1240767 九、發明說明： 劈"月戶斤屬^^技術領域】 發明領域 為明確起見’相關名詞在本申請中做下屬解釋： 5 先進材料：泛指不能用傳統電鍍技術鍍出的材料。 鍛覆：泛指在物體表面沈積塗層或薄膜的所有方法。 薄膜：泛指厚度在一個寬廣範圍變動的塗層。 等離子：指因輝光或弧光放電而產生的電離的氣態分 子集合體。該集合體含在數目上等同的正，負離子，此外 10也可含部分未電離的原子或分子。 包括：做廣義名詞解，帶類似“包含，，之義。“包栝 在本申請中也理解成涉及所敘述到的一個整體或步驟， 或一群整體或步驟，卻不排除末敘述到的一個整體或步驟 ，或一群整體或步驟。 15 【先前技術】 發明背景 電鍍這一術語指一種工藝，一種眾所周知的在物體表 面鍍覆金屬的技術。 典型的電鍍工藝在一電解槽中進行。該電解槽中設有 20陽極，陰極和電解液。陰極通常由待鍍物體構成，電解液 則含待鍍金屬離子。在陽極和陰極之間施加一個電位差， 電場力驅使金屬離子在陰極上析出。應用該技術在金屬表 面鍍覆銅，錫，辞和金等金屬已有很長的歷史。在物體表 面用傳統電鍍技術可鍍覆的其他金屬還有鉻，鎳，鐵，鈷 1240767 ’ m铟^等。金屬電錢具有廣泛的用途，例 如在金屬表面鍍覆，可降低腐姓傾向，或增加美學觀感和 價值。 儘管電鑛技術可鍍出不少材料，有許多材料，如所 5謂的先進材料，卻是用傳統電鑛技術所不能鑛出的。一個 簡單的解釋是金屬電化序本身就排斥了這些材料在習用電 壓範圍電極析出的可能性。 顯然，如果能夠發明一種技術，可在物體表面沈積或 嫉覆那些先進材料，則该技術就有很大優越性。它將在廣 10為興趣的領域展現許多新的選擇機會，產生許多新的可能 性來擴大可鏟覆材料品種，從而大大增加薄膜沈積的新應 用。 當前沈積先進材料的方法有物理離子氣相沈積和等離子增 強化學氣相沈積。實用中，這些工藝必須在真空室中進行 15 ，因而有很大的局限性。首先，實施這些工藝要求先進的 真空裝備配套。其次，不少氣相沈積技術員方向性，其繞 向性差，無法簡單地應用於形狀複雜’空間構型變化大的 物體。物體數量與尺寸也受真空室的尺寸限制。再之，生 產周期長。此外，有些工藝伴隨高溫過程，這對那些精密 20或溫度敏感材料的鍍覆是不適用的。 本發明側重在克服這些弊病。 【明内3 發明概要 本發明的一個方面，是提供一種在物體表面沈積材料 1240767 的新方法，包括： 提七、们&有電解液和分離對電極的電解槽，此分 離對電極乃由一電極構成此物體； 在構成此物體之電解液附近，由此電解液(物)產生一連 5串帶有欲鍍材料來源的氣泡族團· 在上述的電極間加上一個電位差，電位差大得足以在 上述氣泡族團區域形成輝光放電，而且上述物質是被儲存 於上述物體之上的離子。 述專离隹子體中產生的高能離子通過與待鍵固體表面 10 的相互作用而實現沈積。 δ亥等離子體中的離化分子氣處於啟動或高能狀態，因 而能夠越過界面能壘兩著實地沈積在所述電極表面。等離 子實質上強化了沈積過程。 所述在電極鄰近形成輝光放電區，係電極周邊氣泡族 15團的介電擊穿所致。氣泡是介電的，導電性报低，結果在 電極鄰近的氣泡族團結集帶形成高電位降，導致最線的氣 泡墼穿。 、^ 入電解液 上述等離子體產生於電解液所含的氣泡内。電解液的 功用’相當於電離氣泡的容體。該氣泡含有電解液中產生 二:材料先行物。該先行物可以通過擴散與蒸發從液相 帽遞到氣相卜也可以直接㈣❹卜借絲或混氣法輸 或表面預鍍 待鍍物體可以是任何種類的導電性材料， 導電塗層的非導電性材粒。 20 1240767 推薦的導電性材料包括鋼鐵，鋁及鋁合金，鈦及鈦合 金等等，也包括半金屬和半導體材料如矽，包括導電有機 材料如ABS塑膠。非導電性材料表面塗複導電塗層的例子 ，有塗複銦-錫氧化物(ΙΤ0)的玻璃，塗複有機導電塗層或經 5銀鏡處理的陶瓷，塑膠，玻璃等。典型應用材料包括鋼鐵 ’矽材，ITO玻璃，鈦合金及鋁合金等。 上述氣泡的產生方法，可以是下列方法中的一種或多 種的混合，即 電解法，沸騰法，氣穴法，氣液混合法，充氣法，化 10學反應法，電子或離子碰撞分解法。 電解法是通過在電極之間施加電位差而導致電極上氣 泡析出。例如，氫氣泡在陰極上的電解析出，和氧氣泡在 陽極上的電解析出。沸騰法是在電極區域將電解液加熱到 局部或全部沸騰狀態而形成氣泡和蒸氣，這可借直接通電 15加熱電極，或通電加熱在電解液中移動或靜止的栅網，或 在槽外部加熱槽内電解液等方法實現。 紅外線加熱，微波加熱，或鐳射加熱也可用於產生沸 騰氣泡。 氣穴氣泡可由超聲波發生器產生，或使液相流體或充 20氣的多相流強制性注入電極鄰近而產生。按流體動力學原 理在電極鄰近流動的電解液中也可產生氣穴氣泡。 直接將氣泡注入電極鄰近也可用來產生氣泡。 氣泡也可通過電解液中的化學反應生成氣體產物的方 法產生。典型的這類反應涉及電解液中的熱分解，或酸碱 1240767 反應。在電解液中添加發泡劑的方法也可用來產生所需氣 泡。 本發明中的氣泡特徵，是在電極周圍鄰近區域形成氣 泡殼。該氣泡殼厚度在幾個納米到50毫米之間。典型的氣 5 泡殼厚度在1到5毫米。不難理解，氣泡殼在整體上可以是 非均勻的。 氣泡可從電解液的組分中產生，或由電解槽外引入氣 體或蒸氣或氣液混合體的方法產生。 氣泡區形成輝光放電的步驟，可以由提高電極之間的 10 電位差，使之超過某一特定價而實現。 推廣之，所述輝光放電的形成步驟，還可以借助其他 手段實施輔助，例如磁場，可發射熱電子的熱絲，錯射， 微波，或射頻感應及超聲波。 氣泡内所含的氣態物質可以直接來自電解液，或產生 15 於電解液。輝光放電使氣泡内的氣體電離而形成等離子體 。本發明的重要特徵之一是電解液起容納等離子的作用。 本工藝一般在環境大氣壓下實施，雖然氣泡内的壓力 可以與環境大氣壓有差別。明確地說，本工藝並不要求在 真空條件下實施。但也可以在低於一個大氣壓的壓力條件 20 下實施。 所述電解液包括： 作為載體的液體； 供給在某電極上沈積的材料來源或先行物。 所述電解液可包括如下添加劑：改善電解液電導率的 1240767 =速:低電解液表面張力的表面活性劑類添加劑，提 ==的催化劑類添加劑’氣泡促進劑，緩衝劑，和 文σ贫性旎和鍍層質量的添加劑。 =電解液導電率的添加劑包括有機鹽和無機鹽，例 如氣化鉀，氯化鎂，醋酸鈉等。 欲鑛材料可由所述電解液中通過擴散和蒸發進入氣泡 ，然後因輝光放電而在氣泡内形成電離。 10 本發明可沈積那些經普通電鑛就可鑛覆的材料，包括 絡，辞，銅，錄，鐵，銘，録，錫，絡，銀，金，銦和艇 等金屬，也包括其合金，以及半導體材料如鎵。 本方法或工藝的顯著功用，是沈積許多傳統電鑛工藝 無法鍍出的先進材料，例如碳，硼，矽等半金屬及其化合 物如氮化碳，碳化硼等。 此外，傳統電鍍無法單獨鍍出或難以鍍出的金屬有鈦 ，鋁，鎢，錳，鉬，鈮等。這些金屬在水溶液中的電極電 位很負。用本發明的方法可以鍍出這些金屬及合金或化合 物。 二元化合物半導體如鱗化錄，碗化姻，坤化錄，硫化 福，磁化編，銘化編，三硫化二Μ，硫化二銅，碼化辞， 20 鉈化銦，硒鉬或硒鎢化合物，矽氧化物，銅或鈦氧化物等 ，以及三元化合物半導體，聚合物，生物促進劑（女口叫Ir203 ’ Rb2〇3，Ru〇2等），和生物材料如經基鱗酸4¾等，也可以 用本發明的等離子電鍍工藝沈積出。 本方法或工藝也可鍍鉻而不採用六價鉻為主鹽。傳統 !240767 電鍍鉻工藝離不開六價鉻，該化合物毒性大，有害健康並 污染環境。 本專利特別適宜的應用場合，由待鍍物體構成的某電 極為陰極，欲鍍材料為先進材料，例如碳，矽，鈦等。 但在其他應用場合，待鍍物體構成的某電極也可以是 陽極，則對偶電極為陰極，從而進行沈積，氧化處理，等 離子電泳，或等離子陽極化處理等。 通#，對偶電極可以是惰性的，或者是可溶性的。可 ’合性對偶電極可提供在另一電極上發生沈積的材料源泉。 10所述對偶電極的典型材料為金屬材料，例如紹及紹合金， 不銹鋼，或石墨。 陰極形狀不限，可以是長條形，如軸狀物。相應的陽 極可包含多塊板狀體，環布在陰極四周。 陰極也可以是具有兩個待鍍表面的平板件，對應的陽 15極可由兩塊隔開放置的板狀物構成，以一定距離各對應於 陰極的一待鍵表面。 氣泡也可以從電解槽外輸入氣體而產生，讓氣體可以 包含欲鍵材料或先行物。欲錢材料或先行物同樣在等離子 體中電離，隨後沈積在物體表面。 20 祕槽形狀沒有嚴格限制。通常可以為-長方形的帶 底與壁的容器’電極自槽頂部所設的開口處插入，浸於電 解液。電解槽尺寸也無嚴格限制。此外，電極也可按與槽 底平行或垂直的方式佈置。 本工云可進步包括對電解液實施冷卻，以便散發因 1240767 等離子反應而產生的多餘熱。也可包括對電解液實施調節 和維遵的措施’使電解液的某組分或多個組分以及液面保 持穩定。 冷部方式包括從電解槽中抽出電解液，使之通過冷卻 5器，然後返回到電解槽中。 在傳統電鑛工藝中，氣泡被視為材料沈積的一個妨礙 <障礙’所以在電解槽中作業時，往往要力圖避免氣泡的 產生’本發明工藝則恰洽相反，在作業中是有意去產生氣 /包’並利用某電極鄰近區域的氣泡，這是本發明的基本特 徵％繞某電極的氣泡殼是建立等離子區的關鍵，而等離 子區的建立’導致了物體表面的等離子沈積。 此外，傳統電鍍限與以水溶液為電解液。本發明則不 文此限制。固此，本發明中所採用的電解液有更廣泛的選 擇範圍’它還可包括有機溶劑體系，有機金屬化合物體系 5和金屬有機化合物體系。次之，本發明工藝並不要求將金 屬離子溶於水溶液來提供欲鍍品種。所要求的只是欲鍍材 料來源或先行物被包容在電極鄰近區域的氣泡中。 本發明的另一組成部分，是以系統的方式提供物體表 面材料沈積的裝置，包括： 20 電解裝置，含電解槽，以及分離的對電極，即浸於電 解液的陽極和陰極，且待鍍物體為對電極的其中之一； 盛於電解槽中的液態電解質： 陰極鄰近產生氣泡族團的設施；和 所述電解液可含一個或多個組分，或具有在發明第一 12 1240767 口 p刀中所敘述的其他特徵。 產生氣泡族團的設施可包括電解作用引起的電極析出 氣泡’也可包括將超聲波傳播入電解液的超聲波發生器。 在對電極之間施加電位差的設施可包括一個輪出_壓 5在3000伏特下的電源。典型的輸出電壓應滿足工作電壓在 250到1500伏特之間。電源輸出可以是直流，或脈動的，如 高頻脈衝電源，或非平衡的。 等離子電鍍裝置可進一步包括將電解槽分割為沈積與 迴圈兩個空間。 1〇 該裝置可包括從迴圈空間抽出電解液，冷卻電解液， 和將電解液輸回電解槽中的設施。 該電解液可進一步包括必要時使電解液液面保持穩定 水平的設施，和電解液組分調節維護的設施。 概括說’所述工藝提供一個沈積先進材料的新技術和 15 —個在傳統電鍍技術基礎上改進的簡便的鍍覆系統。該工 藝的核心在於某電極臨近引入一個非平衡狀態過程，使氣 >包殼所含的先行物材料得到充分的能量和速度，實現有效 的沈積。該過程通過施加一個電場，電場場強大到足以在 氣泡内產生輝光放電而形成等離子。電離產生的高能離子 2〇卩思著發生沈積，在局域化高溫下與電極表面結合而形膜。 欲鍍先行物或材料來源，是在液體所包圍的氣泡中電 離。該液體有效地容納了種種所發生的反應。 在該電解裝置中產生輝光放電並形成等離子體是容易 實現的。因為氣泡殼的存在，電解槽中的電壓降在陰極前 13 1240767 沿的氣泡殼層中達到很高的數值。電壓降集中在這薄層中 ，而非線性分佈在兩電極空間。如此則提供產生輝光放電 和離子沈積的驅動力。 闡明物體上沈積先進材料方法及其實施裝置的方式有 5 許多種，為方便起見，下文將以典型例子以及所附的圖例 進行詳細說明，將本發明具體化。採用這種闡述方式的目 的，是便於那些對本發明有興趣的人明確和掌握如何將本 發明實用化。不言而喻，這種描述方法所帶的具體特性， 並不掩蓋前述部分所揭示的普遍特性。 10 圖式簡單說明 第1圖所示為本發明相應的等離子電鍍工藝原理示意； 第2圖所示為實施本發明的電解裝置及輔助裝置的佈 局不意， 第3圖所示為第2圖中的電解槽附加超聲波發生器以及 15 氣穴氣泡的示意； 第4圖所示為電解槽中的電壓-電流特性曲線； 第5圖所示為在電極之間施加電壓時，環繞陰極所產生 的氣泡殼； 第6圖所示為電解槽中形成穩定輝光放電時的環繞陰 20 極的氣泡殼； 第7圖所示為電解槽中陰極與陽極設置一例的俯視圖； 第8圖所示為電解槽中陰極與陽極設置另一例的俯視 圖； 第9圖所示為本發明相應的陰極鍍碳後，沿樣品長度方 14 1240767 向呈現的不同區域； 第10圖所示為絲狀陰極未鑛前的掃描電鏡表面形貌； 第】1圖所不為第9圖中陰極A區的掃插電鏡表面形貌； 帛12圖所示為第9圖中陰極B及C區的掃描電鏡表面形 5貌； 第13圖所示為第9圖中陰極BAC區的高倍掃描電鏡表 面形貌； 第】4圖所示為板狀陰極上與第9A圖區大略對應區域的 掃插電鏡表面形貌； 1〇 第15圖所示為板狀陰極上與第9B圖區大略對應區域的 掃描電鏡表面形貌； 第16圖所示為板狀陰極上與第9C圖區大略對應區域的 掃描電鏡表面形貌； 第17圖所示為第9圖中陰極鍍碳後的表面能譜分析結 15 果； 第18圖所示為鍍碳層的鐳射拉曼譜； 第19圖所示為絲狀陰極鍍鈦後的掃描電鏡表面形貌； 第20圖所示為第19圖中鍍鈦層的高倍掃描電鏡表面形 貌； 20 第21圖所示為第19圖中的鍍鈦層的能譜分析結果； 第22圖所示為銅網陰極的鍍鈦層在透射電鏡所附能譜 儀上測定的成分； 第23圖所示為絲狀陰極鍍矽層的掃描電鏡表面形貌； 第24圖所示為第23圖中鍍矽層的高倍掃描電鏡表面形 15 1240767 與液體混合後輪入電解槽而形成。 第3圖所示為第2圖所示電解裝置的擴展，是將超聲波 發生器佈置在電解槽周圍，該發生器產生的超聲波通過電 解液傳播，產生圍繞陰極的氣泡族。 5 第4圖所示為該電解裝置中逐步增加電壓時得到的典 型電壓-電流特性曲線。曲線起始部分，為電流隨電壓呈比 例增長的歐姆區。隨之而來的是震盪區，電流開始震盪。 申請人認為’電流震盪係因電極氣泡析出並形成電極局域 化遮蔽效應所致。當在氣泡中形成等離子時，氣泡内產生 10輝光，隨之氣泡破裂。無數輝光放電的氣泡族，可形成包 容電極的等離子殼。表觀電流密度在震盪區尾端顯著下降 ，是因為此時已形成數量眾多的氣泡，電極遮蔽效應增大 〇 陰極析出氣泡主要是電解氫氣泡，但陰極表面還存在 15電解液電加熱弓1起的蒸發氣泡。前述的其他方法也可產生 氣泡，例如超聲波引發的氣穴氣泡。 ^過定時間’氣泡數量與密度增加到足以覆蓋整個 陰極表面達到臨界電壓時，輝光放電開始。對—個給定 的體系’ S品界電壓是一個確定值，稱為起火點。實驗觀察 2〇表月輝光放電疋在陰極表面為一層准連續的氣泡殼所包 圍時產生的。 在、為狀陰極條件下，對應於起火點，-小火球或火球 團通兩首先出現於絲狀電極侵入電解液的末端。進一步增 加電壓’則輝光放電將逐步擴及整個陰極侵入表面。輝光 17 1240767 放電是個動態過程’且可明眼觀察到輝光放電族團與閃光 貫穿氣泡殼。 輝光放電的產生’疋由於氣泡在南電場場強下的介電 擊穿所致。陰極表面由於存在氣泡殼，自陽極到陰極的距 5離内，絕大部分電麈降將落在陰極鄰近區域的氣泡殼層内 。此處電場強度可達lxlO4到lxl〇5V/m。 工作電壓可設定在高於起火點50-100伏之間的某一值 。