201204496 六、發明說明： 【發明所屬之技術領域】 [0001] 本發明涉及一種金屬與陶瓷的連接方法及製得的連接件 ，尤其涉及一種碳鋼與氡化锆陶瓷的連接方法及製得的 連接件。 【先前技術3 [〇〇〇2] 碳鋼被廣泛應用於製造工程結構（比如船舶、發動機、 高壓容器等）和機械零件（如齒輪、轴等）❶然而碳鋼 0 存在耐磨性較差、硬度較低、抗熱衝擊性及高溫耐蝕性 較低等缺點，已經很難滿足藏代生產拽術對材料綜合性 能的進一步需求。而氧化锆陶瓷具有硬度高、高溫抗腐 蝕、耐磨損、抗熱衝擊等優點。碳鋼和氧化錘連接在— 起製備成複合結構，對於碳鋼在高溫環^_中應用具有非 常重要的意義。 [0003]由於這兩種材料的物理、化學性能差異較大，使得兩者 之間的連接非常困難，目前主要採用熔焊、釺焊、固相 〇 擴散連接及瞬間液相連接來實丨現陶瓷與金屬的連接。但 每些方法存在許多不足：難於製得高結合強度的接頭； 對金屬件表面的清潔度及設備真空度要求很高 ;固相擴 散連接及瞬間液相連接溫度要求較高，保溫時間長，導 致兩者間的連接耗時、耗能；溶焊容易產生裂紋；釺桿 雖然連接溫度較低，但由於釺料的魅普遍較低’因此 奸焊難於製得能在高溫下使用的接頭。 【發明内容】 有鑒於此，有必要提供一種加工時間短、可獲得較高結 099124622 表單編號A0101 第3頁/共13頁 0992043292-0 201204496 合強度的碳鋼與氧化錯陶瓷的連接方法。 [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] 一種碳鋼與氧化鍅陶瓷的連接方法，包括以下步驟： [0007] 提供一待連接的碳鋼、一氧化锆陶瓷及一鈦箔； [0008] 對該鈦箔、碳鋼及氧化锆陶瓷的待連接表面進行打磨、 清洗並吹幹； [0009] 提供一石墨模具，該模具包括上壓頭、下壓頭及中模； [0010] 將該鈦箔、碳鋼及氧化鍅陶瓷放入石墨模具中，使鈦箔 夾放於碳鋼與氧化锆陶瓷之間，並且用所述上、下壓頭 壓緊； [0011] 將該石墨模具放入一放電等離子體燒結設備的爐膛中， 開啟直流脈衝電源，以對碳鋼及氧化鍅陶瓷施加脈衝電 流而進行放電等離子體連接，設置工藝參數為：軸向壓 力為10〜50MPa，升溫速率為50〜600°C/min，連接溫度 為800〜1100°C，保溫時間為10〜50分鐘，爐膛内的真空 度為6〜10Pa ; [0012] 待冷卻後取出碳鋼與氧化锆陶瓷的連接件。 [0013] 一種碳鋼與氧化鍅陶瓷的連接件，該碳鋼與氧化鍅陶瓷 的連接件包括一碳鋼件、一氧化鍅陶瓷件及連接該碳鋼 件與該氧化錯陶曼件的連接部，該連接部包括一第一過 渡層、一欽金屬層及一第二過渡層，該第一過渡層位於 該碳鋼件與該鈦金屬層之間，該第一過渡層位於該氧化 099124622 表單編號A0101 第4頁/共13頁 0992043292-0 201204496 [0014] ❹ [0015] [0016] 0 _ [0018] 陶究件與該欽金屬層之間，該第一過渡層由欽與鐵的 炫體及妖鐵金屬間化合物組成，該第二過渡層主要由 欽乳化合物、敛錯化合物組成。 於1知技術，上述碳鋼與氧化锆陶瓷的連接方法採 放电等離子體燒結設傷（或者稱脈衝電流加熱設備 山對碳鋼件與氧化錯喊件施加脈衝電流及壓力來實現 ^鋼與氧化_:£的連接，保溫時間短，能耗低，對設 備真空度要求較低。由财法製得的伽與氧化結陶究 的連接件具有較大的剪切強度。 【實施方式】 明參閱圖1，本發明較佳實施例的碳鋼與氧化錯陶究的連 接方法主要藉由—放電轉子體燒結設備㈣完成，該 方法主要包括如下步驟： (1) 提供-待連接的碳鋼件2〇、_氧化錯陶竞件3〇及_ 活性中間層4G。該活性中間層⑽鈦笛，其厚度大約為 〇·卜0.5111111，較佳厚度為0.2~0 3關6 (2) 對活性中間層4〇及碳鋼件2()和氧化錯陶变件3〇的待 連接表面進行㈣、清洗，並吹幹。本實_中可以使 用400〜800目的金相砂紙對活性中間層4〇、碳鋼件別及 氧化錯陶瓷件30打磨；然後用稀鹽酸或稀硫酸溶液進行 清洗；酸清洗後用水沖洗並吹幹。以下將活性中間層4〇 、碳鋼件20及氧化锆陶瓷件3〇統稱為工件。 (3) 提供一石墨模具50，該石墨模具5〇包括上壓頭51、 下壓頭52及中模53,該中模53具有一模腔（圖未示）， 099124622 表單編號A0101 第5頁/共13頁 0992043292-0 201204496 用於容置待連接工件。 [0019] [0020] [0021] (4)將工件放入石墨模具5〇中，使活性中間層4〇失放於 碳鋼件20與氧化鍅陶瓷件30之間，並且用上壓頭51和下 壓頭52壓緊。 (5)提供一放電等離子體燒結設備1〇，比如可採用日本住 友石炭公司生產的SPS3. 20ΜΚ-IV型放電等離子燒結設備 。該放電等離子體燒結設備1〇主要包括：軸向壓力系統 π ’用於對燒結工件提供軸向壓力；正、負電極12;爐 膛13 ;直流脈衝電源14，用於對燒結工件提供脈衝電流 ，使工件升溫；溫度測量單元（圖未示）及控制系統1 5等 。該直流脈衝電源脈寬比為12 : 2，最大電流可達5〇〇〇a 〇 ... (6)將石墨模具5〇放入該放電等離子體燒結設備1〇的爐 膛13中，並且用上壓頭51與下壓頭52分別與放電等離子 體燒結設備10的正、負電極12舞率連接，爐膛13抽真空 至真空度為6〜10Pa，開啟:£流脈衝趣瓿14，設置如下工 藝參數對工件進行放電等離子體連接：轴向壓力為 10~50MPa ’升溫速率為50〜600°C/min ;當溫度為 800〜ll〇〇°C時’保持該溫度範圍約1〇~50分鐘時長，該 溫度即為連接溫度，此時對應施加的脈衝電流強度大約 為2500〜4500A。其中所施加的軸向壓力可根據氧化錯陶 瓷件30的大小、厚度進行具體調整。所述升溫速率較佳 為50〜300°C/min ’連接溫度較佳為850〜105(TC，保溫201204496 VI. Description of the Invention: [Technical Field of the Invention] [0001] The present invention relates to a method for joining metal and ceramics and a connector formed thereby, and more particularly to a method for joining carbon steel and zirconium sulphide ceramic and a method for producing the same Connector. [Prior Art 3 [〇〇〇2] Carbon steel is widely used in manufacturing engineering structures (such as ships, engines, high-pressure vessels, etc.) and mechanical parts (such as gears, shafts, etc.). However, carbon steel 0 has poor wear resistance. The shortcomings of low hardness, thermal shock resistance and low temperature corrosion resistance have made it difficult to meet the further demand for comprehensive performance of materials in Tibetan production. The zirconia ceramic has the advantages of high hardness, high temperature corrosion