M336270 •八、新型說明： 【新型所屬之技術領域】 ^ 本新型係一種超臨界表面處理裝置，尤其是有關於一 ' 種能減少沉積層鑄孔，並提升沉積層械性性質及品質之電 化學表面處理裝置。 【先前技術】 . 傳統的電化學處理，包括電鍍、電鑄、電化學沉積等， 是在含水溶液的電化學處理液中進行電化學反應，因水的 • 電解作用會有氫氣泡產生，造成沉積層中含有針孔，影響 到沉積層品質。 超臨界電化學處理技術，是一種在高壓下將高密度相 流體、電化學處理液及介面活性劑藉由攪拌作用，以形成 一具導電性乳膠狀之複方高密度相電化學處理流體，前述 之高密度相流體係包括二氧化碳、三氟甲烷、乙烷、丙烷、 丁烷、苯、氣仿、氮、氬、甲醚等，或其組合者；由於高 密度相流體一般屬於疏水的非極性物質，電化學處理液一 般係為欲沉積物質之水溶液例如鎳瓦特液電鍍液，其係屬 ， 於極性物質，一般條件下此兩種物質的互溶性極低，故必 須加入介面活性劑，藉由攪拌作用使其乳化形成一具導電 性乳膠狀之複方高密度相電化學處理流體。 此外，在進行電化學處理時，因水的電解過程所產生 的氫氣泡，在高壓下可被抑制並更易脫離待處理物表面， 因此超臨界電化學處理技術可減少待處理物沉積層針孔的 產生，且因高密度相流體具有低黏度係數、低表面張力、 高擴散性等優點，使其更容易沉積至具微細特徵尺寸之溝 6 M336270 槽，並有利於欲沉積離子的質傳效率，因此，與傳統電化 學處理技術比較’此種方法可獲得更南品質的沉積層’包 ' 括減少沉積層針孔的產生、可獲得更緻密的沉積層組織、 v 更高的硬度、更小的結晶粒徑、更好平整度、機械強度等 優點，並可應用在具微小特徵尺寸或具高深寬比之微結構 件，及較快之沉積速率。 _ 超臨界電化學處理之先前技術，如中華民國發明專利 第201574號、第1232896號、中華民國新型專利M317435 φ 號等，並無提供超臨界電化學處理滾鍍之相關技術，鑒於 該技術在產業應用上具有實際之需求，因此本案之創作人 乃提出本新型，以應用超臨界電化學處理技術之優點，提 昇傳統電化學滾鍍技術工件沉積層之品質。 【新型内容】 鑑於上述習知技術之問題及產業應用上之需求，本新 型係一種超臨界電化學處理裝置，可應用超臨界電化學處 ⑩- 理技術之優點，以提昇傳統電化學滾鍍技術工件之沉積層 _ 品質，例如更緻密的沉積層組織、更高的硬度、更小的結 晶粒徑、更好的平整度、更佳的機械強度等優點，並可應 用在具微小特徵尺寸或具高深寬比工件之鍍層沉積。 為達上述目的，本新型提供一種超臨界電化學處理裝 置，係運用高密度相流體、電化學處理液及界面活性劑藉 攪拌混合成複方高密度相電化學處理流體，以進行待處理 物電化學處理作業，此超臨界電化學處理裝置包含，具有 呈絕緣性之槽本體及蓋體之壓力容器、夾固件、分別設置 7 M336270 ，於槽本體底部與侧邊且為絕緣性之第一及第二止推軸承單 元、穿設於第一止推軸承單元並貫穿槽本體之攪拌旋轉單 ' 元、穿設於槽本體側邊之至少一陽極導電單元、可迴轉固 ' 設於壓力容器内之迴轉容器，及位於陽極導電單元一侧之 陰極旋轉導電單元，且陰極旋轉導電單元穿設於槽本體側 邊，並連結具有複數孔以方便之電化學處理流體進出之迴 , 轉容器，當欲實施超臨界電化學處理作業時，係將待處理 物置入陰極旋轉單元之迴轉容器内後蓋上容器之上蓋，然 Φ 後將壓力容器之蓋體覆蓋於槽本體形成容置空間，以儲存 複方高密度相電鍍流體，並維持複方高密度相電鍍流體保 持在作業狀態（即保持高密度相流體於超臨界或亞臨界狀 態），且夾固件夾固槽本體與蓋體，以使容置空間形成密閉 狀態，，並令二止推軸承單元分別抵固於槽本體底部及侧 邊，且陽極導電單元與槽本體保持絕緣狀態，而陰極導電 旋轉單元與槽本體及該迴轉容器保持絕緣狀態，並藉由攪 拌旋轉單元於容置空間進行攪拌，以形成乳膠狀具導電性 之複方高密度相電化學處理流體，而陰極導電旋轉單元進 ^ 行旋轉連動迴轉容器進行迴轉，且乳膠狀之複方高密度相 電鍍流體進出迴轉容器所開設之通孔接觸待處理物，並藉 陽極導電單元與陰極旋轉導電單元形成導電迴路，以使複 方高密度相電化學處理流體析出欲沉積物質至待處理上。 本新型係一種超臨界電化學處理裝置，具備下述數點 優於習知技術，並具備如下所述之顯著功效增進。 藉由本新型超臨界電化學處理裝置之實施運用，係能 藉由迴轉容器與攪拌軸之配置整合，及以乳膠狀之複方高 8 M336270 ^ 密度相電鍍流體作為電化學處理液，以使待處理物之沉積 層品質提升，包括沉積層組織更緻密、硬度更高、結晶粒 ’ 徑更小、平整度更好、機械性質更佳等優點，並可應用在 " 具微小特徵尺寸或具高深寬比工件之鍍層沉積，而攪拌軸 之攪拌係令電化學處理液保持流動進而使電化學處理液之 濃度及導電性不因電化學處理時間影響，因而維持電鍍液 . 之濃度均勻及保持乳化，提升待處理物沉積層品質。 為使對本新型的目的、構造特徵及其功能有進一步的 Φ 了解，茲配合相關實施例及圖式詳細說明如下： 【實施方式】 請參閱第1A圖及第1B圖，本新型係一種超臨界電化 學處理裝置，此超臨界電化學處理裝置l〇a係運用一高密 度相流體31、一電化學處理液32及一界面活性劑33，混 合成為一複方高密度相電化學處理流體30 (如第3B圖所 示），用以將至少一待處理物20進行超臨界電化學處理作 業，此超臨界電化學處理裝置10a第一實施例係包含，一 ⑩-壓力容器11、一夾固件12、一迴轉容器13、第一止推軸 ^ 承單元14a、第二止推軸承單元14b、一陽極導電單元15、 一陰極導電旋轉單元16及一攪拌旋轉單元17，上述壓力 容器11係還包含為絕緣性之槽本體111及為絕緣性之蓋體 112，且蓋體112係覆蓋於槽本體111上，並形成一容置空 間S1並用以儲存上述複方高密度相電化學處理流體30， 並形成壓力以維持複方高密度相電化學處理流體30保持 在作業狀態，即該高密度相流體31係保持在超臨界狀態或 亞臨界狀態，且能為超臨界二氧化碳流體或亞臨界二氧化 9 M336270 碳流體’如第3圖所示。 再者，請再參閱第u圖及第ΐβ 夾固於槽本體U1與蓋體112，、 _，上述夹固件12係 置空間S1形成密閉狀；，而迴C麗力容器η之容 式，固設於壓力容器u中，其（谷裔u係以可迴轉之方 容器槽體及-容器上蓋所構成糸二具有圓形或多邊型之- 電性之材質例如塑膠或經表面處理亥疫::：是由不具導 屬，設置於壓力容器11之容署办 蜍电性之金製成 供前述待處理物20容置，=3 S1，且迴轉容器13係 複數通孔131，供上述複方轉谷為13表面係開設有 以接觸待處理物化學處理流體進出 於槽本體m底部與本n二14a係設置 於槽本體111侧邊與本體嗯 ^止推軸承14b設置 , 巴緣更具體而言，第一止推軸 潯早兀14a係開設至少一螺固 固第一止推軸承14a於槽本體lu底=一螺固件141螺 咬右s 9尽體111底部，且此螺固孔係套 於心體142’因而當第一止推軸承單元14a螺固 一1 曰本體111底部之絕緣固定環143時，第一止推轴承單 ^ :與_件141與槽本體U1絕緣，同樣，第二止推M336270 • Eight, new description: [New technical field] ^ This new type is a supercritical surface treatment device, especially for a kind of electroporation that can reduce the casting hole and improve the mechanical properties and quality of the deposition layer. Learn surface treatment equipment. [Prior Art] Traditional electrochemical treatment, including electroplating, electroforming, electrochemical deposition, etc., is an electrochemical reaction in an aqueous solution containing an aqueous solution. Hydrogen bubbles are generated due to water electrolysis. The deposit contains pinholes that affect the quality of the deposit. The supercritical electrochemical treatment technology is a compound high-density phase electrochemical treatment fluid which is formed by a high-density phase fluid, an electrochemical treatment liquid and an interface active agent under high pressure to form a conductive latex-like compound. The high-density phase flow system includes carbon dioxide, trifluoromethane, ethane, propane, butane, benzene, gas, nitrogen, argon, methyl