典型的約在25〇-15〇()伏之間，對應第4圖所示特徵曲線的 低段平臺部分，即輝光放電區。 3 ，由料光放電，氣泡⑽成等離子體。第5圖係陰極表 :形成=泡殼的示意；第6_為陰極表面形成穩定輝光放 =不意。如_示’中請人觀察到穩定輝纽電時，陰 示。面臨近形成兩個不同的區域。整個工藝特徵由第碉： 15 塗複導極材料’可以是導體’半導體，或 鎖，軟鋼，二鋼:;Γ實驗驗證的可行陰極材料 筛狀，杆1^。==，極雜可从平板狀，網 。 °數里，形狀與尺寸沒有嚴袼限制 陽極可用任咅1 石墨，〜本專利申請人曾成功地採用 合金作陽極材料。雖2子電鑛。—般推薦採用紹及紹 該工藝有影继,r 、、、沈積是在陰極表面進行，但陽極對 化導致電-電轉在轉㈣產生不純物，純 8大，阻滞或甚至中斷沈積過程。類似 18 1240767 _，陽極的數量，形狀與尺寸也沒有嚴格限制。有時， 陽極可直接以導電的電解槽構成。 第7圖和第8圖給出電極配置的兩種模式。 是，這兩種模式只是例子，實際上有多種多樣的電極配置 5模式可供採用。第7圖巾，四塊平板狀陽極均布於四周，中 心是-杆狀陰極，陽極以—定距離呈放射性分佈。該模式 可滿足杆狀陰極外圓表面的均勻沈積。陰極與陽極之間的 距離-般大於10毫米，以防陽極過程對陰極形成氣泡殼的 干涉。典型的極間距為1〇到4〇毫米。 10 第8圖中，一平板狀陰極具有兩個待鍍表面，故可採用 相隔-定距離約兩平行陽極，各對應於陰極的一個待錢表 面等距放置。如果只採用一個陽極，則因電流分佈特徵所 限，沈積只能在該陰極的一個表面有效發生。 電解槽内注入合宜的電解液。電解液包含溶劑或載體 15，以形歧相環境，促使電解過程發生，且支援等離子產 生，即它是產生等離子的空間。電解液也可包含稱為先行 物的待錄材料來源。電解液還可包含各類添加劑，如提^ 電解液電導的導電劑，協助氣泡形成的促泡劑，和維持^ 解液pH值在適宜範圍的緩衝劑。 20 實用上，待鍍物體置為電解槽並浸於電解液中，通常 當作陰極。但有時也可作為陽極。 书 在電極間施加一電位差，電壓值需達到起火點以上水 平，在該水平，系統或電解槽中可達到穩定的輝光敌電， 並使放電族團覆蓋陰極待鍍表面。 ， 19 1240767 陰極表面臨近區域1主要由輝光放電族團構成，等離子 在這兒形成殼體，直接包裹著陰極表面。等離子沈積即在 此區域内進行。等離子體與陰極固體表面相互作用而產生 沈積，其過程類似離子鍍。經過形核與生長過程，陰極表 5 面逐步形成薄膜。 區域2等離子-化學反應區，係電解液與輝光放電區的 介面。該區包裹著等離子沈積區，通常呈乳色狀，肉眼可 將之與等離子沈積區和電解液主體辨別開來。 區域2或稱外區，電解液組分包括先行物在此區分解， 1〇可此還發生部分電離。由此提供欲在陰極表面沈積的所需 品種或電離先行物。這些品種是借電遷移，擴散和對流作 用，由區域2輸運到區域丨即内區。 只要維持這些條件，且電解液中存在先行物材料，沈 積即可隨之發生。 15 §輝光放電開始後，電解液溫度在很短時間内就可上 升許多。電解液溫度必須維持在適宜範圍。為此可將電解 液自槽中抽出’泵送到冷卻系統，如第2圖所示。冷卻後的 電驗可輸回槽中。電解液冷卻的因由有2, -是維持體系 穩疋，一是確保安全。這在電解液含有易燃組分時尤其必 2〇要此外，電解液在沈積反應中產生消耗，需適時補充電 解液使液面水平保持穩定。另設置一個盛有電解液的蓄 液槽可達到此目的。 申明人進彳τ 了實驗，來驗證本技術沈積3種材料，即碳 欽和石夕的有效性。實驗細節分別閣述如下。 20 1240767 碳 在第2圖所示的電解裝置上，待鍍物體做陰極，進行碳 膜的沈積實驗。 電解液組成 組分 材 料 體積分量(％) 主份」 乙醇（分析級） 50-100 溶劑 去離子水 0-50 添加劑 κα，KAc，或 MgCl 微量 組衝劑 pH7標準緩衝溶液 Wi 在建立穩定輝光放電後進行試驗沈積30分鐘，工作電 壓為-450伏。 結果由掃描電鏡等分析證明得到碳膜沈積。碳膜沈積 10在若干絲狀和平板狀表面，以及用作透射電鏡的鎳網篩上 〇 第9圖給出陰極沈積碳膜的不同區域示意。第1〇到15圖 係絲狀和平板狀陰極對應薄膜的掃描電鏡形貌。 掃描電鏡形貌清楚地顯示陰極基材上碳膜的生長。能 15譜成分分析結果揭示薄膜的主要成分為碳，且存在鉀，氧 ，氣等微量雜質。 申請人認為，鉀和氯來源於電解液中所用的氣化鉀添 加劑，而氧則主要來源於樣品長時在空氣中的暴露。 對該薄膜進行镭射拉曼譜分析，以便確定薄膜結構， 20 結果見第18圖。 第]8圖表明拉曼峰出現在波數1300-1400，及 21 1240767 1550-160(^111-1 ’與非晶態碳對應，該結論為透射電鏡分析 結果所進一步證實。 小結：陰極表面確實沈積了碳膜。該碳膜係氳致非晶 態碳，含類金剛石結合性質。薄膜本身緻密，光滑平整。 5 座 在第2圖所示的電解裝置上也對數種陰極進行了鈦薄 膜或稱塗層的沈積試驗。 用於實驗的電解液成分如下。 組分 材 料 體積分量(％) 主份 Ti(〇pr)4 50 溶劑 乙醇 50 其中主份採用Ti(〇Pr)4。作為沈積鈦材的來源，在包圍 陰極表面的氣泡殼中因等離子作用產生離化，隨後沈積於 陰極表面。 其反應過程可能如下： 15 Ti(OPr)4(l)-Ti(OPr)4(g)1240767 IX. Description of the invention: "Introduction to the month of households" Technical field] For the sake of clarity, related terms are explained below in this application: 5 Advanced materials: Broadly refers to materials that cannot be plated with traditional electroplating technology . Forging: Generally refers to all methods of depositing a coating or film on the surface of an object. Film: Broadly refers to a coating whose thickness varies over a wide range. Plasma: refers to a collection of ionized gaseous molecules produced by glow or arc discharge. The aggregate contains an equal number of positive and negative ions, and may also contain partially unionized atoms or molecules. Include: do broad noun solutions with meanings like "including,". The baggage is also understood in this application to refer to a whole or step described, or a group of wholes or steps, but does not exclude the last described Whole or step, or group of wholes or steps. 15 [Prior Art] Background of the Invention The term electroplating refers to a process, a well-known technique for plating metal on the surface of an object. A typical electroplating process is performed in an electrolytic cell. The electrolytic cell is provided with 20 anodes, a cathode and an electrolyte. The cathode usually consists of an object to be plated, and the electrolyte contains metal ions to be plated. A potential difference is applied between the anode and the cathode, and the electric field forces the metal ions to precipitate on the cathode. The technology has been used to plate copper, tin, copper and other metals on metal surfaces for a long time. Other metals that can be plated on the surface of the object using conventional electroplating techniques are chromium, nickel, iron, cobalt 1240767 'm indium ^ and the like. Metal electric money has a wide range of uses, such as plating on metal surfaces, which can reduce the tendency to rot names, or increase aesthetics and value. Although the power mining technology can plate a lot of materials, there are many materials, such as the so-called advanced materials, which cannot be mined with traditional power mining technology. A simple explanation is that the metal electrification sequence itself excludes the possibility of these materials precipitating in the conventional voltage range electrodes. Obviously, if you can invent a technology that can deposit or envy advanced materials on the surface of an object, the technology will have great advantages. It will show many new choices in a wide range of areas of interest, creating many new possibilities to expand the variety of materials that can be covered, thereby greatly increasing new applications for thin film deposition. Current methods for depositing advanced materials include physical ion vapor deposition and plasma enhanced chemical vapor deposition. In practice, these processes have to be carried out in a vacuum chamber 15 and therefore have significant limitations. First, implementing these processes requires advanced vacuum equipment. Secondly, many vapor deposition technicians have poor directivity and poor orientation, and cannot be simply applied to objects with complex shapes and large spatial configuration changes. The number and size of objects are also limited by the size of the vacuum chamber. Moreover, the production cycle is long. In addition, some processes are accompanied by high-temperature processes, which are not suitable for plating of precision 20 or temperature-sensitive materials. The present invention focuses on overcoming these disadvantages. [Akimoto 3 Summary of the Invention One aspect of the present invention is to provide a new method for depositing material 1240767 on the surface of an object, including: mentioning seven &men; an electrolytic cell having an electrolyte and a separation counter electrode, the separation counter electrode is caused by An electrode constitutes this object; in the vicinity of the electrolyte that constitutes this object, a series of 5 bubble clusters with the source of the material to be plated is generated by the electrolyte (object). A potential difference is added between the electrodes, and the potential difference