200928004 九、發明說明： 【發明所屬之技術領域】 本發明係關於一種工業用c型夾之銘陽極處理方法，特 別指將工業用c型夾以直流與交流重疊使用之硬性陽極處 理，並控制酸性電解質的溫度，進而增加陽極塗層的緻密 性者。 【先前技術】 按’紹陽極處理 作為在銘及其合金所製成的 Ο 形成保護膜的一種過程，而實質上，在鋁之工件上所形成 的氧化鋁薄膜是利用直流電在適當的電壓下經由適合的酸 性電解質，其中以鋁為陽極，並以另一種適當的材料作為 陰極。最後，將鍍件經由封孔（sealing)處理使氧化鋁薄膜 表面形成一種更具化學穩定性的水化物（hydrate)，它將更 此抵抗大氣及化學溶液的侵蝕，如中華民國專利發明公開 號第200600614號厂形成具抗熱致裂縫腐钱之陽極氧化紹 Ο膜的方法」’係揭示—種於銘合金表面形成陽極氧化紹膜 之方法，該陽極氧化紹膜具備抗熱致裂縫腐钱之特性，乃 使用直流脈衝加上直流電作為陽極處理電源，所形成 極處理膜於高溫下不會形成直達基材表面的開口型裂 提隸合金基材於高溫下具高抗純質，然，習知的 湄=處理方法，施加直流電或脈衝電流作為陽極處理電 對於陽蹄層的生絲率並無法難，於卫業生 電解液溫度上升較快，溫度越高二件與 '、水孔化越厲害，膜的形成速度越快，但其粗糙 200928004 •度也隨之增加’對於需硬質陽極處理之件較為不利，因 此少用於C型夾等銘合金工件上。 & 5幾年來’半導體產業在台灣蓬勃發展，伴隨而來的 =真工δ又備上的需求，因此許多真空零件應運而生，但許 夕真二零件因製造成本的關係，已由國外製造轉而在台灣 進行生產如做為真空聯結用途的型夾，在一般半導體 廠做為氣體管路連接用之C型夾（clamp)，以一般之鋁合金 ❹或不銹鋼所製成，後者因價格高較少為半導體場所使用， 而别者部潛藏著一些缺點，如：在化學腐蝕性氣體與大氣 的侵蝕下，往往使用數個月或一年，鋁合金製成的c型夾 表面即產生鋁鏽或鋁斑，如此將會對於半導體製造之無塵 環境有所影響，當進行更換動作時，又會造成地球資源與 成本支出上不必要的浪費。 【發明内容】 爰此，本發明係提供一種工業用c型夾之鋁陽極處理方 ◎法，係將工業用C型夾以直流與交流重疊使用之硬性陽極處 理，使用較高之電流密度，來改變工業用C型夾氧化膜的生 長速率；並控制酸性電解質的溫度，進而增加陽極塗層的 緻密性。 本發明係一種工業用C型夾之鋁陽極處理方法，包括： A.建立·一可控溫之酸性電解環境：將酸性電解質溶於 水中解離而形成一酸性電解環境，並控制其溫度； 6 200928004 Β·配置陽極工件與陰極材料：在前述之可控溫之酸性 電解環境中，以鋁合金C型夾之作為陽極，並以一導電材料 為陰極； C.施加一電壓：在陽極及陰極間施加一直流交流交替 之電壓，藉其生成之電流使電解液與陽極之〇型夾反應，而 在c型夾之表面生成氧化膜； D·封孔處理.將生成有氧化膜之c型夾自可控溫之酸 性電解環境取出後另進行封孔處理，而於c型夾產生一陽 極塗層。 上述之步驟Α之酸性電解質係選自硫酸、草酸、鉻酸、 硝酸、碟酸及續基有機酸其中任一種或其組合。 上述之步驟A係以一冷凍循環機控制溫度。 上述之步驟B，該C型夾配置前須先清潔。 本發明具有下列之優點： 1. 本發明將鋁合金之c型夾經由陽極處理於表面生成 〇緻密的氧化膜，經由封孔處理後，將形成更具抗蝕能力之 陽極塗層，應用於半導體產業時，更可抵抗化學腐蝕性氣 體與大氣的侵蝕，降低c型夾更換機率及使用成本。 2. 本發明係以直流與交流重疊使用之硬性陽極處理c 型夾，使用較高之電流密度，來改變陽極塗層的生長速率 且可因應不同的情形調整C型夾氧化膜之厚度。 3. 本發明並由一冷凍循環機控制酸性電解質的溫度， 進而增加陽極塗層的緻密性。 7 200928004 ·- 4.本發明之方法可廣泛應用於半導體產業所需零件， 如·乾式蝕刻之晶圓承載盤、反應室内襯及電漿誘發化學 氣相沈積（PECVD)之加熱板…等，並可依據不同鋁合金工件 進行適當的鋁陽極處理。 【實施方式】 本發明之實施例，請參考第一圖之方法流程圖，係提 供一種工業用C型夾之鋁陽極處理方法，包括： ❹ A·建立一可控溫之酸性電解環境··將酸性電解質溶於 水中解離而形成一酸性電解環境，並控制其溫度，該酸性 電解質係選自硫酸、草酸、鉻酸、頌酸、填酸及確基有機 酸其中任一種或其組合，係以一冷凍循環機控制酸性電解 質的溫度，本實施例係以之硫酸作為酸性電解質。 B·配置陽極工件與陰極材料：在前述之可控溫之酸性 電解環境中，以紹合金c型夾之作為陽極，並以一導電材 料為陰極，步驟B之c型夾配置前須先清潔，以清除累積 〇在C型夾表面之污染源，如：剩餘含有碳質的積層、以油 質為主要濁滑劑所留下的痕跡及與油脂㈣所留下來_ 體物質分子和熱處理所引起的氧化薄膜等。 C. 施加一電壓：在陽極及陰極間供應一直流交流交替 之電Μ ’藉其生叙錢使電解液與陽極之G熟反應，而 在C型夾之表面生成氧化膜。 D. 