ether, etc., or a combination thereof; since the high-density phase fluid is generally hydrophobic and non-polar The substance, the electrochemical treatment liquid is generally an aqueous solution of a substance to be deposited, such as a nickel watt liquid plating solution, which belongs to a polar substance. Under normal conditions, the mutual solubility of the two substances is extremely low, so it is necessary to add an interface active agent. It is emulsified by stirring to form a conductive latex-like compound high-density phase electrochemical treatment fluid. In addition, when electrochemical treatment is performed, hydrogen bubbles generated by the electrolysis process of water can be suppressed under high pressure and are more easily separated from the surface of the object to be treated, so that supercritical electrochemical treatment technology can reduce pinholes of the deposited layer of the object to be treated. The high-density phase fluid has the advantages of low viscosity coefficient, low surface tension, high diffusivity, etc., making it easier to deposit into the groove 6 M336270 with fine feature size, and is beneficial to the mass transfer efficiency of the ions to be deposited. Therefore, compared with the traditional electrochemical treatment technology, 'this method can obtain a more south quality deposit layer' package, including reducing the formation of pinholes in the sediment layer, obtaining denser deposit layer structure, v higher hardness, and more Small crystal grain size, better flatness, mechanical strength, etc., and can be applied to microstructured parts with small feature sizes or high aspect ratios, and faster deposition rates. _ The prior art of supercritical electrochemical treatment, such as the Republic of China invention patent No. 201574, No. 1232896, the Republic of China new patent M317435 φ, etc., does not provide the relevant technology of supercritical electrochemical treatment barrel plating, in view of the technology The industrial application has practical needs, so the creator of this case proposed this new type to apply the advantages of supercritical electrochemical processing technology to improve the quality of the workpiece deposition layer of the traditional electrochemical barrel plating technology. [New content] In view of the above-mentioned problems of the prior art and the demand for industrial application, the present invention is a supercritical electrochemical treatment device which can apply the advantages of the supercritical electrochemical treatment technology to enhance the conventional electrochemical barrel plating. Deposition of technical workpieces _ quality, such as denser deposit structure, higher hardness, smaller crystal size, better flatness, better mechanical strength, etc., and can be applied to small feature sizes Or plating deposition with high aspect ratio workpieces. In order to achieve the above object, the present invention provides a supercritical electrochemical treatment device which utilizes a high-density phase fluid, an electrochemical treatment liquid and a surfactant to be stirred and mixed into a compound high-density phase electrochemical treatment fluid for electrochemical treatment of a substance to be treated. For the processing operation, the supercritical electrochemical treatment device comprises a pressure vessel having an insulating groove body and a cover body, and a clamper, respectively provided with 7 M336270, the first and the insulation on the bottom and the side of the groove body, and a second thrust bearing unit, a stirring rotating single unit that is disposed in the first thrust bearing unit and penetrates the groove body, and at least one anode conductive unit that is disposed on a side of the groove body and is rotatably disposed in the pressure vessel The rotary container and the cathode rotating conductive unit on one side of the anode conductive unit, and the cathode rotating conductive unit is disposed on the side of the