is so large It is sufficient to form a glow discharge in the bubble group region, and the substance is an ion stored on the object. The high-energy ions generated in the ionizing protons are deposited by interaction with the solid surface 10 to be bonded. The ionized molecular gas in the delta-hai plasma is in an activated or high-energy state, and thus can be deposited on the surface of the electrode across the interface energy barrier. Plasma substantially strengthens the deposition process. The formation of a glow discharge region near the electrode is caused by dielectric breakdown of 15 groups of bubble groups around the electrode. The bubbles are dielectric and the conductivity is low. As a result, a high potential drop is formed in the unity cluster of bubble groups near the electrode, causing the most linear bubbles to pierce. Into the electrolyte The plasma is generated in the bubbles contained in the electrolyte. The function of the electrolytic solution is equivalent to the container of ionized bubbles. The bubbles contained in the electrolyte are produced in two: material precursors. The antecedent can be transferred from the liquid phase cap to the gas phase through diffusion and evaporation. It can also be directly transferred by wire or air-mixing method or the surface can be pre-plated. The object to be plated can be any kind of conductive material. Granules of conductive material. 20 1240767 Recommended conductive materials include steel, aluminum and aluminum alloys, titanium and titanium alloys, etc., as well as semi-metals and semiconductor materials such as silicon, including conductive organic materials such as ABS plastic. Examples of non-conductive materials coated with a conductive coating include glass coated with indium-tin oxide (ITO), ceramic coated with organic conductive coating or 5 silver mirror treated ceramics, plastics, glass, etc. Typical application materials include steel ’silicon, ITO glass, titanium alloy and aluminum alloy. The above-mentioned bubble generation method may be one or more of the following methods, namely, electrolytic method, boiling method, cavitation method, gas-liquid mixing method, aeration method, chemical reaction method, electron or ion collision decomposition method. Electrolysis is the application of a potential difference between the electrodes to cause precipitation of bubbles on the electrodes. For example, the electrolysis of hydrogen bubbles on the cathode and the electrolysis of oxygen bubbles on the anode. The boiling method is to heat the electrolyte to a partial or full boiling state in the electrode area to form bubbles and vapors. This can be heated by directly energizing the electrode 15 or by heating the moving or stationary grid in the electrolyte, or outside the tank. The method such as the electrolyte in the tank is realized. Infrared, microwave, or laser heating can also be used to generate boiling bubbles. Cavitation bubbles can be generated by ultrasonic generators, or by forcing liquid phase fluids or gas-filled multiphase flows into the vicinity of the electrodes. Cavitation bubbles can also be generated in the electrolyte flowing near the electrode according to the principle of hydrodynamics. Injecting bubbles directly next to the electrode can also be used to generate bubbles. Air bubbles can also be generated by chemical reactions in the electrolyte to produce gaseous products. Typical reactions of this type involve thermal decomposition in the electrolyte, or acid-base 1240767 reactions. The method of adding a foaming agent to the electrolyte can also be used to generate the desired bubbles. The bubble characteristic in the present invention is that a bubble shell is formed in an adjacent area around the electrode. The bubble shell is between a few nanometers and 50 millimeters thick. Typical gas bubble thickness is 1 to 5 mm. It is not difficult to understand that the bubble shell may be non-uniform as a whole. Air bubbles can be generated from the components of the electrolytic solution, or by introducing gas or vapor or a gas-liquid mixture outside the electrolytic cell. The step of forming a glow discharge in the bubble region can be achieved by increasing the potential difference between the electrodes by more than a certain valence. To generalize, the formation steps of the glow discharge can also be assisted by other means, such as a magnetic field, a hot wire that can emit thermionic electrons, stray radiation, microwaves, or RF induction and ultrasonic waves. The gaseous substances contained in the bubbles can come directly from the electrolyte or be generated in the electrolyte. Glow discharge ionizes the gas inside the bubbles to form a plasma. One of the important features of the present invention is that the electrolyte functions to contain plasma. This process is generally carried out at ambient atmospheric pressure, although the pressure inside the bubble can be different from the ambient atmospheric pressure. Specifically, the process is not required to be performed under vacuum. However, it can also be carried out under pressure conditions 20 below atmospheric pressure. The electrolyte includes: a liquid as a carrier; and a source or precursor for supplying a material deposited on an electrode. The electrolyte may include the following additives: 1240767 to improve the conductivity of the electrolyte = speed: surfactant additives with low electrolyte surface tension, catalyst additives to improve = 'bubble promoters, buffers, and σ lean Rhenium and coating quality additives. Additives for electrolyte conductivity include organic and inorganic salts such as potassium gasification, magnesium chloride, sodium acetate, and the like. The ore-tolerant material can enter the bubbles through diffusion and evaporation from the electrolyte, and then form ionization in the bubbles due to glow discharge. 