200817530 玖、發明說明： 【發明所屬之技術領域】 。 本發明為一種薄膜元件的表面處理系統，以二氧化碳(c〇2)超臨界 流體將薄膜元件的表面不純物去除，使得薄膜元件的表面積得以提 幵，本技藝在α除過程中'無須添加強酸驗化合物，所以處理過程安全 無危險。 【先前技術】 物質通常具有氣體、液體及固體三相，當固體物質隨著溫度與壓 力的增加，而使狀態介於氣體與液體之間的流體時，稱為「超臨界流 體」（叫critical fkid，SCF)。「超臨界流體」（SCF)為操作溫度和壓力 超過臨界值(critical value)的流體，其液體和氣體間的界面消失，性質介 於液體和氣制，_具核體的高密度、高簡度的優點，以及氣 體的無表面張力、讎度、高擴散性、高f量傳輸的優點。此外，可 利用操作溫度和壓力的變化而改變溶解度。針對不同的物質，產生選 擇性,的，，此為一般液體所沒有的性質，所以「超臨界流體」（set) 可以况是一種「超級溶劑」（supers〇lvent)，它具有高質 可二進入材料的深處，將内部的物質溶解出來，或是將溶解專斗=至 冰處，此為「超臨界流體」（SCF)具有氣體特性的優越特性。 向輕目前，，子、資訊，及通訊等3C產業的高性能薄膜元件，皆是朝 #材骸S、小之目_展。塗佈技術制範圍涵蓋光學塗膜與儲 =材抖寻，可使賴印和_型_塗佈等技術製造。 =印^膠和高分子分散劑混合成_aste〇rslurry)後，利用網3 為了使得薄膜元件能夠發揮最大的效率，除了在混合材料的均句分 200817530 烤箱機5之rii。果題之外丄還必須注意個別材料在混合以後’經過 α °一理以後的高表面積醜持更是關鍵。通常，粉末-顆 =2越小，分散性越好。所以，當我們使用奈米等級的顆粒日 準備塗佈㈣料所需要添加的分散劑(dis卿ant)就越多，這種情況下， ::政綱里增多日寺，烤乾以後，過多的分散劑會遮蔽⑽職㈣薄膜 成中的粉末雛的表面，將使得「_元件」組射顆粒之裸 路的有效表面積降低。 和例如薄膜電極體(ηΐ_· dectr〇de assembly)是質子交換膜燃料 4的核心7G件，中間是質子交細，兩侧為觸媒電極層(陰極、陽極) 的一明/σ構造。觸媒電極為「氣體擴散層」（牌⑴腕⑽la㈣和「觸 媒?」「(C-ySt 一〕的雙層結構。氣體擴散層為「碳紙_ 或疋炭布」（carbon cloth)，提供氣體進出的通道。觸媒層以碳黑為載 體，在載體上沈積貴金屬元素例如：白金㈣、或是釕_，作為催化 劑0 —對燃料電池而言，高表面積的電極代表的是高容量、高功率、高 女王性。奈米觸媒m塗佈在高表面積的碳紙基底上形成電極。觸 媒聚料的塗佈方式為網印、刮刀、轉印、喷塗等。—般而言，電極在 塗佈後，由於添加黏合劑(binder)、界面活性劑(surfactant)等，會對漿料 產生遮蔽效應(screening effect)，影響到電極内觸媒的使用效率，使其 物1±以及化性降低。此外，界面活性冑彳也會將原來具有高表面積的碳 材的孔隙遮蔽住，使得碳材的表面積喪失高達約3〇_4〇%· 目丽，在薄膜元件上的表面處理方面，尚未見到有應用超臨界流 體者。習知的超臨界流體製備多孔性結構，係使用超臨界流體搭配溶 劑的使用，來製備親水性生物可分解高分子之多孔性結構。使用之方 法包括下列主要步驟：⑻將一生物可分解高分子與一溶劑置於一容器 中，（b)將一超臨界流體注入容器中，維持一既定溫度與時間，使超臨 6 200817530 界流體溶入該生物可分解高分子中 出超臨界流體與溶劑，得到—多孔性⑼之壓力’以相 可見”民國專利公報第丨73235，^，子材科。已知的先前技術:， .㈣丨細和顯專利公報第6,673,286中:。 習知熱處理法，須要在高溫 子界面活性齡除，然而，所制 〜_伟合劑、高分 胺爾面的不純物。奈米觸媒漿料顆粒的 文:除:亡 的催化劑的表面若是能夠完全裸露 厂^ 所u μ尬几4田一… 卜欲雜貝所遮敝，則可以得到較好 勺催化效果，溥膜元件的性能才可以提升。 【發明内容】 、隹-以一氧化碳(c〇2)超臨界流體(supercriticai脑)對薄膜元件 理’去除不純物，提昇表面積，且_中無須添加強酸驗 化口物，衣程安全且大幅提高薄膜元件的品質和性能。 一氧化故無t性、不自燃、不具腐姓性、不產生有害廢棄物、價 格低，應:用潛力非常大。#溫度與壓力達到臨界點(criticalp〇int)，使物 體的狀祕為固、液或氣體，而為_均勻流體，此稱為超臨界流體， 此壓力為臨界壓力（critical pressure，Pc),溫度為臨界溫度⑽出― temperature，Tc)°二氧化碳超臨界流體的臨界溫度低接近室溫(tc=3i.i °C)、臨界壓力低(pc=72.8atm 或 7.38MPa)。 物質在超臨界狀態下，兼具有氣體的高擴散性與液體的高溶解力 特性。一氧化碳超臨界流體可深入薄膜元件的孔隙中，將其中的不純 物有效去除，而使純化度提高，並打通阻塞處，造成多孔性結構，而 使表面積提高。此外，並可添加共溶劑，以調整不純物的溶解度，是 為最具發展潛力的表面改質技術。 200817530 一氧化碳超臨界流體與薄膜元件反應後，二氧化碳在減壓下揮發成 氣體，使溶解在二氧化碳内的物質可沈澱折出，而與其他固、液體:物 貝勺尚隹。一氧化碳不會造成污染，為符合環保要求的綠色溶劑，f取 代傳統的有機溶劑，又可回收使用，無溶劑殘留問題。 一氧化碳超臨界流體對於薄膜元件的表面改質技術可為靜態方式 (static mode)或動態方式(dynamic mode)，靜態方式為直接將薄膜元件置 於高壓處理槽中，把高壓處理槽封閉後加熱及加壓到達所設定的溫度 及壓力，並保持一段時間平衡後，打開高壓處理槽，將薄膜元件取出。 另一方面，動態方式為常時加熱及加壓，二氧化碳超臨界流體持續進 出高壓處理槽。 ' 由於二氧化碳超臨界流體具有類似氣體擴散性與液體溶解能力，使 其滲透速率比液體似同時具錢體所無·解能力。因此用於表面 ^質時’▲速率比液體快而纽，尤其是溶解能力可隨流體溫度、壓力、 密度而變。當越處於超臨界狀態時，其雜增加，·質的作用亦 增加，對洛質的溶解度進而增加。溶解度高，表示對於薄膜元件之表 面改質愈容易進行。 、 & 二氧化碳超臨界流體的表面改質社要優點包括可於低溫下操 作’避免物料因溫度提高而改變其原有特性，尤其是薄膜元件，對溫 度相當敏感，於低溫下操作，可維持膜請產品質地與外觀，且無殘 ㈣有栈4卜由於為二氧化碳雜性，可添加共賴(e⑽〇『 entrainer or modifier)，以提高表面改質能力。 、本發明除以二氧化碳(c〇2)超臨界流體(亭rcritkai fl卿對薄膜元 件進行表面處理，此為二氧化碳超臨界流體表面處理法(亭rcridcal 心如⑽邮咖♦基於相同原理和方式，尚可應用在二氧祕 fluid partide dispersi〇n/thin 200817530 film forming)和二氧化碳超臨界流體再生法（5叩沉诎—η— regeneration) 〇 , 【實施方式】 圖1顯^本發明之二氧化石炭超臨界流體的薄膜元件表面改質系統 之不意圖。此系統的基本元件包含液態二氧化碳、高壓幫浦、高壓處 理槽、減壓閥、低壓分離槽、收集容器。 首先使二氧化碳溶劑1 〇通過高壓幫浦2〇升壓到超臨界狀態，超臨 =流體進入高壓處理槽30與薄膜元件4〇接觸而進行超臨界表面改 質。溶解於二氧化碳超臨界流體巾的不純物，隨二氧化碳流體離開高 壓槽後，再通過減壓閥50，進行節流雜，以降低二氧化碳超臨界流 體的密度，從而使不純物與二氧化碳溶劑在低壓分離槽⑼内分離。不 純物以收集容器70的收集。 ，態二氧化碳10 :液態二氧化碳，以二氧化碳的高壓鋼瓶供應。 ，高壓幫浦2〇 :高壓幫浦為超臨界二氧化碳流體的驅動領，用於 壓縮二氧化碳，提高二氧化碳之壓力。 高壓處理槽30 :高壓處理槽為樣品反應槽，材質要财高壓、耐熱、 且不會與樣品發生反應，材料可錢用補鋼。高壓處職以加熱器 ^制槽内的溫度，而以壓力調整器控制槽内的壓力。高壓處理槽須經 常打開與_，以便更換樣品，設計上必須要求拆卸方便而且防漏。 減壓閥50 ·利用壓力調節，進行樣品分離的工作，樣品於高壓槽 表面改質後，含有溶質的二氧化碳超臨界流體通過減壓閥後釋^ 心質，二氧化碳流體可釋放於大氣中或經由壓縮機回收再使用。減壓 閥依序降低壓力，以期得不同不純物。此外，可在不同壓力下，調整 9 200817530 流速。 低麼分離槽60 ··低麼分離槽材質要对高麼耐熱，使用不錄鋼。& =刀紙’以加熱器控制溫度，而以m力調整碰力。低壓分離槽的 壓力依序降低，以期得不同不純物。 曰、 —收集容^ 70 :不純物以收餘器的方式收集，收集容^置於怪㈤ =水槽内。超臨界流體賴時，降溫造成冷卻，不純物留置在收^ 炫舉燃料電池為例，圖2a顯示二氧化碳超臨界流體的薄膜元件表 面改質前之示意圖。燃料電池的電極，使用奈米級的歸t)催化劑(觸 媒）’漿料塗佈在碳紙基材20上形成電極。奈米粉體材料包含碳材211 與鉑212，由於顆粒微小，所以具高表面能，粉體粒子間容易產生凝團 見象刀政性差，使用日守，需要添加南分子黏合劑22、高分子界面活 ，劑23，以便在塗佈漿料時，可以充分分散奈米粉體材料顆粒。例如， 陽極催化劑(觸媒)漿料為將含有界面活性劑Trit〇n χι〇〇的去離子水溶 液’與觸媒鉑-釕/碳黑(Pt-Ru/C)及Nafion溶液混合搜拌。陰極觸媒漿料 為將觸媒鉑/碳黑(Pt/C)、去離子水及Nafion溶液混合攪拌。然而，分 政的奈米粉體材料，有許多區域的表面，會被黏合劑、高分子界面活 性劑所覆蓋遮蔽，無法發揮功效。圖2a顯示奈米粉體材料包含碳材 211、始212被黏合劑22、高分子界面活性劑23所覆蓋遮蔽的狀況。 被覆蓋的碳材211、鉑212便無法發揮功能。 圖2b顯示二氧化碳超臨界流體可以將的薄膜元件表面黏合劑22、 向分子界面活性劑23清洗乾淨，碳材211、始212可以完全裸露，充 分發揮功能。應用超臨界流體，由於反應溫度降低，可減少傳統之高 /JHL乾你方法所導致的部分固體觸媒因為南溫燒結(sintering)碳而喪失活 性(deactivation)的缺點。