groove body, and is connected with a plurality of holes to facilitate electrochemical treatment of fluid in and out, and the container is In order to carry out the supercritical electrochemical treatment operation, the object to be treated is placed in the back cover of the rotary container of the cathode rotating unit, and the upper cover of the container is closed. After Φ, the cover of the pressure vessel is covered on the groove body to form a accommodating space for storing the compound high-density phase plating fluid, and the compound high-density phase plating fluid is maintained in the working state (that is, the high-density phase fluid is maintained in supercritical or sub- a critical state), and the clamping member clamps the groove body and the cover body to form a sealed state of the accommodating space, and the two thrust bearing units are respectively fixed to the bottom and the side of the groove body, and the anode conductive unit and the groove body are respectively Maintaining an insulated state, the cathode conductive rotating unit is insulated from the tank body and the rotating container, and is stirred in the accommodating space by stirring the rotating unit to form a latex-like conductive high-density phase electrochemical treatment fluid. The cathode conductive rotating unit rotates and rotates the rotary container to rotate, and the through-hole formed by the latex-shaped compound high-density phase electroplating fluid enters and exits the rotary container contacts the object to be treated, and forms a conductive state by the anode conductive unit and the cathode rotating conductive unit. The loop is such that the compound high-density phase electrochemically treats the fluid to deposit the material to be deposited to be treated. The present invention is a supercritical electrochemical treatment apparatus having the following advantages over conventional techniques and having significant enhancements as described below. Through the implementation of the novel supercritical electrochemical treatment device, it can be integrated by the configuration of the rotary container and the stirring shaft, and the latex-like compound high 8 M336270 ^ density phase plating fluid is used as the electrochemical treatment liquid to make the treatment to be processed. The quality of the sedimentary layer of the material is improved, including the denser structure of the sediment layer, higher hardness, smaller crystal grain diameter, better flatness, better mechanical properties, etc., and can be applied to "with small feature size or high depth The coating of the width ratio of the workpiece is deposited, and the stirring of the stirring shaft keeps the electrochemical treatment liquid flowing so that the concentration and conductivity of the electrochemical treatment liquid are not affected by the electrochemical treatment time, thereby maintaining the concentration of the plating solution and maintaining the emulsification. Improve the quality of the deposited layer of the object to be treated. In order to further understand the purpose, structural features and functions of the present invention, the related embodiments and drawings are described in detail as follows: [Embodiment] Please refer to FIG. 1A and FIG. 1B, which is a supercritical The electrochemical treatment device, the supercritical electrochemical treatment device 10a uses a high-density phase fluid 31, an electrochemical treatment liquid 32 and a surfactant 33 to be mixed into a compound high-density phase electrochemical treatment fluid 30 ( As shown in FIG. 3B, for performing supercritical electrochemical processing on at least one object to be treated 20, the first embodiment of the supercritical electrochemical processing device 10a includes a 10-pressure vessel 11 and a clamp. 