10 The present invention can deposit materials that can be covered by ordinary electric ore, including metals such as copper, copper, copper, iron, inscriptions, copper, tin, copper, silver, gold, indium, and boats, and alloys , And semiconductor materials such as gallium. The significant function of this method or process is to deposit many advanced materials that cannot be plated by traditional electric mining processes, such as carbon, boron, silicon and other semi-metals and their compounds such as carbon nitride and boron carbide. In addition, metals that cannot be plated or difficult to be plated by conventional electroplating include titanium, aluminum, tungsten, manganese, molybdenum, niobium, and the like. These metals have negative electrode potentials in aqueous solutions. These methods can be used to plate out these metals and alloys or compounds. Binary compound semiconductors such as scales, bowls, marriages, sulfide blessings, magnetization series, Minghua series, 2M trisulfide, copper sulfide, code word, 20 indium halide, selenium molybdenum or tungsten Compounds, silicon oxides, copper or titanium oxides, etc., as well as ternary compound semiconductors, polymers, biological promoters (women's names are Ir203 'Rb203, Ru〇2, etc.), and biomaterials such as tribasic acid 4¾ Etc., can also be deposited by the plasma plating process of the present invention. The method or process can also be chromium-plated without using hexavalent chromium as the main salt. The traditional! 240767 electroplating chromium process is inseparable from hexavalent chromium. This compound is highly toxic, harmful to health and pollutes the environment. This patent is particularly suitable for the application of a certain electrode made of an object to be plated, and the material to be plated is an advanced material, such as carbon, silicon, titanium, and the like. However, in other applications, an electrode formed by the object to be plated may also be an anode, and the dual electrode is used as a cathode to perform deposition, oxidation treatment, plasma electrophoresis, or plasma anodization. Through #, the dual electrode can be inert or soluble. The combinable dual electrode can provide a source of material for deposition on another electrode. The typical material of the dual electrode is a metal material, such as Shao and Shao alloy, stainless steel, or graphite. The shape of the cathode is not limited, and may be an elongated shape, such as a shaft. The corresponding anode can consist of multiple plate-like bodies, with a ring around the cathode. The cathode can also be a flat piece with two surfaces to be plated, and the corresponding anode 15 can be composed of two plates placed at a distance, each corresponding to a surface of the cathode to be bonded at a certain distance. Bubbles can also be generated by supplying gas from the outside of the electrolytic cell, so that the gas can contain materials to be bonded or precursors. Money-rich materials or precursors are also ionized in the plasma and subsequently deposited on the surface of the object. 20 The shape of the slot is not strictly limited. Usually, a rectangular-shaped container 'with a bottom and a wall can be inserted from an opening provided at the top of the tank and immersed in an electrolytic solution. There is no strict limit on the size of the electrolytic cell. Alternatively, the electrodes can be arranged parallel or perpendicular to the bottom of the tank. Advancements in this industry include cooling the electrolyte to dissipate excess heat from the 1240767 plasma reaction. It may also include measures to regulate and maintain the electrolyte 'to keep one or more components of the electrolyte and the liquid surface stable. The cold section method involves withdrawing the electrolyte from the electrolytic cell, passing it through a cooler, and returning it to the electrolytic cell. In the traditional electric mining process, air bubbles are regarded as a hindrance to material deposition < obstacles " so when working in an electrolytic cell, it is often necessary to try to avoid the generation of air bubbles " The generation of gas / packets and the use of bubbles in the vicinity of an electrode is a basic feature of the present invention. The bubble shell around an electrode is the key to establishing a plasma region, and the establishment of a plasma region 'results in plasma deposition on the surface of an object. In addition, traditional electroplating is limited to using an aqueous solution as the electrolyte. The invention is not so limited. As such, the electrolytic solution used in the present invention has a wider range of options. It may also include an organic solvent system, an organometallic compound system 5 and a metal-organic compound system. Secondly, the process of the present invention does not require dissolving metal ions in an aqueous solution to provide the species to be plated. All that is required is that the source or precursor of the material to be plated is contained in a bubble near the electrode. Another component of the present invention is a device for providing material deposition on the surface of an object in a systematic manner, including: an electrolytic device, including an electrolytic cell, and a separate counter electrode, that is, an anode and a cathode immersed in an electrolyte, and to be plated The object is one of the counter electrodes; the liquid electrolyte contained in the electrolytic cell: a facility for generating bubble clusters near the cathode; and the electrolyte may contain one or more components, or it may have Other features described in p-knife. The means for generating the bubble group may include electrode precipitation caused by electrolysis, and may also include an ultrasonic generator that transmits ultrasonic waves into the electrolyte. A facility for applying a potential difference between the counter electrodes may include a power source with a voltage of 3,000 volts. Typical output voltages should be between 250 and 1500 volts. Power output can be DC, or pulsating, such as high-frequency pulsed power, or unbalanced. The plasma electroplating apparatus may further include dividing the electrolytic cell into two spaces of a sedimentary and a loop. 10. The device may include facilities for extracting the electrolyte from the loop space, cooling the electrolyte, and returning the electrolyte to the electrolytic cell. The electrolytic solution may further include facilities for maintaining a stable level of the electrolytic solution level when necessary, and facilities for regulating and maintaining the components of the electrolytic solution. In a nutshell, the process described provides a new technology for depositing advanced materials and 15 simple and convenient plating systems that are improved over traditional electroplating techniques. The core of this process is the introduction of a non-equilibrium state process