resistance, wear resistance and thermal shock resistance. Carbon steel and oxidizing hammer are connected to form a composite structure, which is of great significance for the application of carbon steel in high temperature ring. [0003] Due to the large difference in physical and chemical properties between the two materials, the connection between the two materials is very difficult. At present, fusion welding, brazing, solid-phase diffusion bonding and instantaneous liquid phase connection are mainly used. Ceramic to metal connection. However, there are many shortcomings in each method: it is difficult to produce a joint with high bonding strength; the cleanliness of the surface of the metal parts and the vacuum of the equipment are very high; the solid phase diffusion connection and the instantaneous liquid phase connection temperature are high, and the heat preservation time is long. The connection between the two is time-consuming and energy-consuming; the welding is prone to cracks; although the connection temperature of the mast is low, the charm of the material is generally low, so it is difficult to produce a joint that can be used at high temperatures. SUMMARY OF THE INVENTION In view of the above, it is necessary to provide a method for connecting carbon steel and oxidized ceramics with a short processing time and a high junction 099124622 Form No. A0101 Page 3/13 page 0992043292-0 201204496. [0005] In addition, it is also necessary to provide a connector 制 [0006] a method of connecting carbon steel and yttria ceramic, comprising the following steps: [0007] providing a carbon steel to be connected, a zirconia ceramic and a titanium foil; [0008] grinding, cleaning and drying the surface to be joined of the titanium foil, carbon steel and zirconia ceramic; [0009] providing a graphite mold, the mold comprising an upper pressing head, a lower Indenter and middle mold; [0010] placing the titanium foil, carbon steel, and yttria ceramic into a graphite mold, sandwiching the titanium foil between the carbon steel and the zirconia ceramic, and using the upper and lower indenters [0011] The graphite mold is placed in a furnace of a discharge plasma sintering apparatus, and a DC pulse power source is turned on to apply a pulse current to the carbon steel and the yttria ceramic to perform a discharge plasma connection, and the process parameters are set as follows: The axial pressure is 10~50MPa, the heating rate is 50~600°C/min, the connection temperature is 800~1100°C, the holding time is 10~50 minutes, and the vacuum in the furnace is 6~10Pa; [0012] Remove carbon steel and zirconia ceramics after cooling Connector. [0013] A connecting member of carbon steel and cerium oxide ceramic, the connecting member of the carbon steel and cerium oxide ceramic comprises a carbon steel member, a cerium oxide ceramic member and a connection between the carbon steel member and the oxidized fault ceramic member The connecting portion includes a first transition layer, a metal layer and a second transition layer, the first transition layer is located between the carbon steel member and the titanium metal layer, and the first transition layer is located at the oxidation 099124622 Form No. A0101 Page 4 / Total 13 Page 0992043292-0 201204496 [0014] [0016] 0 _ [0018] Between the ceramic piece and the metal layer of the Qin, the