12. A rotary container 13, a first thrust shaft bearing unit 14a, a second thrust bearing unit 14b, an anode conductive unit 15, a cathode conductive rotating unit 16, and a stirring rotating unit 17, wherein the pressure vessel 11 is further The insulating body 111 and the insulating cover 112 are included, and the cover 112 covers the groove body 111 and forms an accommodating space S1 for storing the compound high-density phase electrochemical The fluid 30 is fluidized and pressure is maintained to maintain the compound high density phase electrochemical treatment fluid 30 in a working state, i.e., the high density phase fluid 31 is maintained in a supercritical or subcritical state and can be a supercritical carbon dioxide fluid or sub Critically oxidized 9 M336270 carbon fluid 'as shown in Figure 3. Furthermore, please refer to FIG. u and the ΐβ clamped to the groove body U1 and the lid body 112, _, the clamp 12 is placed in a space S1 to form a sealed shape; and the capacitance of the C-little container η is returned. It is fixed in the pressure vessel u, which is made of a rotatable square container tank and a container upper lid. The crucible has a circular or polygonal type - an electrical material such as plastic or surface treatment. ::: is made of a non-conducting, gold-filled gold provided in the pressure vessel 11 for the preparation of the object to be treated 20, = 3 S1, and the rotary container 13 is a plurality of through holes 131 for the above The compound turning valley is provided with a surface layer of 13 to be in contact with the chemical treatment fluid to be treated into the bottom of the trough body m, and the n 2 14a system is disposed on the side of the trough body 111 and the body is provided by the thrust bearing 14b. In other words, the first thrust shaft 浔 14A is provided with at least one screw-solid first thrust bearing 14a at the bottom of the groove body = a screw 141 screw bites the bottom of the right s 9 body 111, and the screw hole The sleeve is sleeved on the core body 142' and thus the first thrust bearing unit 14a is screwed to the bottom of the body 111. When the first thrust bearing is single ^ : and the _ member 141 is insulated from the groove body U1, similarly, the second thrust
^:元14b係開設至少—螺固孔，供至少-螺固件W '、口弟一止推軸承單元141)於槽本體m側邊，且此螺固 孔係套設有絕緣間隔環142，因而當第二止推軸承14b螺 固於槽本體111側邊之絕緣固定環143，第二止推軸承單 元14b與螺固件141與槽本體ill絕緣。 又，上述之陽極導電單元15係穿設於槽本體lu侧 邊，且容置於呈密閉狀態之容置空間S1中，並與槽本體 M336270 111保持絕緣狀態。而陰極導電旋轉單元16係穿設於第二 止推軸承14b，並貫穿槽本體ill，且連結於上述迴轉容器 ’ 13，陰極導電旋轉單元16係還容置於呈密閉狀態之容置空 ' 間S1中，而位於陽極導電旋轉單元15 —側，並與槽本體 111及迴轉容器13保持絕緣狀態。 請再參閱第1B圖及第1C圖，當上述超臨界電化學處 - 理裝置10a組構完成後，係將上述複方高密度相電化學處 理流體30,藉由槽本體ill所包含之一流體入口 Fi導入， _ 其位於槽本體111之週邊，並以攪拌旋轉單元17進行攪拌 複方焉密度相電化學處理流體3〇於容置空間si，以形成 乳膠狀之複方高密度相電鍍流體3〇a，保持複方高密度相 電化學處理流體30a之流動狀態維持濃度均勻及保持在乳 化狀態，而陰極導電旋轉單元16進行旋轉連動迴轉容器 13進行迴轉，進而使待表面處理物2〇於迴轉容器13迴轉 時’翻滾於迴轉容器13中，透過上述通孔131乳膠狀之複 方高密度相電化學處理流體30a得以接觸待處理物2〇，並 豢藉陽極導電單元15與陰極導電旋轉單元16形成導電迴 ‘路，以使複方高密度相電化學處理流體30a析出一欲沉積 物質，沉基於待處理物2〇上， 請參閱第2圖，圖中槽本體ln係還再包含一流體出 口 F2、’同樣位於槽本體lu之週邊，且當將上述流體入口 F1與肌體出口 F2分別連結於一流體循環單元如&時，此 =體循環單元4Qa係能承置上述複方高密度相電化學處理 :體30 II以將複方尚密度相電化學處理流體循環於 才曰本體111中’組構成—超臨界電化學處理系統，當然此 11 M336270 流體循環單元40a係也能如後述承置前述高密度相流體 31、電化學處理液32及界面活性劑33之個別流體，並將 高密度相流體、電化學處理液及界面活性劑於槽本體Ul 中，混合而呈複方高密度相電化學處理流體30，另外，超 臨界電化學處理裝置1〇b第二實施例之槽本體1U，請束 閱第3A ®及第3B目，更能再包含一廢棄流體排放口… 其係位於槽本體111之底部，用以卸除複方高密度相電化 -學廢液流體裏至—廢液收集槽50，而上述流體入口 η 及流體出口 F2與槽本體ln之接口處為保持絕緣狀離，係 旎將其接口處鍍覆有一絕緣層，或採用絕 呈絕緣狀態。 衣1以 凊再次麥閱第1B圖，前述攪拌旋轉 拌驅動單元m及-擾拌旋轉轴173,其 授 元m係連接於_旋轉轴173，且與 絕緣’並帽拌旋轉軸173進行上述之二：m 而為增加其攪拌面積，攪拌旋轉軸173 動作， -延伸於攪拌旋轉軸173 一端，供授拌 Y、—葉片174 於容置空間S1中，或者，將攪拌旋轉二=旋轉攪拌 換成一授拌子（圖中未示），其大致類似 ^片Π4置 樣延伸於攪拌旋轉軸173 一 ，其係同 摔於容置空間，又為錢掉旋轉旋轉授 持絕緣狀態，係於搜拌旋轉軸173還、槽本體U!保 位於槽本體U1及祕旋轉轴173間，：、巴、、豪轴承14C， 向滾问軸承、止推滚珠轴承等之其中— 狀^=緣t!14c係可包含徑向滚珠轴二 種。除此，攪拌旋 12 M336270 #軸173翻設有—轴封纟且μ 封狀態。而為維持整體之高密度相〜寺总容置空f曰1 S1呈密 度’以持續析出欲沉積物浙了 $化學處理流體3〇濃 可旋轉的陽極導電單元/ 4於待處理物2G上，係能在 s丨中’且陽極設―陽極環丨55位於容置空間 當然，上述陽極導物㈣朗如錄、金等。 導電單元亦可採用可早側或成對設置。另外陽極 .即可^狀此時，陽極環155 第-旋轉接頌包含-旋轉機構162、- 係連接於陰極旋_ 16 Λ H =旋轉機構162 轉，以連動避轉容器13動_轉轴164進行旋 =於陰極編164，並舆上^^轉^貝16=用以 接形成導電迴路，此外，在 才h早凡15電性連 與迴轉容器13固接處，另164貫穿槽本體111 旋轉軸164,並從第二旋“=旋轉接頭165於陰極 物2〇接觸，使陰極與陽極通入電、=伸一導線與待處理 路。又為使陰極旋轉軸164與 ^ ’能形成一導電迴 係於陰極旋轉軸164還套# 一二_ 11保持絕緣狀態， 111與陰極旋轉軸164㈤广使、、^承14d ’位於槽本體 緣轴承Ud係可包含經向滾吏[者保持絕緣狀態，該絕 场滚珠轴承等之其中—種。〜，Μ、徑向滾筒轴承、 設有—軸封組18,以保持容置陰。