near an electrode, so that the precursor material contained in the gas > cladding can obtain sufficient energy and speed to achieve effective deposition. This process involves the application of an electric field that is strong enough to generate a glow discharge within the bubble to form a plasma. The high-energy ions produced by ionization are deposited for 20 minutes, and are combined with the electrode surface at a localized high temperature to form a film. The source or material to be plated is ionized in a bubble surrounded by a liquid. This liquid effectively holds all the reactions that occur. It is easy to generate a glow discharge and form a plasma in this electrolytic device. Because of the existence of the bubble shell, the voltage drop in the electrolytic cell reaches a very high value in the bubble shell layer along the front of the cathode. The voltage drop is concentrated in this thin layer, while the nonlinear distribution is in the two electrode space. This provides a driving force for generating glow discharge and ion deposition. There are five ways to clarify the method of depositing advanced materials on an object and the device for implementing it. For convenience, the following examples will be described in detail with typical examples and accompanying drawings to embody the present invention. The purpose of this elaboration is to make it clear for those interested in the present invention how to put the present invention into practical use. It goes without saying that the specific characteristics of this description method do not hide the general characteristics revealed in the previous section. 10 Brief description of the drawings Figure 1 shows the principle of the corresponding plasma plating process of the present invention; Figure 2 shows the layout of the electrolytic device and auxiliary devices implementing the present invention, and Figure 3 shows the second figure Figure 4 shows the ultrasonic generator and 15 cavitation bubbles. Figure 4 shows the voltage-current characteristic curve of the electrolytic cell. Figure 5 shows the voltage generated by the electrode surrounding the cathode. Bubble shell; Figure 6 shows a bubble shell around the cathode when forming a stable glow discharge in an electrolytic cell; Figure 7 shows a top view of an example of a cathode and anode arrangement in an electrolytic cell; Figure 8 shows electrolysis Top view of another example of the arrangement of cathode and anode in the tank; Figure 9 shows the different areas of the sample along the length of the sample after the carbon plating of the corresponding cathode in the direction of 14 1240767; Figure 10 shows the filament cathode before ore The topography of the SEM surface in Fig. 1 is not shown in Fig. 1 is the surface morphology of the scanning electron microscope in the area of cathode A in Fig. 9; Fig. 12 shows the surface shape of the SEM in the area of cathode B and C in Fig. 5 Appearance; Figure 13 shows the 9th Surface morphology of a high-power scanning electron microscope in the BAC region of the middle cathode; Fig. 4 shows the surface morphology of a swept-inserted electron microscope on a plate-shaped cathode that roughly corresponds to the region of Fig. 9A; 10 Fig. 15 shows a plate-shaped cathode The SEM surface morphology of the area roughly corresponding to the area in FIG. 9B; FIG. 16 shows the SEM surface morphology of the plate cathode on the area roughly corresponding to the area in FIG. 9C; and FIG. 17 shows FIG. 9 15 results of surface energy spectrum analysis after middle cathode carbon plating; Fig. 18 shows a laser Raman spectrum of a carbon coating layer; Fig. 19 shows a scanning electron microscope surface morphology of a filamentary cathode after titanium plating; The figure shows the surface morphology of the high-powered SEM of the titanium coating in Figure 19; 20 Figure 21 shows the results of the energy spectrum analysis of the titanium coating in Figure 19; Figure 22 shows the copper grid cathode Composition of the titanium plating layer measured on the spectrometer attached to the transmission electron microscope; Figure 23 shows the scanning electron microscope surface morphology of the filamentous cathode silicon coating; Figure 24 shows the high magnification of the silicon coating in Figure 23 The scanning electron microscope surface shape 15 1240767 is mixed with the liquid and then formed into the electrolytic cell. Fig. 3 shows the expansion of the electrolytic device shown in Fig. 2. The ultrasonic generator is arranged around the electrolytic cell. The ultrasonic wave generated by the generator is propagated through the electrolytic solution to generate a bubble group surrounding the cathode. 5 Figure 4 shows a typical voltage-current characteristic curve obtained when the voltage is gradually increased in this electrolytic device. The beginning of the curve is the ohmic region where the current increases proportionally with the voltage. What followed was an oscillating area, and the current began to oscillate. The applicant believes that the 'current oscillation is caused by the precipitation of electrode bubbles and the formation of an electrode localized shielding effect. When a plasma is formed in a bubble, a glow is generated inside the bubble, and the bubble bursts. Countless glow discharge bubble groups can form the plasma shell of the electrode. The apparent current density decreases significantly at the end of the oscillating area, because a large number of bubbles have been formed at this time, and the electrode shielding effect has increased. The cathode precipitation bubbles are mainly electrolytic hydrogen bubbles, but there are 15 electrolyte heating bows on the cathode surface Evaporating bubbles. Other methods described above can also generate air bubbles, such as cavitation air bubbles caused by ultrasound. ^ Over a certain time 'When the number and density of bubbles increase enough to cover the entire cathode surface and reach a critical voltage, glow discharge begins. For a given system, the S-boundary voltage is a certain value, called the ignition point. The experimental observation of the surface of the glow discharge discharge on the surface of the cathode was generated when the cathode surface was surrounded by a layer of quasi-continuous bubble shells. Under the condition of a cathode, corresponding to the ignition point, a small fireball