
爐中藉由施加㈣和㈣作為中間介質層’實現竣 陶免件與料銅狀附目擴朗接。切化㈣竟件— 側施加膨脹係數與礙切陶餘近之”作為連接介質 ，銘與碳切陶練容易發生反應結合，在錫青銅一侧 施加熱膨脹係數㈣青銅㈣之料作為賴介質，且 錄之膨脹係數介⑽青触|3之間，同時鎳祕能實現 良好結合；如此，碳切m鎳、錫青銅之熱膨 脹係數逐漸增大，《了碳切m料銅之階梯式 變化，有效降低了熱應力，提高了結合力。且各金屬間 產生之金屬間化合物較少，不會造成結合強度下降。 【實施方式】 剛m㈣本發⑱佳實_之料鋼_切喊複合件 1〇剖面示意圖。錫青銅與碳切㈣複合㈣包括該碳 化㈣竞件20、該錫青銅件3G及連接&青銅㈣與該 碳化石夕陶究件2G之連接層8G。該連接層8Q包括一第一過 渡層8卜-銘層82、一第二過渡層83、一錄層^及一第 三過渡層85。該第一過渡層81位於碳化矽陶瓷件2〇與鋁 層82之間。第一過渡層μ主要由鋁碳化合物及矽鋁化合 物組成’如碳化鋁等。該第二過渡層83位於鋁層82與該 鎳層84之間，其為銘層μ與錄層84連接之過渡層。第二 過渡層83主要由铭錄化合物及銘錄固溶體組成。該第三 過渡層85位於鎳層84與錫青銅件3〇之間，其為鎳層84與 錫青銅件30連接之過渡層。第三過渡層85主要由鎳銅固 溶體及鎳銅化合物組成。因為錫青銅中含有原子百分含 量不命於10%之錫（Sn)，因此第三過渡層85還包括錄錫 099145093 化合物及鎳錫固溶體。 表單編號A0101 第5頁/共13頁 0992077814-0 201226205 [0015] [0016] 該錫青銅與碳切Μ複合件 無裂縫，無孔隙。經測試，該錫青^層8G緻密均勾， ㈣之錫青鋼/碳化石夕陶究介面之剪4化石夕陶竟複合 5〇〜8〇MPa，抗拉強产、W切強度可達 拉強度達6〇〜100MPa。 請參閱圖2,所述複合件 : 取&方法主要包括如下步驟 [0017] [0018] 提例切㈣件2Q和锡青銅㈣，同時 =:_〇作為連接介質。該一度大 二= 陶㈣〇、锡青銅件3。、_刚 ::丁打磨、清洗，並吹幹。本實施例用金_ ==_牛2〇’用碳切砂紙對錫、 f和職5G進行打磨，使碳切陶伽、錫青銅 件3〇、㈣40和鎳㈣表面較為平整4切喊件2〇 、錫青銅件3G、㉝㈣和鎳咖放人盛裝有乙醇溶液之 超聲波清洗H巾進行振動祕5〜15謂，赠去碳化梦 陶瓷件20、錫青鋼件3〇、鉬箔40和鎳箔50表面雜質及油 污等。清洗後吹幹備用。 [0019] (3)將碳化矽陶瓷件2〇、鋁箔4〇、鎳箔5〇、錫青銅件 30依序層疊放置於放入一連接模具7〇中，使鋁箔4〇和鎳 箔50位於碳化矽陶瓷件2〇與錫青銅件30之間，並且鋁箔 40與碳化矽陶瓷件2〇相鄰，鎳箔50與錫青銅件3〇相鄰。 該連接模具70包括上壓頭72、下壓頭74及中模76。該中 模76具有一模腔（圖未標），用於容置待連接工件。該 099145093 表單編號A0101 第6頁/共13頁 0992077814-0 201226205 上g頁m下壓頭74分別從兩端將放置於模腔中之工件 壓緊。該連接模具70可以為石墨材料製成。 [0020] Ο [0021] 〇 [0022] ⑷將連接&具7()放人—熱壓燒職_巾，在保護氣 氛㈣相擴散連接。連接模具7q放入献壓燒 結爐1GG後對熱壓燒結爐⑽抽真空至μ%級，本實施 射，對熱壓燒結爐則抽真空至5χΐ(Γ3ρ&。然後充入氮 氣作為保護氣氛’充人氬氣直至熱壓燒結爐1GG内壓力為 0.3 0.6MPa。在保護氣氛下將熱壓燒結爐刚升溫，並 在如下，藝參數下對工件進行固相擴散連接：升溫速率 為1 2〇C/min，連接時温度為68〇~98〇<^，連接時溫度 之保溫時間為40〜80min，轴向壓力為1〇 5〇,。軸向 壓力之具體施加方法為：上屋頭72和下屋頭⑽始對工 件施加lGMPa之轴向壓力’加熱’在溫度到達3啊後慢 慢增大軸向壓力，直至溫度為連接時溫度時，抽向壓力 為最大值。 、 .y (5 )待冷卻後取丨錫t鋼件3()與碳化$陶究件之複合 件。 上述錫青銅與碳切喊複合件之製造方法在熱壓燒結 爐100中藉由鋁箔40和鎳箔50作為中間介質層，實現碳化 矽陶瓷件20與錫青銅件30之固相擴散連接。在碳化矽陶 瓷件一側施加膨脹係數與碳化矽陶瓷相近之鋁箔作為連 接介質，鋁與碳化矽陶瓷較容易發生反應結合，在錫青 銅一側施加熱膨脹係數與錫青銅相近之鎳羯作為連接介 質，且錄之膨脹係數介於錫青銅與銘之間，同時結與錄 能實現良好結合；如此，碳化矽陶瓷、鋁、鎳、錫青銅 099145093 表單編號A0101 第7頁/共13頁 0992077814-0 201226205 之熱膨脹係數逐漸增大，形成了碳化矽陶瓷至錫青銅熱 膨脹係數之階梯式變化，有效降低了熱應力提高結合力 。且各金屬間產生之金屬間化合物較少，不會造成結合 強度下降。 【圖式簡單說明】 [0023] 圖1為本發明較佳實施例之錫青銅與碳化矽陶瓷複合件之 剖面示意圖。 [0024] 圖2為製造圖1所示之錫青銅與碳化矽陶瓷複合件之設備 示意圖。 【主要元件符號說明】 099145093 表單編號 A0101 第 8 頁/共 13 頁 0992077814-0 [0025] 錫青銅與碳化矽陶瓷複合件：10 [0026] 碳化矽陶瓷件：20 [0027] 錫青銅件：3 0 [0028] 鋁箔：4 0 [0029] 鎳箔：50 [0030] 連接模具：70 [0031] 上壓頭：72 [0032] 下壓頭：74 [0033] 中模：76 [0034] 連接層：80 [0035] 第一過渡層：81 201226205 [0036] 鋁層 ：82 [0037] 第二 過渡層： ：83 [0038] 鎳層 ：84 [0039] 第三 過渡層： ：85 [0040] 熱壓燒結爐： ：100 Ο 099145093 表單編號Α0101 第9頁/共13頁 0992077814-0In the furnace, by applying (4) and (4) as the intermediate medium layer, the enamel-free parts and the copper-like attachments are realized. Cutting (4) the actual part - the side exerts the expansion coefficient and the obstruction of Tao Yu near" as the connecting medium, Ming and carbon cut ceramics are easy to react and combine, and apply the thermal expansion coefficient (4) bronze (4) material on the tin bronze side as the medium. And the expansion coefficient is recorded between (10) and blue touch|3, and the nickel secret can achieve a good combination; thus, the thermal expansion coefficient of carbon-cut m-nickel and tin-bronze gradually increases, "the stepwise change of carbon-cut m-material copper, The thermal stress is effectively reduced, the bonding force is improved, and the intermetallic compound generated between the metals is less, and the bonding strength is not lowered. [Embodiment] Just m (four) of the hair of the 18 good _ material steel _ shouting composite parts 1〇 Schematic diagram. Tin bronze and carbon cut (4) composite (4) including the carbonization (4) competition 20, the tin bronze piece 3G and the connection & bronze (four) and the carbonized stone ceremonial piece 2G connection layer 8G. The connection layer 8Q The first transition layer 8 includes a first transition layer 82, a second transition layer 83, a recording layer, and a third transition layer 85. The first transition layer 81 is located on the tantalum carbide ceramic member 2 and the aluminum layer 82. The first transition layer μ is mainly composed of aluminum carbon compound and yttrium aluminum. The compound composition 'such as aluminum carbide, etc.. The second transition layer 83 is located between the aluminum layer 82 and the nickel layer 84, which is a transition layer connecting the layer μ and the recording layer 84. The second transition layer 83 is mainly composed of a compound And the inscription solid solution composition. The third transition layer 85 is located between the nickel layer 84 and the tin bronze member 3〇, which is a transition layer connecting the nickel layer 84 and the tin bronze member 30. The third transition layer 85 is mainly composed of nickel. Copper solid solution and nickel-copper compound composition. Because tin bronze contains 10% tin (Sn) atomic percentage, the third transition layer 85 also includes tin 099145093 compound and nickel tin solid solution. No. A0101 Page 5 of 13 0992077814-0 201226205 [0016] [0016] The tin bronze and carbon cut composite parts have no cracks and no pores. After testing, the tin blue layer 8G is densely hooked, (4) tin Qinggang/carbonized stone ceremonial ceramic interface cut 4 fossil eve Tao actually composite 5〇~8〇MPa, tensile strength, W cut strength up to 6〇~100MPa. See Figure 2, the composite The method of taking & mainly includes the following steps [0017] [0018] The following example cuts (four) pieces of 2Q and tin bronze (four), while =: _ In order to connect the medium, the first sophomore = pottery (four) 〇, tin bronze parts 3., _ just:: ding, grinding, and drying. This example uses gold _ == _ 2 2 ' carbon cutting paper Tin, f and 5G are polished, so that the carbon cut taoga, tin bronze parts 3 〇, (4) 40 and nickel (four) surface are relatively flat 4 smashing pieces 2 〇, tin bronze pieces 3G, 33 (four) and nickel coffee put people with ethanol solution Ultrasonic cleaning H towel for vibrating secret 5~15, gifted carbonized dream ceramic parts 20, tin blue steel parts 3〇, molybdenum foil 40 and nickel foil 50 surface impurities and oil stains, etc. After washing, blow dry and spare. [0019] (3) The tantalum carbide ceramic piece 2, the aluminum foil 4 inch, the nickel foil 5 inch, and the tin bronze piece 30 are sequentially stacked and placed in a joint mold 7〇, so that the aluminum foil 4〇 and the nickel foil 50 are located in the tantalum carbide ceramic. The piece 2〇 is placed between the tin bronze piece 30, and the aluminum foil 40 is adjacent to the tantalum carbide ceramic piece 2〇, and the nickel foil 50 is adjacent to the tin bronze 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 099145093 Form No. A0101 Page 6 of 13 0992077814-0 201226205 The upper g-sheet m lower pressing head 74 presses the workpiece placed in the cavity from both ends. The joining mold 70 may be made of a graphite material. [0020] 002 [0022] (4) The connection & 7() is placed in a hot-pressed _ towel, and the protective atmosphere (four) phase is diffusion-bonded. After the connection mold 7q is placed in the pressure-sintering