極^轉軸164還固 6亥陰極迴轉單开讯罟女 王岔封狀悲。此外， 陰-爾器之二元如^ 在破處理物進行取放作業時，係 13 M336270 在容易取放之位置。 請續參閱第1B圖，前述第一止推轴承單元14a還包含 一絕緣固定環143,設置於止推軸承單元14a與槽本體111 間，以使二者呈絕緣狀態，同樣，絕緣固定環143也設置 於第二止推轴承單元14b與槽本體111間以呈絕緣，又或 者，係能令第一止推轴承單元14a具有一絕緣層，形成於 第一止推轴承單元14a與槽本體111間，而第二止推軸承 單元14b也具絕緣層於第二止推軸承單元14b與槽本體111 間，同樣能使第一止推軸承單元14a與槽本體111及第二 止推軸承單元14b與槽本體111保持絕緣狀態，此絕緣層 之材質係為鐵氟龍材質。另外，槽本體111與蓋體112還 設置有一墊圈19，用以保持容置空間S1呈密封狀態。 另外，請參閱第4圖，上述電化學處理裝置10a第一 實施例係也能包含二陽極導電單元15，組構成為電化學表 面處理裝置10c第三實施例，以增加沉積之效率，而其組 構方式及沉積方式係同上述。 上述複方高密度相電化學處理流體30之界面活性劑 33，其係選用自於由陰離子性界面活性劑、非離子性界面 活性劑、陽離子性界面活性劑及兩性離子性界面活性劑所 組成的群組。 而上述陰離子性界面活性劑係選用自於肥皂、α —烯煙 磺酸鹽、烷基苯磺酸鹽、烷基硫酸酯鹽、烷基醚硫酸酯鹽、 苯基醚硫酸酯鹽、甲基牛磺酸鹽、硫基琥珀酸鹽、醚磺酸 鹽、硫酸化油、磷酸酪、全氟烯煙磺酸鹽、全氟烷基苯磺 酸鹽、全氟烷基苯磺酸鹽、全氟烷基硫酸酯鹽、全氟烷基 M336270 醚硫酸酯鹽、全氛苯基醚硫酸酯鹽、全氟曱基牛磺酸鹽、 .磺基全氟琥珀酸鹽及全氟醚磺酸鹽所組成的群組。 再者’非離子性界面活性劑係選用自於C1〜C25烷基 笨紛系、C1〜C20烧醇、聚伸烧基二元醇系、烧基醇酿胺 系、C1〜C22脂肪酸酯系、C1〜C22脂族胺、烷基胺環氧乙 烷加成物、芳烷基苯酚、C1〜C25烷基萘酚、C1〜C25烷氧 .基化墙酸（鹽）、山梨糖醇酐酯、苯乙烯化苯酚、统基胺環 、氧乙烷/環氧丙烷加成物、烷基胺氧化物、C1〜C25烷氧基 • 化磷酸（鹽）、全氟壬基苯酚系、全氟高級醇系、全氟聚伸 烷基乙二醇系、全烷基醇醯胺系、全氟脂肪酸酯系、全氟 烷基胺環氧乙烷加成物、全氟烷基胺環氧乙烷、全氟環氧 丙烷加成物、全氟烷基胺氧化物所組成的群組。 而陽離子性界面活性劑係選用自於月桂基三曱基銨 鹽、硬脂基三甲基銨鹽、月桂基二曱基乙基銨鹽、二甲基 苄基月桂基銨鹽、鯨蠟基二曱基节基銨鹽、十八烷基二曱 基苄基叙鹽、二曱基苄基銨鹽、十六烧基吼咬鏽鹽、月桂 •，基吼咬銨鹽、十二烧基曱基吼咬鐵鹽、硬脂胺醋酸鹽、月 '桂胺醋酸鹽、十八烷基胺醋酸鹽、氣化單烷基銨、氯化二 烷基銨、環氧乙烷加成型氯化銨、化烷基节基銨、氣化四 甲基銨、氣化二曱基苯基銨、氯化四丁基銨、醋酸單烷基 銨、咪唑啉鏽甜菜鹼系、丙胺酸系、烷基甜菜鹼系、氣化 單氣烧基銨、氯化二全氟烧基銨、全氟環氧乙烧加成型氣 化鉍、氯化全氟烷基苄基銨、氣化四全氟曱基銨、氯化三 全氟甲基苯基銨、氯化四全氟丁基銨、醋酸單全氟烷基銨、 全氟烷基甜菜鹼系所組成的群組。 女 15 M336270 上述兩性離子性界面活性劑係選用自於甜菜驗、石黃基 甜菜鹼及胺基羧酸所組成的群組。 * 前述兩性離子性界面活性劑係選用自於環氧乙烷、環 ' 氧丙烷、烷基胺或二胺之縮合產物之硫酸化及磺酸化加成 物所組成的群組。 雖然本新型以較佳實施例揭露於上，然其並非用以限 . 定本新型，任何熟習此項技藝者，在不脫離本新型之精神 1 和範圍内，當可做些許之更動與潤飾，因此本新型之保護 Φ 範圍當視後附之申請範圍所界定者為準。 【圖式簡單說明】 第1A圖係本新型超臨界電化學處理裝置第一實施例俯視 不意圖； 第1B圖係本新型超臨界電化學處理裝置第一實施例正視 剖面示意圖； 第1C圖係本新型超臨界電化學處理裝置第一實施例侧視 剖面不意圖， 第2圖係本新型超臨界電化學處理裝置第一實施例連結流 體循環單元示意圖； 第3A圖至第3B圖係本新型超臨界電化學處理裝置第二實 施例連結廢液收集槽不意圖；以及 第4圖係本新型超臨界電化學處理裝置第三實施例示意 圖。 【主要元件符號說明】 10a，10b，10c 超臨界電化學處理裝置 11 壓力容器 16 M336270 111 槽本體 112 蓋體 * 12 失固件 ' 13 迴轉容器 131 通孔 14a 第一止推轴承單元 .14b 第二止推軸承單元 ，14c，14d 絕緣軸承 • 141 螺固件 142 絕緣間隔環 143 絕緣固定環 15 陽極導電單元 155 陽極環 16 陰極導電旋轉單元 162 旋轉機構 163 第一旋轉接頭 .164 陰極旋轉軸 165 第二旋轉接頭 166 陰極延伸導線 17 攪拌旋轉單元 171 攪拌驅動單元 173 攪拌旋轉軸 174 葉片 18 軸封組 19 墊圈 17 M336270 20 待處理物 30 複方高密度相電化學處理流體 30a 乳膠狀之複方高密度相電化學處理流體 30b 複方南密度相電化學處理廢液流體 31 高密度相流體 32 電化學處理液 33 界面活性劑 40a，40b 流體循環單元 50 廢液收集槽 SI 容置空間 FI 流體入口 F2 流體出口 F3 廢棄流體排放口 18^: Element 14b is provided with at least a screw-hole, for at least a screw W', a tongue-and-pin thrust bearing unit 141) on the side of the groove body m, and the screw-hole hole sleeve is provided with an insulating spacer ring 142. Therefore, when the second thrust bearing 14b is screwed to the insulating fixing ring 143 on the side of the groove body 111, the second thrust bearing unit 14b and the screw 141 are insulated from the groove body ill. Further, the anode conductive unit 15 is disposed on the side of the groove body lu, and is accommodated in the accommodating space S1 in a sealed state, and is kept insulated from the groove body M336270 111. The cathode conductive rotating unit 16 is disposed through the second thrust bearing 14b and penetrates the groove body ill, and is coupled to the rotating container '13. The cathode conductive rotating unit 16 is also accommodated in a sealed state. In the middle S1, it is located on the side of the anode conductive rotating unit 15, and is kept insulated from the groove body 111 and the rotary container 13. Referring to FIG. 1B and FIG. 1C again, after the supercritical electrochemical device 10a is completed, the compound high-density phase electrochemically treats the fluid 30, and the fluid contained in the tank body ill The inlet Fi is introduced, and is located at the periphery of the tank body 111, and is stirred by the stirring and rotating unit 17 to perform a compounding of the density phase electrochemical treatment fluid 3 in the accommodating space si to form a latex-like compound high-density phase plating fluid. a, maintaining the flow state of the compound high-density phase electrochemical treatment fluid 30a to maintain a uniform concentration and maintaining the emulsified