or a fireball cluster first appeared at the end of the filament-shaped electrode invading the electrolyte. Increasing the voltage further will cause the glow discharge to gradually spread across the entire cathode intrusion surface. Glow 17 1240767 Discharge is a dynamic process, and the glow discharge clusters and flashes can be clearly seen through the bubble shell. The generation of glow discharge is caused by the dielectric breakdown of the bubble under the electric field strength of the south electric field. Due to the existence of bubble shells on the surface of the cathode, the distance between the anode and the cathode is within 5 meters, and most of the electrical drop will fall in the bubble shell layer in the vicinity of the cathode. The electric field strength here can reach lxlO4 to lx105V / m. The working voltage can be set to a value between 50 and 100 volts above the ignition point. It is typically between about 25 and 15 volts, corresponding to the lower plateau part of the characteristic curve shown in Figure 4, which is the glow discharge area. 3, from the discharge of light, bubbles bubble into a plasma. Figure 5 is the cathode table: formation = schematic representation of the bubble shell; 6_ is the formation of a stable glow on the cathode surface = unintentional. As shown in _Indication ', it is indicated when a stable Huinuo electricity is observed. The two areas are adjacent to each other. The characteristics of the whole process are as follows: 15: Coated conductive material ’can be a conductor’ semiconductor, or lock, soft steel, second steel: Γ experimentally verified feasible cathode material sieve-shaped, rod 1 ^. ==, extremely miscellaneous can be made from flat plate, net. There are no strict restrictions on the shape and size of the anode. The anode can be made of any graphite. ~ The applicant of this patent has successfully used alloys as anode materials. Although 2 sub-electric mines. —Generally, Shao and Shao are recommended. This process has shadowing. R, ,, and deposition are performed on the surface of the cathode, but the anode pairing causes the electro-electric conversion to produce impurities in the transition. The purity is large, which blocks or even interrupts the deposition process. Similar to 18 1240767 _, there are no strict restrictions on the number, shape and size of anodes. Sometimes the anode can be constructed directly from a conductive electrolytic cell. Figures 7 and 8 show two modes of electrode configuration. Yes, these two modes are just examples. Actually, there are various electrode configurations. 5 modes are available. In Fig. 7, the four flat anodes are all distributed around the center, and the center is a rod-shaped cathode. The anode is radioactively distributed at a certain distance. This mode can meet the uniform deposition of the outer surface of the rod-shaped cathode. The distance between the cathode and the anode is generally greater than 10 mm to prevent the anode process from interfering with the formation of a bubble shell on the cathode. Typical pole pitch is 10 to 40 mm. 10 In Figure 8, a flat cathode has two surfaces to be plated, so approximately two parallel anodes can be used at a fixed distance apart, each corresponding to one surface of the cathode to be placed at equal distances. If only one anode is used, deposition can only occur effectively on one surface of the cathode due to the current distribution characteristics. The electrolytic cell is filled with a suitable electrolyte. The electrolytic solution contains a solvent or a carrier 15 to form a disproportionate environment, promote the electrolytic process, and support the generation of plasma, that is, it is a space for generating plasma. The electrolyte may also contain a source of material to be recorded called a precursor. The electrolyte may also contain various additives, such as a conductive agent that improves the conductivity of the electrolyte, a foaming agent that assists in the formation of bubbles, and a buffer that maintains the pH of the solution in an appropriate range. 20 Practically, the object to be plated is placed in an electrolytic cell and immersed in the electrolyte, which is usually used as a cathode. But sometimes it can also be used as anode. Book Apply a potential difference between the electrodes, and the voltage value needs to reach the level above the ignition point. At this level, the system or the electrolytic cell can reach a stable glow enemy electricity, and the discharge group covers the surface of the cathode to be plated. , 19 1240767 The adjacent area 1 of the cathode surface is mainly composed of glow discharge clusters. The plasma forms a shell here and directly surrounds the cathode surface. Plasma deposition takes place in this area. The plasma interacts with the solid surface of the cathode to produce a deposition, which is similar to the process of ion plating. After nucleation and growth, a thin film is gradually formed on the surface of the cathode. Zone 2 is the plasma-chemical reaction zone, which is the interface between the electrolyte and the glow discharge zone. This area surrounds the plasma deposition area, which is usually cream-colored and can be distinguished from the plasma deposition area and the electrolyte body by the naked eye. Zone 2 or outer zone. The electrolyte components including the precursors are decomposed in this zone, and some ionization may occur. This provides the desired species or ionization precursor to be deposited on the cathode surface. These varieties are used for migration, diffusion, and convection by electricity, and are transported from area 2 to area 丨 the inner area. As long as these conditions are maintained and the antecedent material is present in the electrolyte, deposition can occur. 15 § After the glow discharge starts, the temperature of the electrolyte can rise a lot in a short time. The electrolyte temperature must be maintained in a suitable range. To this end, the electrolytic solution can be pumped out of the tank and pumped to the cooling system, as shown in FIG. 2. The cooled test can be returned to the tank. The reasons for the electrolyte cooling are 2,-to maintain the stability of the system, and to ensure safety. This is especially necessary when the electrolytic solution contains flammable components. In addition, the electrolytic solution is consumed in the sedimentation reaction, and the electrolytic solution needs to be supplemented in a timely manner to keep the liquid level stable. An additional storage tank containing the electrolyte can be used for this purpose. The declarants conducted experiments to verify the effectiveness of this technology in depositing three materials, namely carbon and Shi Xi. The experimental details are described below. 