二氧化碳超臨界流體，可以克服奈米尺度的表 10 200817530 - 面張力，具高滲透性可侵入奈米微孔和奈米間隙，可將其中覆蓋在薄 膜元件表面的黏合劑、界面活性劑等不純物有效去除，而提高催化濟! 之有效面積，可降低昂貴的鉑(Pt)催化劑的使用量，進而提高催化^應 速率。另一方面，可同時打通碳材阻塞處，製備多孔性結構，使反應 氣體能通暢流動，氣體滲透性高。孔隙為反應氣體所經過的路徑，= 好的孔洞性結構，有利於燃料及氧分子從儲槽傳輸至觸媒進行電化學 反應，氣體分子可充份接觸到鉑催化劑，提昇反應速率，大幅提高燃 料電池的效率。 本發明的薄膜元件技藝可以應用在燃料電池、鋰離子電池、電容 器、超級電容器(supercapacitor)等薄膜元件之表面雜質之去除，此為二 氧化碳超臨界流體表面處理法(supercritical fluid Surface m〇diflcati〇n)。 更進一步，也可利用二氧化碳超臨界流體將顆粒均勻的分散在基材 上’此為一氧化兔超臨界流體顆粒分散法(SUpercritiCal制d particle dispersion)。兹舉將翻(Pt)奈米顆粒催化劑分散在奈米碳管上為例，傳統 方法為球磨法(ball grinding)和官能基化學法(_ functionalizati〇n)。球磨 法為將翻和奈米碳管在添加界面活性劑的溶液中，球磨數小時，成為 黏稠狀。球磨製知導致聚集且成束的奈米碳管，大幅的降低翻沈積的 有效表面積。另一方面，溼式官能基化學法為先將奈米碳管官能基化， 再將鉑附著在奈米碳管上。溼式處理方式經由鉑溶解在奈米碳管懸浮 液，而將鉑附著在奈米碳管的外表面，須要繁複耗時的化學處理，且 產生化學液廢物。 固體顆粒在二氧化碳超臨界流體易於均勻分散，非常適於取代傳統 的球磨法和官能基化學法。二氧化碳超臨界流體顆粒分散法為將鉑(pt) 奈米顆粒催化劑和奈米碳管載體置於二氧化碳超臨界流體的高壓容器 内，使其達到反應平衡後，再卸除壓力，利用超臨界流體的特性，可 使齡米顆粒催化劑均勻分散附著於奈米碳管載體，較不會有麵催化 200817530 劑凝集問題，形成具催化機能的薄膜結構，此為二氧化碳超臨界流體 顆粒分散 / 成膜法（supercr*itical fluid partide dispersi〇n/thin flim forming)。二氧化碳超臨界流體可沈積高密度鉑奈米顆粒在奈米碳#上 且形成薄膜結構，提供較高的催化劑表面積，提昇催化劑的活性 (activity) 〇 更進一步，也可利用二氧化碳超臨界流體將使用前和使用後回收的 活性碳、碳紙的多孔性結構的阻塞處打通，進而使比表面積衝高，此 分別為二氧化碳超臨界流體表面處理法(supercritical血记 modification)和一氧化喊超臨界流體再生法（SUpercriticai打砲 regeneration) ° 多孔性的碳材，例活性碳、碳紙，其比表面積可達幾百甚至上千 m2/g。活性碳一般為圓球形顆粒’活性碳的孔隙，依孔徑的大小可分為 三種··微孔（半徑1.5〜1.6mn)、中孔（半徑L5〜2〇〇nm)、大孔（半徑 500〜2000nm)。當活性碳作為催化劑載體時，較大的孔隙是催化劑沉積 的地方。因此催化劑主要沉積在大孔和中孔内，也有少量沉積在微孔 内/舌兔的‘ ^ 一般分為兩步驟：碳化(c^〇nizati〇n)及活化 (act—)。碳化通常在500〜75〇t和無氧的條件下進行。氣體活化通 入的氣體大部分採用蒸氣、二氧化碳或是二者的混合物，反應溫度約 750〜1000 C。化學活化為將化學品添加在碳化料中活化，再水洗以除 去化學活性劑(氣化鋅、磷酸)而製得。 活性碳的活化傳統上採用氣體活化或化學活化。在活化氣體中活 化，或用化學活化劑活化。但氣體在低壓下擴散進入碳材料中孔洞的 速率較慢。碳材與氣體的反應速率較慢，微孔的生成受到限製。化學 活化容易導性活化碳機械強度的降低，且有化學活性劑的殘留問題。 兹舉活性碳的活化為例，在活性碳的使用前的活化，以二氧化碳超 臨界流體處理方面，二氧化碳超臨界流體兼具有如氣體般的低黏度、 12 200817530 高擴張係數、低表面張力，有如液體般的高密度、溶解能力，和對物 質的溶解能力可隨溫度與壓力改變等性質。所以，可深入微米和奈.:米 等級的柱形孔洞及深窄溝槽中，將停留在其中的不純物有效的去 仗而發揮二軋化喊超臨界流體表面處理法(SUpercritical fluid surface modification)的特性。 使用過的活性碳可藉由除去孔隙中的污染物而再生。活性碳的再生 (regeneration)傳統上採用熱再活化法(thermal reactivation)，必須置於高 溫下加熱，活性碳會因為高温而產生化學反應，有價值的物質在熱再 活化過程中被摧毀。熱再活化法產生燃燒火焰，造成環境污染問題， 且消耗掉約15 voL%的活性碳。熱再活化法對奈微米級顆粒尤不適合， 奈微米級顆粒會被熱氧化再活化所消耗掉。舊活性碳必須搬來搬去， 損毀活性碳的多孔性結構，花費高困難大。 在活性碳的使用過的回收，以二氧化碳超臨界流體移除吸附物以再 生活性碳，相對於傳統的熱再活化方法，二氧化碳超臨界流體再生法 ^supercritical fluid regeneration)具有無火焰無熱損失、無顆粒尺寸改 變三活性碳内部的多孔性結構不會改變、無副產品、費用低等特性。 一氧化奴超臨界流體具高擴散性和低黏性，可滲透到小面積内，可得 到較高的均勻性。 ' 太…奈米材料包括零維奈米顆粒材料、一維奈米材料(奈米管、奈米線、 奈米棒、奈米帶、奈米纜）、二維奈米薄膜、奈米多層膜以及由奈米顆 粒米纖維構成的三維奈米體材料。中空奈米管一般為線材，擁有 7 σ南勺表面積及孔隙度。當元件尺寸愈來愈小時，表面處理程序變 ^相§具有挑戰性，無法深入既小且深的地方，例如深溝槽、深孔， 砟多殘留物無法完全移除。 圖3a顯不二氧化碳超臨界流體的中空奈米管表面改質前之示意 13 200817530 圖。相同於活性碳和碳紙等多孔性的碳材，可利用二氧化碳超臨界流 " 將’、夕孔性結構的阻基處打通’進而使比表面積衝高。中空奈-:米 吕也可利用二氧化碳超臨界流體，將奈米線的中空管的阻塞處打違， 形成南度多孔結構。圖中顯示習知奈米管30的管中回有殘留雜質31 局部阻塞奈米管的中心通道。 圖3b顯示二氧化碳超臨界流體的中空奈米管3〇表面改質後之示意 S 利用一氣化石反超6¾界流體，能有效的在早一反應槽中，將奈米管 3〇中殘留雜質31清洗乾淨。由於二氧化碳超臨界流體的表面張力和黏 度非#的低，所以能有效而且快速的將二氧化碳帶到奈米微細組織結 構中彳文而發揮一氧化碳超臨界流體表面處理法(SUpercr[tical打u|d surface modification)的特性。 再舉一例，場發射顯示器的陰極漿料，以奈米碳管、銀奈米顆粒導 電銀膠和高分子粘合劑混合而成，再以網印製程塗佈在IT〇玻璃上。 相同於燃料電池的電極，可利用二氧化碳超臨界流體，將覆蓋在薄膜 元件表面的黏合劑、界面活性劑等不純物有效去除，而提高催化劑有 效面積，降低昂貴_催化劑的使用量，進而提高催化反應速率。從 而，發揮二氧化碳超臨界流體表面處理法(supercritical fluid surface modification)的特性。 場發射顯示裔的陰極漿料，也可利用二氧化碳超臨界流體，進行表 面處理，將水氣和不純物去除，達到表面改質的目地。傳統方法須使 甩有機溶劑、界面活性鮮。伴隨元件尺寸縮小，將使得所使用的水 和溶劑無法有效的將元件潤溼(wetting)，進而將殘留物去除。尤其當達 奈米尺度或深度，更使得傳統製程難以勝任。二氧化碳超臨界流體具 有接近零值的表碰力，制:¾並清洗最小部分，去除殘留物和液體。 以二氧化碳超臨界流體清洗，無溶賴留，可取代傳統的方法，從而， 發揮二氧化碳超臨界流體表面處理法（supercritical fluid surfkce 14 200817530 modification)的特性。 本驗為-突剌知技藝的新穎方法及裝置，因此上文所述的· 義性而雜制性。财改變只要合乎本案的專辦請範圍所定 義或與其範Μ效者，都應包含在本技藝之制範圍内。 【圖式簡單說明】 固1 本發明之一氧化竣超臨界流體的薄膜元侔>而 一 圖2a二氧化碳超臨界流體的薄膜元件表面改質^之示不意圖 固办一氧化奴超臨界流體的薄膜元件表面改質後之二二° 1化碳超臨界流體的中空奈米管表面改質“: ° 一氧化碳超臨界流體的中空奈米管表面改質後之乂立: 15200817530 玖, invention description: [Technical field to which the invention belongs]. The invention relates to a surface treatment system for a thin film component, which removes the surface impurities of the thin film component by a carbon dioxide (c〇2) supercritical fluid, so that the surface area of the thin film component can be improved, and the art does not need to add a strong acid test during the α removal process. Compound, so the process is safe and safe. [Prior Art] A substance usually has three phases of gas, liquid, and solid. When a solid substance changes its temperature and pressure to cause a fluid between a gas and a liquid, it is called a "supercritical fluid" (called critical). Fkid, SCF). "Supercritical Fluid" (SCF) is a fluid whose operating temperature and pressure exceed a critical value. The interface between liquid and gas disappears. The properties are between liquid and gas. High density and high simplicity of nucleus. The advantages, as well as the advantages of gas surface tension, twist, high diffusivity, high f mass transmission. In addition, the solubility can be varied by varying the operating temperature and pressure. For the different substances, the selectivity is generated. This is a property that is not found in general liquids. Therefore, "supercritical fluid" (set) can be a "super solvent" (supers〇lvent), which has high quality and can be Enter the depth of the material, dissolve the internal material, or dissolve the counter = to the ice, which is the superior characteristic of the "supercritical fluid" (SCF) with gas characteristics. To the current, high-performance thin-film components of the 3C industry, such as sub-, information, and communications, are all aimed at #材骸S, 小目目_展. The coating technology range covers optical coatings and storage materials, and can be manufactured by technologies such as Lai Yin and _ type coating. =Printing glue and polymer dispersant are mixed into _aste〇rslurry), using mesh 3 in order to make the film element to maximize efficiency, except for the mixed sentence material in the 200817530 oven machine 5 rii. Beyond the question, you must also pay attention to the fact that after the mixing of individual materials, the high surface area ugly after α° is more important. Generally, the smaller the powder-particle = 2, the better the dispersibility. Therefore, when we use the nano-grade particles to prepare the coating (four) material, the more dispersant (disqingant) needs to be added. In this case, :: the political platform increases the number of temples, after drying, too much The dispersant will mask the surface of the powdered body in the (4) film formation, which will reduce the effective surface area of the bare line of the "_ component" group. And, for example, a thin film electrode body (ηΐ_· dectr〇de assembly) is a core 7G member of the proton exchange membrane fuel 4, with a proton interlaced in the middle and a bright/σ structure of the catalyst electrode layer (cathode, anode) on both sides. The catalyst electrode is a two-layer structure of a "gas diffusion layer" (brand (1) wrist (10) la (four) and "catalyst?" (C-ySt). The gas diffusion layer is "carbon paper" or carbon cloth. Providing a channel for gas in and out. The catalyst layer is made of carbon black as a carrier, and a precious metal element such as platinum (four) or 钌_ is deposited on the carrier as a catalyst 0. For a fuel cell, a high surface area electrode represents a high capacity. High power, high queen. Nano-catalyst m coating on high surface area carbon paper substrate to form electrodes. The coating method of catalyst material is screen printing, scraping, transfer, spraying, etc. In other words, after the electrode is applied, a binder or a surfactant is added to cause a screening effect on the slurry, which affects the efficiency of use of the catalyst in the electrode. ± and the reduction of the chemical properties. In addition, the interfacial activity 遮蔽 will also cover the pores of the carbon material which originally had a high surface area, so that the surface area of the carbon material is lost up to about 3 〇 4% ·, on the film element. Surface treatment, no application has been seen A critical fluid. A conventional supercritical fluid is used to prepare a porous structure by using a supercritical fluid in combination with a solvent to prepare a porous structure of a hydrophilic biodegradable polymer. The method of use includes the following main steps: (8) The biodegradable polymer and a solvent are placed in a container, and (b) a supercritical fluid is injected into the container to maintain a predetermined temperature and time, so that the supercritical fluid is dissolved into the biodegradable polymer. The supercritical fluid and the solvent are obtained as the pressure of the porosity (9), which is visible in the Republic of China Patent Gazette No. 73235, ^, Sub-materials. Known prior art: (4) 丨 细 and patent patent publication No. 6,673,286: Conventional heat treatment method requires the removal of the active age at the high temperature sub-interface. However, the impurities of the ~_wei mixture and the high-alloy aurethane are prepared. The nano-catalyst slurry particles are: except: the surface of the catalyst that is dead is Can completely expose the factory ^ u μ 尬 4 4 ... ... ... ... 