state, and the cathode conductive rotating unit 16 rotates and rotates the rotary container 13 to rotate, thereby causing the surface-treated material 2 to be smashed in the rotary container When 13 is rotated, it is tumbled in the rotary container 13, and the compound high-density phase electrochemical treatment fluid 30a which is in the form of a latex through the through hole 131 is brought into contact with the object to be treated 2, and is formed by the anode conductive unit 15 and the cathode conductive rotating unit 16. Conducting back to the road so that the compound high-density phase electrochemical treatment fluid 30a precipitates a substance to be deposited, based on the object to be treated 2, see Figure 2 In the figure, the groove body ln further includes a fluid outlet F2, which is also located at the periphery of the groove body lu, and when the fluid inlet F1 and the body outlet F2 are respectively coupled to a fluid circulation unit such as &, the body circulation unit 4Qa The device can be subjected to the above-mentioned compound high-density phase electrochemical treatment: the body 30 II is used to circulate the compound still-density phase electrochemical treatment fluid in the body of the body 111 to form a supercritical electrochemical treatment system, of course, this 11 M336270 fluid circulation The unit 40a can also hold the individual fluids of the high-density phase fluid 31, the electrochemical treatment liquid 32, and the surfactant 33 as described later, and the high-density phase fluid, the electrochemical treatment liquid, and the surfactant in the tank body U1. Mixing and forming a compound high-density phase electrochemical treatment fluid 30. In addition, the supercritical electrochemical treatment apparatus 1bb of the second embodiment of the tank body 1U, please refer to the 3A ® and 3B, and can further include a The waste fluid discharge port is located at the bottom of the tank body 111 for removing the compound high-density phase electro-chemical waste liquid to the waste liquid collection tank 50, and the fluid inlet η and the fluid outlet Ln interface F2 of the body shaped from the groove to hold the insulation, laying line interface which has an insulating layer coated, or must use an insulated state. 1A, the agitating rotary mixing drive unit m and the spoiler rotating shaft 173 are connected to the rotating shaft 173, and the insulating 'and capping rotating shaft 173 is used to perform the above. The second is: m, in order to increase the stirring area, the stirring rotating shaft 173 acts, - extends to one end of the stirring rotating shaft 173, for mixing Y, the blade 174 in the accommodating space S1, or, the stirring rotation 2 = rotating stirring It is replaced by a stirrer (not shown), which is similar to the piece of Π4 and extends to the agitating rotating shaft 173, which is slid into the accommodating space, and is in a state of insulting rotation for rotating and rotating. In the search mixing shaft 173, the groove body U! is located between the groove body U1 and the secret rotating shaft 173, and: the bar, the ho-bearing bearing 14C, the rolling bearing, the thrust ball bearing, etc. The t!14c system can include two types of radial ball bearings. In addition, the stirring screw 12 M336270 #axis 173 is turned over - the shaft is sealed and the μ is sealed. In order to maintain the overall high-density phase ~ the total capacity of the temple is set to empty f曰1 S1 density "to continue to precipitate the deposits of the chemical. The chemical treatment fluid 3 〇 rich rotatable anode conductive unit / 4 on the object 2G , the system can be in s丨 'and the anode is set - the anode ring 丨 55 is located in the accommodating space. Of course, the above anode lead (4) is like a record, gold, and the like. The conductive units can also be arranged on the early side or in pairs. In addition, the anode can be shaped. At this time, the anode-ring 155 first-rotating joint includes a -rotating mechanism 162, - is