封孔處理·將生成有氧化膜之G ^爽自可控溫之酸 性電解環境取出後另進行封孔處理，而於c型爽產生一陽 極塗層》 200928004 當c型夾置於一硫酸為電解質的酸性電解環境中，以c 型夾為陽極，此時適合電流通過的硫酸就開始進行分解， 而在陰極產生氫氣，在陽極產生硫酸根離子被吸引到鋁陽 極上去’在陽極表面上’鋁離子與氧陽離子結合形成氧化 銘遂造成氧化膜’而超額的鋁離子無法與氧離子結合就在 電解質中溶解，硫酸根離子有時亦有作用，在氧化膜上有 12-15%是硫酸鹽，它可以協助正電荷通過氧化膜的活動， ❹一旦達到一定厚度後，酸就會開始分解氧化膜，造成薄膜 成長過程與薄膜分解過程之間達到動態平衡，而在氧化膜 上形成許多小“孔”，這些孔一旦建立就會保存下來，因 為每個小孔皆有一個電區聯結’使得每個小孔傾向於相等 距離’而形成一個氧化牆或細胞。 而此氧化膜充滿著孔隙，而且可能含有大量水份，必 須再經封孔處理。封孔的操作方式係在近沸騰的水中浸潰 k時間，使氧化膜的陽極塗層變成一種更具化學穩定性 〇的水化物外表，實際上是氧化鋁變成一種穩定的氫氧化 銘，在這種變化過程中，塗層會擴大，小孔會被封閉。如 此，形成更具化學侵蝕的抵抗性之陽極塗層。封孔處理， 除了在水中進行之外，也可以在重鉻酸溶液（例如&的重 絡凌鉀）進行，此種封孔處理之後可以大幅度提高抗钱 性。 如第一圖所示，可看出硫酸電解質濃度的影響，在硫 酸浪度為30%時’有最佳的傳導率〇 7，外加之電壓將形 成個特疋的電流密度，在正常情況來說，會隨著電解質 200928004 • 中濃度增加而減少，亦會增加電解質的溫度，同時對於陽 極處理氧化膜外層部分的侵蝕程度將會增加。 如第三圖所示’可知氧化膜厚度對硬度與電解質溫度 的關係’在一定薄膜厚度之下，硫酸電解質的溫度將會嚴 重影響硬性陽極處理所生成之氧化膜的硬度，在同樣厚度 下，電解質溫度0°C時較25。(：時的所生成之氧化膜厚度硬 度更佳，故本發明係以一冷凍循環機控制酸性電解質的溫 0度，可良好地控制電解質的溫度上昇效應，。 如附件所示’可知陽極處理的電壓及電流密度之關 係’在陽極處理中，電壓將會影響陽極氧化物塗層的多孔 性及陽極塗層的硬度，同時，亦會影響陽極處理系統中電 解質的熱量及所需冷卻系統的容量，由附件可知在同樣電 壓下，在-3(TC時較在在-37.5〇c進行陽極處理有較大的電 流密度。 如第四圖所示，可知電流密度對厚度的影響，氧化物 ◎陽極塗層的厚度會隨著電流密度增加而減少，但電流密度 持續增加至陽極塗層焦化前，此使陽極塗層將會趨近一定 之厚度。 【圖式簡單說明】 第一圖係本發明之方法流程圖。 圖係本發明硫酸電解質濃度與傳導率之關係圖。 一圖係本發明氡化膜厚度對硬度與電解質溫度的關係 圖。 第四圖係本發明電流密度對厚度之關係圖。 200928004 - 附件係本發明陽極處理的電壓及電流密度之關係圖。 【主要元件符號說明】 無 ，200928004 IX. Description of the invention: [Technical field of the invention] The present invention relates to an industrial anode c-type sandwich anode treatment method, in particular to the industrial c-type clamp with DC and alternating current hard anode treatment, and control The temperature of the acidic electrolyte, which in turn increases the density of the anode coating. [Prior Art] A process in which a protective film is formed as a film made of yttrium and its alloy, and substantially, the aluminum oxide film formed on the aluminum workpiece is made of direct current at a suitable voltage. Via a suitable acidic electrolyte, with aluminum as the anode and another suitable material as the cathode. Finally, the plated part is treated by sealing to form a more chemically stable hydrate on the surface of the alumina film, which will resist the erosion of the atmosphere and chemical solutions, such as the Republic of China Patent Invention Publication No. No. 200600614, the