杂 杂 杂 杂 杂 杂 杂 杂 杂 杂 杂 杂 杂 杂 杂 杂 杂 杂 杂 杂 杂 杂 杂 杂 杂 杂 杂 杂 杂 杂 杂 杂 杂 杂 杂隹- Using carbon monoxide (c〇2) supercritical fluid (supercriticai brain) to remove impurities, improve surface area, and do not need to add strong acid test mouth, safe process and greatly improve the quality and performance of thin film components If it is oxidized, it has no t-sex, no self-ignition, no rot, no harmful waste, and low price. It should have a very high potential. #温度与压力 reaches the critical point (criticalp〇int), making the object secret For solid, liquid or gas, it is _ uniform fluid, this is called supercritical fluid, this pressure is critical pressure (Pc), temperature is critical temperature (10) out - temperature, Tc) ° criticality of carbon dioxide supercritical fluid The temperature is close to room temperature (tc = 3i.i °C) and the critical pressure is low (pc = 72.8 atm or 7.38 MPa). In the supercritical state, the substance has both high diffusivity of the gas and high solubility of the liquid. The carbon monoxide supercritical fluid can penetrate into the pores of the membrane element to effectively remove the impurities therein, thereby improving the degree of purification and opening the blockage, resulting in a porous structure and an increase in surface area. In addition, co-solvents can be added to adjust the solubility of impurities, which is the most promising surface modification technology. 200817530 After the carbon monoxide supercritical fluid reacts with the thin film element, the carbon dioxide is volatilized into a gas under reduced pressure, so that the substance dissolved in the carbon dioxide can be precipitated and folded, and the other solid and liquid materials are still smashed. Carbon monoxide does not cause pollution. It is a green solvent that meets environmental requirements. It is a traditional organic solvent that can be recycled and has no solvent residue. The surface modification technology of the carbon monoxide supercritical fluid for the thin film component may be a static mode or a dynamic mode. The static mode is to directly place the thin film component in the high pressure processing tank, and the high pressure treatment tank is closed and heated. After the pressure reaches the set temperature and pressure and is maintained for a period of time, the high pressure treatment tank is opened to take out the film member. On the other hand, the dynamic mode is constant heating and pressurization, and the carbon dioxide supercritical fluid continues to enter and exit the high pressure treatment tank. Since the carbon dioxide supercritical fluid has similar gas diffusibility and liquid solvency, its penetration rate is more than that of the liquid. Therefore, when used for surface quality, the rate of ▲ is faster than that of liquid, and especially the solubility can vary with fluid temperature, pressure, and density. When the supercritical state is reached, the amount of impurities increases, the effect of the mass increases, and the solubility of the lozenge increases. The high solubility means that the surface modification of the film member is easier. & The advantages of surface modification of carbon dioxide supercritical fluid include the ability to operate at low temperatures' to avoid changes in the original properties of the material due to temperature increase, especially for thin-film components, which are sensitive to temperature and operate at low temperatures. The film should have the texture and appearance of the product, and there is no residue. (4) There is a stack of 4 Bu. Because it is carbon dioxide, it can be added (e(10)〇 entrainer or modifier) to improve the surface modification ability. The present invention is divided by a carbon dioxide (c〇2) supercritical fluid (the surface treatment of the thin film element by