20 1240767 Carbon In the electrolytic device shown in Figure 2, the object to be plated is used as the cathode, and a carbon film deposition experiment is performed. Electrolyte composition material material volume content (%) main part "ethanol (analytical grade) 50-100 solvent deionized water 0-50 additive κα, KAc, or MgCl trace group powder pH7 standard buffer solution Wi is establishing stable glow discharge After 30 minutes of experimental deposition, the working voltage was -450 volts. The results were confirmed by scanning electron microscope and other analysis. Carbon film deposition 10 on several wire-like and flat-plate surfaces, and nickel mesh screens used as transmission electron microscopes. Figure 9 shows a schematic representation of the different areas of the carbon film deposited by the cathode. Figures 10 to 15 are scanning electron microscopy morphologies of the corresponding thin and flat cathodes. SEM morphology clearly shows the growth of carbon film on the cathode substrate. The 15-spectrum component analysis results reveal that the main component of the film is carbon, and there are trace impurities such as potassium, oxygen, and gas. The applicant believes that potassium and chlorine are derived from potassium vaporized additives used in the electrolyte, while oxygen is mainly derived from the sample's long-term exposure to air. The film was subjected to laser Raman spectroscopy to determine the film structure. 20 The results are shown in Figure 18. Fig. 8 shows that the Raman peak appears at wave numbers 1300-1400, and 21 1240767 1550-160 (^ 111-1 'corresponds to amorphous carbon, and this conclusion is further confirmed by the results of transmission electron microscope analysis. Summary: cathode surface A carbon film is indeed deposited. The carbon film is a pseudo-amorphous carbon with diamond-like carbon bonding properties. The film itself is dense, smooth and flat. Five titanium films have also been applied to several cathodes on the electrolytic device shown in Figure 2 Or deposition test of coating. The composition of the electrolyte used in the experiment is as follows. Component material volume (%) Ti (〇pr) 4 50 solvent ethanol 50 Ti (〇Pr) 4 is used as the main component. The source of titanium material is ionized in the bubble shell surrounding the cathode surface due to plasma, and then deposited on the cathode surface. The reaction process may be as follows: 15 Ti (OPr) 4 (l) -Ti (OPr) 4 (g)
Ti(OPr)4(g)—Ti+40Pr· 2H20( 1 )+2e_— H2(g)+2(OH)_ 申請人認為離化先行物與等離子體中可包含一種或多 種下列物質：鈦離子，氫離子（質子），氧離子（負離子），和 2〇 碳氫活性分子CH4+，C2H2+，C+等。 實驗是在電解裝置中建立穩定輝光放電後，工作電壓 -800伏，電流250毫安培下沈積30分鐘。 22 1240767 沈積貫驗結束後，陰極表面在掃描電鏡下做形貌觀察 ，如第19，20圖所示。結果清楚地表明絲狀陰極表面生長 了塗層。該塗層較厚，最厚處厚度約達1〇微米。申請人估 计塗層沈積速率可咼達每分鐘0.33微米。形貌觀察可發現 5塗層存在裂紋，係過高的沈積速率和氫夾雜所致。 第21圖給出此δ普分析結果。能譜圖顯示的欽強峰表明 塗層成分主要是鈦。雖然採用了鋁陽極，但未見銘在塗層 中的夾雜。 在该體糸還進行了只存在氣泡條件下的電解沈積實驗 10 。工作電壓設定在起火點之下，從而不存在輝光放電過程 。沒有證據表明經如此處理的電極表面有薄膜生長，這充 分指明等離子電鍍在I-V特性曲線的輝光放電區操作的重 要作用。 在第2圖所示的電解裝置上還進行了陰極鑛矽實驗。 15 所用電解液組成如下。 —組分 材料 ^* —主份 Si(Oac)4 〇.2-T2M〇[~~ _溶劑 乙醇 餘量 實驗採用醋酸矽作沈積矽材的來源。醋酸矽呈白色於 狀，在乙醇中可溶。 在等離子體與離化先行物中可包含下列物質中的_種 或多種：矽離子，氫離子和氧離子。還可能包含碳氫活性 分子和碳離子。 23 1240767 在體系建立穩定輝 碑先放電後，於-500伏工作電壓和 160-200¾安培的工作 兒成下沈積30分鐘。 在陰極表面塗層上作 ^ 乍知描電鏡形貌分析，結果如第23 係存在矽的極強 :24圖所示。第25圖给出能譜分析結果，係 厚度達〇·5毫米的塗層， 帶裂紋，表明存在高的 陰極上生長了一層土褐色的， 肉眼即可咖。塗層“狀結構， 内應力。 ，述例子中闡述的方法，已清楚地表明在電解裝置上 用等離子電鑛可成功地在作為電極的工件或物體表面上沈 積先進材料，如碳，銖，石夕。該工藝可在相對簡單的電解 #和大I壓環境下進行，無須真空設備。電解液本身提供 7/¾相等離子的谷納，從而使得等離子過程既有效又簡單 。等離子提供能量來促進沈積。 15 此外’石夕和欽的沈積速率高，在很短時間内即可獲得 厚塗層°該意義明顯，充分地展示了本技術所含的巨大潛 力。 中清人還提及’電解液可同時包含多種先行物或主份 產生多種離化物質，從而回沈積合金類或化合物類塗層 20 〇 本技術的一個突出優點是可對任意形狀，包括複雜形 狀的物’沿3維空間的所有表面進行均勻鑛覆。可方便地 鍍覆卞板狀物體的任一表面或同時鍍覆兩個表面。 本工勢方法的另—個顯著性是可鍍覆物體的尺寸範圍 24 1240767 寬。製造大尺寸電解槽來容納大尺寸物體技術上顯然不是 一件困難的事。這在需要真空室來實施鍍覆時並非易事。 應當說明的是，本技術還可用於從液相中回收材料， 尤其是微量元素。通過本工藝實施沈積，可當作回收材料 5 的一種方法。這個過程類似用電解裝置從溶液中萃取銅離 子。 應當指出，上述只是通過若干應用實例的說明來闡述 本發明◦本發明涉及在上述基礎上明顯持有改進與變異的 一個寬廣範圍。 10 闡述了在物體表面沈積先進材料的一種新方法。該方 法是將待鍍物體放置於具分離對電極和電解液的電解槽内 ，電極之一即為該物體，而電解液含待鍍材料的來源。在 陰極鄰近的電解液中形成氣泡族團，其方法包括電解，沸 騰，氣穴，混氣，和通氣。在陰極與陽極之間施加一電位 15 差，使得氣泡域產生輝光放電，導致氣泡内形成離化分子 氣的等離子體。因該充斥著能量的氣態等離子體的作用， 薄膜在物體表面生長。本方法可在大氣環境中進行，無須 真空設備。電解液在此是作為等離子的包容體。因高電位 差在氣泡族團構成的殼層地帶形成大的電壓降，促使該區 20 域内產生輝光放電，導致待鍍分子的啟動與離化。還闡述 了實施本方法的裝置。 【B3式簡單說明】 圖所示為本發明相應的等離子電鍍工藝原理示意； U圖所示為實施本發明的電解裝置及輔助裝置的佈 25 1240767 局示ί、： 务3圖所示為第2圖中的電解槽附加超聲波發生器以及 氣穴氣泡的不意， 第4圖所示為電解槽中的電壓-電流特性曲線； 5 | 5圖所示為在電極之間施加電壓時，環繞陰極所產生 的氣W殼； $ 6圖所示為電解槽中形成穩定輝光放電時的環繞陰 極的I泡殼； 备，7圖所示為電解槽中陰極與陽極設置一例的俯視圖； 10 I 8圖所示為電解槽中陰極與陽極設置另一例的俯視 圖； 务9圖所示為本發明相應的陰極鍍碳後，沿樣品長度方 向呈圮的不同區域； M0圖所示為絲狀陰極未鍍前的掃描電鏡表面形貌； 15 第Π圖所示為第9圖中陰極A區的掃描電鏡表面形貌； 負12圖所示為第9圖中陰極B及C區的掃描電鏡表面形 貌； I，13圖所示為第9圖中陰極B及C區的高倍掃描電鏡表 面形I己； 20 I 14圖所示為板狀陰極上與第9A圖區大略對應區域的 掃描1:鏡表面形貌； 負15圖所示為板狀陰極上與第9B圖區大略對應區域的 掃描k鏡表面形貌； I 16圖所示為板狀陰極上與第9C圖區大略對應區域的 26Ti (OPr) 4 (g) —Ti + 40Pr · 2H20 (1) + 2e_— H2 (g) +2 (OH) _ The applicant believes that the ionization precursor and plasma may contain one or more of the following substances: titanium Ions, hydrogen ions (protons), oxygen ions (negative ions), and 20 hydrocarbon active molecules CH4 +, C2H2 +, C +, etc. The experiment is to establish a stable glow discharge in an electrolytic device, and the working voltage is -800 volts and the current is deposited at 250 mA for 30 minutes. 22 1240767 After the completion of the deposition test, the surface of the cathode was observed under a scanning electron microscope, as shown in Figures 19 and 20. The results clearly show that a coating is grown on the surface of the filament cathode. The coating is thick, with a thickness of about 10 microns at its thickest point. Applicants estimate that the coating deposition rate can reach 0.33 microns per minute. Morphological observation revealed that the coating was cracked due to excessive deposition rate and hydrogen inclusion. Figure 21 shows the results of this delta general analysis. The strong peak shown in the energy spectrum shows that the coating composition is mainly titanium. Although an aluminum anode was used, no inclusions were observed in the coating. Electrodeposition experiments in the presence of bubbles only were also performed on the body 10. The operating voltage is set below the ignition point, so there is no glow discharge process. There is no evidence of thin film growth on the electrode surface thus treated, which fully indicates the important role of plasma plating in the glow discharge region of the I-V characteristic curve. A cathodic silica experiment was also performed on the electrolytic device shown in FIG. 2. 