first transition layer is made of Qin and iron The composition of the glare and the demon iron intermetallic compound, the second transition layer is mainly composed of a chinchilles compound and a miscible compound. According to the prior art, the connection method of the above carbon steel and zirconia ceramics is caused by the discharge plasma sintering (or the pulse current heating device mountain applies the pulse current and pressure to the carbon steel parts and the oxidized faulty parts to realize the steel and oxidation. _: £ connection, short holding time, low energy consumption, low requirements on equipment vacuum. The connection between gamma and oxidized knots made by the financial method has a large shear strength. 1 , the method for connecting carbon steel and oxidizing ceramics according to a preferred embodiment of the present invention is mainly completed by a discharge rotor body sintering device (4), which mainly comprises the following steps: (1) providing - carbon steel pieces to be connected 2〇, _ oxidized wrong ceramics 3 〇 and _ active intermediate layer 4G. The active intermediate layer (10) titanium flute, the thickness of which is about 〇 · bu 0.5111111, preferably thickness 0.2 ~ 0 3 off 6 (2) on the activity The intermediate layer 4〇 and the surface of the carbon steel 2() and the oxidized ceramic member 3〇 are subjected to (4), cleaned, and blown dry. In this embodiment, a 400-800 mesh metallographic sandpaper can be used for the active intermediate layer 4 〇, carbon steel parts and oxidized ceramic parts 30 polished; then Dilute hydrochloric acid or dilute sulfuric acid solution for cleaning; acid cleaning, rinse with water and blow dry. The active intermediate layer 4〇, carbon steel 20 and zirconia ceramic parts are collectively referred to as workpieces. (3) A graphite mold 50 is provided. The graphite mold 5 includes an upper pressing head 51, a lower pressing head 52 and a middle mold 53. The middle mold 53 has a cavity (not shown), 099124622 Form No. A0101 Page 5 of 13 0992043292-0 201204496 [0019] [001] (4) placing the workpiece into the graphite mold 5〇, causing the active intermediate layer 4 to be displaced between the carbon steel member 20 and the yttria ceramic member 30. And pressing with the upper pressing head 51 and the lower pressing head 52. (5) Providing a discharge plasma sintering apparatus 1〇, for example, an SPS 3.20ΜΚ-IV type discharge plasma sintering apparatus produced by Sumitomo Carbon Corporation of Japan. The plasma sintering apparatus 1〇 mainly comprises: an axial pressure system π′ for providing axial pressure to the sintered workpiece; positive and negative electrodes 12; furnace 13; DC pulse power supply 14 for supplying pulse current to the sintered workpiece to make the workpiece Heating; temperature measuring unit (not shown) Control system 1 5, etc. The DC pulse power supply has a pulse width ratio of 12:2, and the maximum current can reach 5〇〇〇a 〇... (6) Put the graphite mold 5〇 into the discharge plasma sintering equipment The furnace 13 is connected to the positive and negative electrodes 12 of the discharge plasma sintering apparatus 10 by the upper pressing head 51 and the lower pressing head 52, respectively, and the furnace 13 is evacuated to a vacuum of 6 to 10 Pa, and the opening is: Interesting 14, set the following process parameters