the pavilion rcritkai flqing, which is a carbon dioxide supercritical fluid surface treatment method (the pavilion rcridcal heart is like (10) mail coffee ♦ based on the same principle and manner, It can be applied to the fluid partide dispersi〇n/thin 200817530 film forming) and the carbon dioxide supercritical fluid regeneration method (5叩 sinking-η-regeneration), [Embodiment] FIG. 1 shows the oxidation of the present invention. The structure of the surface modification system of the carbon fiber supercritical fluid is not intended. The basic components of this system include liquid carbon dioxide, high pressure pump, high pressure treatment tank, pressure reducing valve, low pressure separation tank, and collection container. The high pressure pump 2 is boosted to a supercritical state, and the fluid enters the high pressure treatment tank 30 to contact the membrane element 4 to perform supercritical surface modification. The impurities dissolved in the carbon dioxide supercritical fluid towel leave the high pressure with the carbon dioxide fluid. After the tank, the pressure reducing valve 50 is used to perform the throttling to reduce the density of the carbon dioxide supercritical fluid, thereby The pure substance is separated from the carbon dioxide solvent in the low pressure separation tank (9). The impurities are collected in the collection container 70. The carbon dioxide 10: liquid carbon dioxide is supplied in a high pressure steel cylinder of carbon dioxide. The high pressure pump 2: the high pressure pump is supercritical carbon dioxide The driving collar of the fluid is used to compress carbon dioxide and increase the pressure of carbon dioxide. High-pressure treatment tank 30: The high-pressure treatment tank is a sample reaction tank, the material is high-pressure, heat-resistant, and does not react with the sample, and the material can be used for supplemental steel. The high pressure is used to control the temperature in the tank, and the pressure regulator controls the pressure in the tank. The high pressure treatment tank must be opened frequently and _ to replace the sample, and the design must be easy to disassemble and leakproof. 50 ·Using pressure regulation to carry out sample separation work, after the sample is modified on the surface of the high pressure tank, the carbon dioxide supercritical fluid containing the solute is released through the pressure reducing valve, and the carbon dioxide fluid can be released into the atmosphere or recovered through the compressor. Re-use. The pressure reducing valve sequentially reduces the pressure in order to obtain different impurities. In addition, it can be used at different pressures. Next, adjust 9 200817530 flow rate. Low separation tank 60 · · Low separation tank material should be high heat resistance, use no steel. & = knife paper to control the temperature with the heater, and adjust the force with m force. The pressure of the low pressure separation tank is sequentially reduced, in order to obtain different impurities. 曰, - collection capacity ^ 70: impurities are collected in the form of a receiver, and the collection capacity is placed in the strange (5) = sink. When the supercritical fluid is lowered, the temperature is lowered. Cooling, the impurities are left in the collection of the fuel cell as an example, Figure 2a shows the surface of the carbon dioxide supercritical fluid before the surface modification of the thin film element. The electrode of the fuel cell, using the nano-grade catalyst (catalyst) The slurry is coated on the carbon paper substrate 20 to form an electrode. The nano-powder material contains carbon material 211 and platinum 212. Because of the small size of the particles, it has a high surface energy. It is easy to produce coagulation between the powder particles. It is difficult to use a knife. It is necessary to add a nano-molecular binder 22 and a polymer. The interface is active, agent 23, so that the nano-powder material particles can be sufficiently dispersed when the slurry is applied. For example, the anode catalyst (catalyst) slurry is a mixture of a deionized aqueous solution containing a surfactant Trit〇n χι〇〇 and a catalyst platinum-rhodium/carbon black (Pt-Ru/C) and a