15 The composition of the electrolyte used is as follows. —Component Material ^ * —Main component Si (Oac) 4 0.2-T2M〇 [~~ _ Solvent Ethanol Balance The experiment used silicon acetate as the source of the deposited silicon material. Silicon acetate is white and soluble in ethanol. The plasma and ionization precursors may include one or more of the following: silicon ions, hydrogen ions, and oxygen ions. It may also contain hydrocarbon-active molecules and carbon ions. 23 1240767 After the system has established a stable monument, it is deposited for 30 minutes at a working voltage of -500 volts and a work of 160-200 ¾ amps. ^ The morphology analysis of the surface coating of the cathode on the surface of the cathode is shown in Fig. 24. Figure 25 shows the results of the energy spectrum analysis. The thickness of the coating is 0.5 mm with cracks, indicating that a layer of earthy brown is grown on the high cathode, which can be treated with the naked eye. Coating "like structure, internal stress. The method described in the examples has clearly shown that the use of plasma power ore on an electrolytic device can successfully deposit advanced materials such as carbon, baht, etc. on the surface of a workpiece or object as an electrode, Shi Xi. The process can be carried out in a relatively simple electrolytic environment and a large I pressure environment, without the need for vacuum equipment. The electrolyte itself provides 7 / ¾ equal ions of Gona, which makes the plasma process effective and simple. The plasma provides energy to Promote deposition. 15 In addition, 'Shi Xi and Qin have high deposition rates and can obtain thick coatings in a short period of time. ° The significance is obvious and fully demonstrates the huge potential of this technology. Zhongqing people also mentioned' The electrolyte can simultaneously contain multiple precursors or main components to produce multiple ionizing substances, thereby depositing alloy- or compound-based coatings. 20 A prominent advantage of this technology is that it can be used for any shape, including complex shapes All surfaces of the space are uniformly ore-coated. It is convenient to plate any surface of the slab-like object or both surfaces at the same time. It is a wide range of sizes of plateable objects 24 1240767. It is obviously not technically difficult to manufacture a large-sized electrolytic cell to accommodate large-sized objects. This is not easy when a vacuum chamber is required to perform the plating. It should be explained Yes, this technology can also be used to recover materials, especially trace elements, from the liquid phase. Deposition through this process can be used as a method for recovering materials 5. This process is similar to the extraction of copper ions from a solution using an electrolytic device. It should be noted The above only illustrates the present invention through the description of several application examples. The present invention relates to a wide range of improvements and variations that are obviously held on the basis of the above. 10 A new method for depositing advanced materials on the surface of an object is described. The method is to The object to be plated is placed in an electrolytic cell with a separate counter electrode and an electrolyte. One of the electrodes is the object, and the electrolyte contains the source of the material to be plated. A method of forming a bubble group in the electrolyte near the cathode includes Electrolysis, boiling, cavitation, gas mixing, and aeration. Apply a potential difference of 15 between the cathode and anode to make bubbles Glow discharge is generated, resulting in the formation of plasma of ionized molecular gas in the bubble. Because of the gaseous plasma filled with energy, the film grows on the surface of the object. This method can be performed in the atmospheric environment without the need for vacuum equipment. This is the inclusion body of the plasma. Due to the high potential difference, a large voltage drop is formed in the shell zone formed by the bubble group, which causes a glow discharge in the 20 area of the region, which causes the activation and ionization of the molecules to be plated. The implementation of the present invention is also explained. Method device [B3 simple description] The figure shows the principle of the corresponding plasma electroplating process of the invention; Figure U shows the cloth 25 1240767 showing the implementation of the electrolytic device and auxiliary device of the invention. Figure 2 shows the accident of adding an ultrasonic generator and cavitation bubbles in the electrolytic cell in Figure 2. Figure 4 shows the voltage-current characteristic curve in the electrolytic cell; Figure 5 | 5 shows the application of voltage between the electrodes At the time, the gas W shell generated around the cathode is shown; Figure 6 shows the I bubble shell around the cathode when a stable glow discharge is formed in the electrolytic cell; Top view of an example of the arrangement of cathode and anode in the tank; Figure 10 I 8 shows a plan view of another example of the arrangement of the cathode and anode in the electrolytic tank; Figure 9 shows the corresponding cathode of the present invention after carbon plating, showing 圮 along the length of the sample The morphology of the SEM surface before uncoated filamentous cathodes are shown in Figure M0. Figure 15 shows the SEM surface features of the cathode A area in Figure 9; Figure 12 shows the first SEM surface morphology of cathodes B and C in Figure 9; Figures I and 13 show the surface shape of the high-power SEM on cathodes B and C in Figure 9; Figure 20 I 14 shows a plate-shaped cathode The top scan of the area roughly corresponding to the area of Figure 9A 1: mirror surface morphology; negative 15 shows the surface morphology of the scanning k mirror on the plate-shaped cathode and the area roughly corresponding to the area of Figure 9B; I 16 shows 26 on the plate-shaped cathode, which corresponds roughly to the area in FIG. 9C