connected to the cathode rotating _ 16 Λ H = the rotating mechanism 162 is rotated to interlock the rotating container 13 164 is rotated = cathode 164, and 舆 ^ ^ ^ ^ 16 16 = used to form a conductive loop, in addition, before the first 15 electrical connection with the rotating container 13 fixed, the other 164 through the groove body 111 rotates the shaft 164 and contacts the cathode 2 从 from the second rotation "= rotary joint 165 to make the cathode and the anode pass electricity, = extend a wire and the path to be processed. Further, the cathode rotating shaft 164 and ^' can form a The conductive return is connected to the cathode rotating shaft 164 and the sleeve #一二_11 remains insulated, and the cathode and the cathode rotating shaft 164 (5) are wide, and the bearing 14d' is located at the groove body edge. The bearing Ud can include a warp roll. State, the end of the ball bearing, etc. -., Μ, radial roller bearing, with - shaft seal group 18, to maintain the yin. The pole 164 is still solid 6 阴极 cathode turn single open 罟The queen is sorrowful. In addition, the binary of the yin-er device is as follows: when the handling of the broken material is carried out, the system 13 The M336270 is in a position where it can be easily accessed. Referring to FIG. 1B, the first thrust bearing unit 14a further includes an insulating fixing ring 143 disposed between the thrust bearing unit 14a and the groove body 111 to insulate the two. In the same manner, the insulating retaining ring 143 is also disposed between the second thrust bearing unit 14b and the slot body 111 to insulate, or alternatively, the first thrust bearing unit 14a has an insulating layer formed in the first stop. The thrust bearing unit 14a is interposed between the bearing unit 14a and the groove body 111, and the second thrust bearing unit 14b also has an insulating layer between the second thrust bearing unit 14b and the groove body 111, and also enables the first thrust bearing unit 14a and the groove body 111. The second thrust bearing unit 14b is insulated from the slot body 111. The material of the insulating layer is made of Teflon. In addition, the slot body 111 and the cover 112 are further provided with a washer 19 for holding the receiving space S1. In addition, referring to FIG. 4, the first embodiment of the electrochemical treatment device 10a described above can also include two anode conductive units 15, which are configured as a third embodiment of the electrochemical surface treatment device 10c to increase deposition. The composition, the deposition mode is the same as above. The above-mentioned compound high-density phase electrochemical treatment fluid 30 surfactant 33 is selected from anionic surfactant, nonionic surfactant, cation a combination of a surfactant and a zwitterionic surfactant. The anionic surfactant is selected from the group consisting of soap, α-methonic acid sulfonate, alkyl benzene sulfonate, and alkyl sulfate. , alkyl ether sulfate salt, phenyl ether sulfate salt, methyl taurate, thiosuccinate, ether sulfonate, sulfated oil, phosphate cheese, perfluoroolefinic sulfonate, perfluoro Alkylbenzenesulfonate, perfluoroalkylbenzenesulfonate, perfluoroalkylsulfate, perfluoroalkyl M336270 ether sulfate, fully phenyl ether sulfate, perfluorodecyl taurine a group consisting of a salt, a sulfo-perfluorosuccinate, and a perfluoroether sulfonate. In addition, 'nonionic surfactants are selected from C1~C25 alkyl stupid, C1~C20 ani alcohol, polyalkylene glycol, alkyl alcohol amine, C1~C22 fatty acid ester , C1~C22 aliphatic amine, alkylamine ethylene oxide adduct, aralkyl phenol, C1~C25 alkyl naphthol, C1~C25 alkoxylated wall acid (salt), sorbitol Anhydride ester, styrenated phenol, alkylamine ring, oxyethane/propylene oxide adduct, alkylamine oxide, C1~C25 alkoxylate (phosphoric acid), perfluorononylphenol, Perfluoro higher alcohol, perfluoropolyalkylene glycol, peralkyl alcohol amide, perfluoro fatty acid ester, perfluoroalkylamine ethylene oxide adduct, perfluoroalkylamine