Nafion solution. Cathode Catalyst Paste The catalyst platinum/carbon black (Pt/C), deionized water and Nafion solution were mixed and stirred. However, the divided nano-powder materials have many areas of the surface that are covered by adhesives and polymer interface agents, and cannot function. Fig. 2a shows a state in which the nano-powder material contains the carbon material 211, and the first 212 is covered by the binder 22 and the polymer surfactant 23. The covered carbon material 211 and platinum 212 cannot function. Fig. 2b shows that the carbon dioxide supercritical fluid can clean the surface element of the thin film element 22, and the molecular surfactant 23 can be cleaned. The carbon material 211 and the beginning 212 can be completely exposed and fully function. The use of supercritical fluids, due to the reduced reaction temperature, can reduce the disadvantages of the traditional high/JHL dry partial solution caused by the loss of activity of some solid catalysts due to southing sintering of carbon. Carbon dioxide supercritical fluid can overcome nanometer scale Table 10 200817530 - Surface tension, high permeability can penetrate nanopores and nano gaps, which can cover impurities such as adhesives and surfactants on the surface of thin film components. Effective removal, while increasing the effective area of the catalyst, can reduce the amount of expensive platinum (Pt) catalyst used, thereby increasing the catalytic rate. On the other hand, the carbon material can be opened at the same time to prepare a porous structure, so that the reaction gas can flow smoothly and the gas permeability is high. The pores are the path through which the reaction gas passes. = Good pore structure is beneficial to the electrochemical reaction of fuel and oxygen molecules from the storage tank to the catalyst. The gas molecules can fully contact the platinum catalyst, which increases the reaction rate and greatly increases the efficiency. Fuel cell efficiency. The thin film component technology of the present invention can be applied to the removal of surface impurities of a thin film component such as a fuel cell, a lithium ion battery, a capacitor, a supercapacitor, etc., which is a supercritical fluid surface m〇diflcati〇n ). Further, the carbon dioxide supercritical fluid can also be used to uniformly disperse the particles on the substrate. This is a mono-oxidized rabbit supercritical fluid particle dispersion method (dpercritiCal d particle dispersion). For example, a Pt nanoparticle catalyst is dispersed on a carbon nanotube. The conventional methods are ball grinding and functional chemistry (_functionalizati〇n). In the ball milling method, the turning and carbon nanotubes are ball-milled for several hours in a solution in which a surfactant is added, and become viscous. Ball milling produces a carbon nanotube that causes aggregation and bunching, which greatly reduces the effective surface area of the tumbling deposit. On the other hand, the wet functional chemistry is to first functionalize the carbon nanotubes and then attach the platinum to the carbon nanotubes. The wet treatment method is dissolved in the carbon nanotube suspension via platinum, and the platinum is attached to the outer surface of the carbon nanotube, which requires complicated and time-consuming chemical treatment and chemical liquid waste. Solid particles are easily and uniformly dispersed in a carbon dioxide supercritical fluid and are well suited to replace conventional ball milling and functional group chemistry. The carbon dioxide supercritical fluid particle dispersion method is to place a platinum (pt) nanoparticle catalyst and a carbon nanotube carrier in a high-pressure vessel of a carbon dioxide supercritical fluid to achieve a reaction equilibrium, and then remove the pressure, using a supercritical fluid. The characteristics of the meter particles can be uniformly dispersed and adhered to the carbon nanotube carrier, and there is no surface catalysis of the agglomeration problem of the 200817530 agent, forming a film structure with catalytic function, which is a carbon dioxide supercritical fluid particle dispersion/film formation method. (supercr*itical fluid partide dispersi〇n/thin flim