to discharge plasma connection of the workpiece: axial pressure is 10~50MPa 'heating rate is 50~600°C/min; when the temperature is 800~ll〇〇°C, keep the temperature The range is about 1〇~50 minutes, and the temperature is the connection temperature. At this time, the corresponding applied pulse current intensity is about 2500~4500A. The axial pressure applied therein can be specifically adjusted according to the size and thickness of the oxidized ceramic member 30. The heating rate is preferably 50 to 300 ° C / min. The connection temperature is preferably 850 to 105 (TC, heat preservation).
時間較佳為10〜30分鐘，脈衝電流強度較佳為6〇〇〜4000A 099124622 表單編號A0101 第6頁/共13頁 0992043292-0 201204496 [0022] ⑺待冷卻後取出碳鋼與氧化錯陶莞的連接件。 [_上述碳鋪氧⑽㈣的連接方法藉由—放電等離子體 燒結設備10 (或者稱脈衝電流加熱設備），對碳鋼件加 與氧化錄陶兗件30施加脈衝電流，以於碳鋼件2〇與氧化 錯陶究件3G的接觸縫隙之間放電產生高熱等離子體等 離子體清潔並活化卫件的表面，提高卫絲面的原子擴 散能力。 ' _] S脈衝電流作用下，碳鋼件2Q、氧化錯陶究件⑽及活性 D 巾間層40鈦fg產生自發熱及局部放電熱，㈣的活化溫 度低於碳鋼件2〇和氧化鎂陶瓷件3〇的軟化溫度，鈦箔首 先活化釋放am原子，Ti原子迅速擴散到伽件2〇和氣 化錯喊侧表φ ’並與钱件2G和氧化細:£件3〇發 生一物理、化學反應’比如π原子奪氧能力較強，可從 氧化錯H件30中奪取氧，形成鈦氧化合物，Ti原子同 時可與糾成鈦錯化合物及與氧化結喊件3()反應形成 ®㈣等’由此於碳鋼/氧化錯料介面形成新的物相結 0 構’該新的物相結構有利於促進:氧化錯陶兗/碳鋼介面的 擴散結合，加之轴向壓力之作用，工件間接觸面積不斷 增大，最終達到緊密接觸而連接在一起。 则_L述碳鋼與氧化鍅陶兗的連接方法保溫時間短，能耗低 ’對爐膛真空度要求較低。 [_]目2所示為由上述連接方法製得的碳鋼與氧化錯陶究的連 接件100，包括該碳鋼件20、該氧化鍅陶瓷件3〇及連接該 碳鋼件20與該氧化鍅陶竟件30的連接部60。該連接部60 099124622 表單編號A0101 第7頁/共13頁 0992043292-0 201204496 包括一第一過渡層61、一欽金屬層62及一第二過渡層63 。該第一過渡層61位於該碳鋼件20與該鈦金屬層62之間 ，該第一過渡層61主要由鈦與鐵的固熔體及鈦鐵金屬間 化合物組成。該第二過渡層63位於該氧化锆陶瓷件30與 該鈦金屬層62之間，該第二過渡層63主要由鈦氧化合物 、鈦锆化合物及極少量的鈦錯固熔體組成。該第一過渡 層61及第二過渡層63的厚度大約均為5~30/zm，較佳地 為 1 0~20 从 m。 [0027] 該碳鋼與氧化銼陶瓷的連接件100的連接部60平整均勻， 無裂縫，無孔隙。經檢測，該碳鋼與氧化锆陶瓷的連接 件100的碳鋼/氧化锆陶瓷介面的剪切強度可達 80〜150MPa。 【圖式簡單說明】 [0028] 圖1為本發明較佳實施例使用一放電等離子體燒結設備進 行碳鋼與氧化鍅陶瓷連接的示意圖。 [0029] 圖2為本發明較佳實施例的碳鋼與氧化鍅陶瓷的連接件的 剖面示意圖。 【主要元件符號說明】 [0030] 放電等離子體燒結設備：10 [0031] 軸向壓力系統： 11 [0032] 電極：12 [0033] 爐膛：13 [0034] 直流脈衝電源： 14 表單編號A0101 第8頁/共13頁 099124622 0992043292-0 201204496 [0035] [0036] [0037] [0038] [0039] [0040] [0041] 0 [0042] [0043] [0044] [0045] [0046] [0047] ❹ 控制系統：1 5 碳鋼件：20 氧化鍅陶瓷件：30 活性中間層：4 0 石墨模具：50 上壓頭：51 下壓頭：52 中模：53 碳鋼與氧化锆陶瓷的連接件：100 連接部：60 第一過渡層：61 欽金屬層：62 第二過渡層：63 099124622 表單編號A0101 第9頁/共13頁 0992043292-0The time is preferably 10 to 30 minutes, and the pulse current intensity is preferably 6 〇〇 to 4000 A. 099124622 Form No. A0101 Page 6 / Total 13 Page 0992043292-0 201204496 [0022] (7) After cooling, remove carbon steel and oxidize the wrong pottery Connector. [_ The above-mentioned method of connecting carbon (10) (4) to carbon oxides by applying a discharge plasma sintering apparatus 10 (or a pulse current heating apparatus) to apply a pulse current to the carbon steel member and the oxidation recording member 30 for carbon steel 2 The discharge between the contact gap of the ruthenium and the oxidized faulty ceramic material 3G produces a high thermal plasma plasma to clean and activate the surface of the guard, thereby improving the atomic diffusion capacity of the wei wire. ' _ _ S pulse current, carbon steel 2Q, oxidation fault ceramics (10) and active D towel layer 40 titanium fg generated self-heating and partial discharge heat, (4) activation temperature is lower than carbon steel 2 〇 and oxidation The softening temperature of the magnesium ceramic part 3〇, the titanium foil is first activated to release the am atom, the Ti atom is rapidly diffused to the gamma 2〇 and the gasification is wrongly called the side table φ 'and the money piece 2G and the oxidation fine: the piece 3 〇 a physics occurs Chemical reaction, such as π atomic oxygen scavenging ability, can take oxygen from the oxidized W component 30 to form a titanium oxide compound, and the Ti atom can be formed by reacting with the titanium compound and the oxidized caller 3 (). ® (4), etc. 