A group consisting of ethylene oxide, perfluoropropylene oxide adducts, and perfluoroalkylamine oxides. The cationic surfactant is selected from the group consisting of lauryl tridecyl ammonium salt, stearyl trimethyl ammonium salt, lauryl dimercaptoethyl ammonium salt, dimethyl benzyl lauryl ammonium salt, cetyl group. Diterpene quaternary ammonium salt, octadecyldidecyl benzyl salt, dimercaptobenzyl ammonium salt, hexadecyl chlorate, laurel, base bite ammonium salt, twelve alkyl group曱 base bite iron salt, stearylamine acetate, lunar o-amylamine acetate, octadecylamine acetate, vaporized monoalkylammonium, dialkylammonium chloride, ethylene oxide addition chlorination Ammonium, alkyl benzyl ammonium, vaporized tetramethylammonium, vaporized dimercaptophenyl ammonium, tetrabutylammonium chloride, monoalkylammonium acetate, imidazoline rust betaine, alanine, alkane Betaine, gasification monogassing ammonium, chlorinated diperfluoroalkylammonium chloride, perfluoroepoxyethane addition molding gasification hydrazine, chlorinated perfluoroalkylbenzylammonium, gasified tetrahydrofluorene A group consisting of ammonium amide, triperfluoromethylphenylammonium chloride, tetraperfluorobutylammonium chloride, monoperfluoroalkylammonium acetate, and perfluoroalkyl betaine. Female 15 M336270 The above zwitterionic surfactants are selected from the group consisting of beet test, flavonoid betaine and aminocarboxylic acid. * The amphoteric ionic surfactant is selected from the group consisting of sulfation and sulfonation addition products of condensation products of ethylene oxide, cyclooxypropane, alkylamine or diamine. Although the present invention is disclosed in the preferred embodiments, it is not intended to limit the scope of the present invention. Anyone skilled in the art can make some modifications and refinements without departing from the spirit and scope of the present invention. Therefore, the scope of protection Φ of this new type is subject to the definition of the scope of application. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1A is a schematic view of a first embodiment of the present invention, and a first embodiment of the present invention; FIG. 1B is a schematic cross-sectional view of a first embodiment of the novel supercritical electrochemical treatment apparatus; The first embodiment of the present invention is not intended to be a side view, and the second embodiment is a schematic diagram of the first embodiment of the supercritical electrochemical treatment device connected to the fluid circulation unit; FIGS. 3A to 3B are the novel The second embodiment of the supercritical electrochemical treatment apparatus is not intended to connect the waste liquid collection tank; and the fourth embodiment is a schematic diagram of the third embodiment of the novel supercritical electrochemical treatment apparatus. [Main component symbol description] 10a, 10b, 10c Supercritical electrochemical treatment device 11 Pressure vessel 16 M336270 111 Slot body 112 Cover body * 12 Loss of firmware ' 13 Rotary container 131 Through hole 14a First thrust bearing unit. 14b Second Thrust bearing unit, 14c, 14d Insulated bearing • 141 Screw 142 Insulation spacer ring 143 Insulation ring 15 Anode conducting unit 155 Anode ring 16 Cathode conductive rotating unit 162 Rotating mechanism 163 First swivel joint 164 Cathode rotating shaft 165 Second Rotary joint 166 Cathode extension wire 17 Stirring rotary unit 171 Stirring drive unit 173 Stirring rotary shaft 174 Blade 18 Shaft seal set 19 Washer 17 M336270 20 Material to be treated 30 Compound high-density phase electrochemical treatment fluid 30a Latex-like compound high-density phase electrification Process fluid 30b compound south density phase electrochemical treatment waste liquid 31 high density phase fluid 32 electrochemical treatment liquid 33 surfactant 40a, 40b fluid circulation unit 50 waste collection tank SI accommodation space FI fluid inlet F2 fluid outlet F3 Waste fluid discharge port 18