forming). The carbon dioxide supercritical fluid can deposit high-density platinum nanoparticle on the nanocarbon # and form a thin film structure, providing a higher catalyst surface area, improving the activity of the catalyst, and further utilizing carbon dioxide supercritical fluid. The blockage of the porous structure of the activated carbon and carbon paper recovered before and after use is opened, and the specific surface area is increased. This is the supercritical fluid surface treatment method (supercritical blood volume modification) and the first oxidation supercritical fluid. Regeneration method (SUpercriticai shot regeneration) ° Porous carbon material, such as activated carbon, carbon paper, its specific surface area can reach hundreds or even thousands of m2 / g. Activated carbon is generally the pore of the spherical spherical particles 'activated carbon. According to the size of the pore size, it can be divided into three types: micropores (radius 1.5~1.6mn), mesopores (radius L5~2〇〇nm), large pores (radius 500). ~2000nm). When activated carbon is used as a catalyst support, the larger pores are where the catalyst is deposited. Therefore, the catalyst is mainly deposited in the macropores and mesopores, and a small amount deposited in the micropores/the tongue is generally divided into two steps: carbonization (c^〇nizati〇n) and activation (act-). Carbonization is usually carried out under conditions of 500 to 75 Torr and anaerobic conditions. Most of the gas activated by the gas is vapor, carbon dioxide or a mixture of the two, and the reaction temperature is about 750 to 1000 C. Chemical activation is carried out by adding a chemical to the carbonized material for activation, and then washing with water to remove the chemical active agent (zinc oxide, phosphoric acid). Activation of activated carbon has traditionally employed either gas activation or chemical activation. Activated in an activating gas or activated with a chemical activator. However, the rate at which the gas diffuses into the pores of the carbon material at a low pressure is slow. The reaction rate of carbon material and gas is slow, and the formation of micropores is limited. Chemical activation easily leads to a decrease in the mechanical strength of the activated carbon and a problem of residual chemical active agents. For example, activation of activated carbon, in the activation of activated carbon before use, in the treatment of carbon dioxide supercritical fluid, carbon dioxide supercritical fluid has a low viscosity like gas, 12 200817530 high expansion coefficient, low surface tension, like The high density of liquids, the ability to dissolve, and the ability to dissolve substances can vary with temperature and pressure. Therefore, it is possible to deepen the microporous and nai.: meter-scale cylindrical holes and deep and narrow grooves, and the impurities remaining in it can be effectively removed to perform the SUpercritical fluid surface modification method. Characteristics. Used activated carbon can be regenerated by removing contaminants from the pores. Regeneration of activated carbon has traditionally been carried out by thermal reactivation, which must be heated at elevated temperatures. Activated carbon produces chemical reactions due to high temperatures, and valuable materials are destroyed during thermal reactivation. The thermal reactivation method produces a combustion flame that causes environmental pollution problems and consumes about 15 voL% of activated carbon. The thermal reactivation method is particularly unsuitable for nanon-sized particles, which are consumed by thermal oxidation and reactivation. Old activated carbon must be moved in and out, and the porous structure of activated carbon is destroyed, which is costly and difficult. In the used recovery of activated carbon, the adsorbent is removed by the carbon dioxide supercritical fluid to regenerate the activated carbon. Compared with the conventional thermal reactivation method, the supercritical fluid regeneration has no flame and no heat loss. No particle size change The porous structure inside the tri-activated carbon does not change, has no by-products, and has low cost. NiOgen supercritical fluid has high diffusivity and low viscosity, and can penetrate into a small area to obtain higher uniformity. 