'There is a new phase structure formed by the carbon steel/oxidized wrong material interface'. This new phase structure is beneficial to promote the diffusion bonding of the oxidized malterite/carbon steel interface, plus the axial pressure. As a result, the contact area between the workpieces continues to increase, eventually reaching tight contact and joining together. Then _L describes the connection method of carbon steel and cerium oxide cerium, the holding time is short, the energy consumption is low ‘the vacuum degree of the furnace is low. [_] Item 2 shows a carbon steel and oxidized ceramic connecting member 100 obtained by the above connecting method, comprising the carbon steel member 20, the yttria ceramic member 3〇, and the carbon steel member 20 and the same The connection portion 60 of the cerium oxide ceramic member 30. The connecting portion 60 099124622 Form No. A0101 Page 7 / Total 13 0992043292-0 201204496 includes a first transition layer 61, a metal layer 62 and a second transition layer 63. The first transition layer 61 is located between the carbon steel member 20 and the titanium metal layer 62. The first transition layer 61 is mainly composed of a solid solution of titanium and iron and a titanium-iron intermetallic compound. The second transition layer 63 is located between the zirconia ceramic member 30 and the titanium metal layer 62. The second transition layer 63 is mainly composed of a titanium oxide compound, a titanium zirconium compound, and a very small amount of titanium miscible melt. The first transition layer 61 and the second transition layer 63 have a thickness of about 5 to 30/zm, preferably 10 to 20 nm. [0027] The connecting portion 60 of the carbon steel and the yttria ceramic connecting member 100 is even and uniform, without cracks and without voids. It has been found that the carbon steel/zirconia ceramic interface of the carbon steel and zirconia ceramic joint 100 has a shear strength of 80 to 150 MPa. BRIEF DESCRIPTION OF THE DRAWINGS [0028] FIG. 1 is a schematic view showing the connection of carbon steel and yttria ceramic using a discharge plasma sintering apparatus according to a preferred embodiment of the present invention. 2 is a schematic cross-sectional view showing a connecting member of carbon steel and cerium oxide ceramic according to a preferred embodiment of the present invention. [Main component symbol description] [0030] Discharge plasma sintering equipment: 10 [0031] Axial pressure system: 11 [0032] Electrode: 12 [0033] Furnace: 13 [0034] DC pulse power supply: 14 Form No. A0101 No. 8 [0047] [0046] [0046] [0046] [0046] [0047] [0047] [0047] ❹ Control system: 1 5 carbon steel parts: 20 yttria ceramic parts: 30 active intermediate layer: 4 0 graphite mold: 50 upper pressure head: 51 lower pressure head: 52 medium mold: 53 carbon steel and zirconia ceramic joints :100 Connection: 60 First transition layer: 61 Metal layer: 62 Second transition layer: 63 099124622 Form number A0101 Page 9 / Total 13 page 0992043292-0