furnace 1GG, the hot-press sintering furnace (10) is evacuated to the μ% level, and the present embodiment is sprayed, and the hot-press sintering furnace is evacuated to 5 χΐ (Γ3ρ & then filled with nitrogen as a protective atmosphere). It is filled with argon until the pressure in the hot press sintering furnace 1GG is 0.3 0.6 MPa. The hot press sintering furnace is just heated under a protective atmosphere, and the workpiece is subjected to solid phase diffusion bonding under the following art parameters: the heating rate is 1 2〇 C/min, the connection temperature is 68〇~98〇<^, the temperature holding time is 40~80min, and the axial pressure is 1〇5〇. The specific application method of axial pressure is: upper roof 72 and the lower roof (10) start to apply the axial pressure 'heating' of the workpiece to the workpiece. After the temperature reaches 3, the axial pressure is gradually increased until the temperature is the temperature at the connection, and the pumping pressure is the maximum value. (5) After the cooling, the composite part of the tantalum tin steel part 3 () and the carbonized ceramic material is taken. The manufacturing method of the above-mentioned tin bronze and carbon shattering composite part is in the hot press sintering furnace 100 by the aluminum foil 40 and the nickel. The foil 50 serves as an intermediate dielectric layer to realize solid phase expansion of the tantalum carbide ceramic member 20 and the tin bronze member 30. Connecting. On the side of the tantalum carbide ceramic part, an aluminum foil with a coefficient of expansion similar to that of tantalum carbide ceramic is used as a connecting medium. Aluminum and tantalum carbide ceramics are more susceptible to reaction, and a nickel crucible having a thermal expansion coefficient similar to that of tin bronze is applied on the side of the tin bronze. The medium is connected, and the coefficient of expansion is between tin bronze and Ming, and the junction and recording energy are well combined; thus, tantalum carbide ceramic, aluminum, nickel, tin bronze 099145093 Form No. A0101 Page 7 / Total 13 Page 0992077814 -0 201226205 The coefficient of thermal expansion gradually increases, forming a stepwise change in the thermal expansion coefficient of tantalum carbide ceramic to tin bronze, which effectively reduces the thermal stress and improves the bonding force. The intermetallic compounds produced between the metals are less and will not cause bonding. BRIEF DESCRIPTION OF THE DRAWINGS [0023] FIG. 1 is a cross-sectional view showing a tin bronze and a tantalum carbide ceramic composite member according to a preferred embodiment of the present invention. [0024] FIG. 2 is a view showing the manufacture of the tin bronze and carbonization shown in FIG. Schematic diagram of equipment for enamel ceramic composite parts. [Main component symbol description] 099145093 Form No. A0101 Page 8 of 13 0992077 814-0 [0025] Tin bronze and tantalum carbide ceramic composite: 10 [0026] Tantalum carbide ceramic parts: 20 [0027] Tin bronze parts: 3 0 [0028] Aluminum foil: 4 0 [0029] Nickel foil: 50 [0030] Connecting mold: 70 [0031] Upper pressing head: 72 [0032] Lower pressing head: 74 [0033] Medium mold: 76 [0034] Connecting layer: 80 [0035] First transition layer: 81 201226205 [0036] Aluminum layer : 82 [0037] Second transition layer: :83 [0038] Nickel layer: 84 [0039] Third transition layer: :85 [0040] Hot pressing sintering furnace: :100 Ο 099145093 Form number Α0101 Page 9 of 13 Page 0992077814-0