'Too... nanomaterials include zero-dimensional nanoparticle materials, one-dimensional nanomaterials (nanotubes, nanowires, nanorods, nanobelts, nanowires), two-dimensional nanofilms, nano-multilayers A film and a three-dimensional nanobody material composed of nano-particles of rice fibers. Hollow nanotubes are generally wire rods with a surface area and porosity of 7 σ. As component sizes get smaller and smaller, surface treatments become challenging and cannot penetrate deep and deep, such as deep trenches, deep holes, and many residues cannot be completely removed. Figure 3a shows the surface of the hollow nanotube before the modification of the carbon dioxide supercritical fluid. 13 200817530 In the same manner as a porous carbon material such as activated carbon or carbon paper, the carbon dioxide supercritical flow can be used to open the resistive base of the solar structure and the specific surface area is increased. Hollow Nai-: Mi Lu can also use carbon dioxide supercritical fluid to break the blockage of the hollow tube of the nanowire to form a south porous structure. The figure shows a central channel in which the residual impurities 31 in the tube of the conventional nanotube 30 partially block the nanotube. Figure 3b shows the surface of the hollow carbon nanotubes of carbon dioxide supercritical fluid after the modification of the surface. The use of a gas fossil anti-63⁄4 boundary fluid can effectively clean the residual impurities 31 in the nanotubes in the early reaction tank. clean. Due to the low surface tension and viscosity of the carbon dioxide supercritical fluid, it can effectively and quickly bring carbon dioxide into the nano-microstructure and play the role of carbon monoxide supercritical fluid surface treatment (SUpercr [tical hit u|d Surface modification). As another example, the cathode slurry of the field emission display is a mixture of a carbon nanotube, a silver nanoparticle conductive silver paste, and a polymer binder, and is coated on the IT glass by a screen printing process. The same as the electrode of the fuel cell, the carbon dioxide supercritical fluid can be used to effectively remove the impurities such as the binder and the surfactant covering the surface of the film element, thereby increasing the effective area of the catalyst, reducing the amount of expensive catalyst, and thereby improving the catalytic reaction. rate. Thus, the characteristics of the supercritical fluid surface modification are exerted. The field emission shows the cathode slurry of the genus, and it can also use the carbon dioxide supercritical fluid to perform surface treatment to remove the water vapor and the impurities to achieve the purpose of surface modification. The traditional method requires an organic solvent and a fresh interface. As the size of the component shrinks, the water and solvent used will not effectively wetting the component, thereby removing the residue. Especially when the nanometer scale or depth makes the traditional process difficult. The carbon dioxide supercritical fluid has a near-zero surface impact force: 3⁄4 and cleans the smallest part to remove residues and liquids. It is replaced by a carbon dioxide supercritical fluid, which can replace the traditional method, so as to exert the characteristics of supercritical fluid surfkce 14 200817530 modification. This test is a novel method and device for knowing the skills of the Turkic, and therefore the above-mentioned meaning and miscellaneous. The change of financials shall be included in the scope of this art as long as it meets the scope of the special requirements of the case. [Simple description of the scheme] Solid 1 is a thin film element of a cerium oxide supercritical fluid of the present invention> and a surface modification of a thin film element of a carbon dioxide supercritical fluid of Fig. 2a is not intended to fix a monohydrate of superoxide fluid. Surface modification of the hollow nanotubes of the TiO2 supercritical fluid after the surface modification of the thin film element": ° The surface of the hollow nanotube surface of the carbon monoxide supercritical fluid is modified: 15