method of forming an anodized film with anti-thermal cracking and decaying money", reveals a method for forming an anodized film on the surface of the alloy, which has anti-thermal cracking and corrosion The characteristic is that DC pulse and direct current are used as the anode treatment power source, and the formed treatment film does not form an open-type cracked alloy substrate which is directly on the surface of the substrate at a high temperature, and has high anti-purity at high temperature. The 湄=processing method, applying direct current or pulse current as the anode treatment electricity can not be difficult for the raw silk rate of the hoof layer, and the temperature of the electrolyte in Weiyesheng rises faster, the higher the temperature, the more the two pieces are, and the more the water hole is, The faster the film is formed, but its roughness 200928004 • The degree is also increased. 'It is more disadvantageous for parts that require hard anodizing, so it is less used for C-clip. Gold on the workpiece. & 5 years of 'semiconductor industry booming in Taiwan, accompanied by the demand for real work δ, so many vacuum parts came into being, but Xu Xizhen two parts due to manufacturing costs, has been Foreign manufacturing is used in Taiwan for production, such as vacuum clamps. It is used as a C-clamp for gas pipeline connection in general semiconductor factories. It is made of general aluminum alloy or stainless steel. The latter is used for semiconductor sites because of its high price, while others have some disadvantages, such as: c-clip made of aluminum alloy, which is often used for several months or a year under the attack of chemical corrosive gases and the atmosphere. The surface will produce aluminum rust or aluminum spots, which will have an impact on the dust-free environment of semiconductor manufacturing. When the replacement operation is carried out, it will cause unnecessary waste of earth resources and cost. SUMMARY OF THE INVENTION Accordingly, the present invention provides an aluminum anode treatment method for industrial c-clamps, which is a hard anode treatment using an industrial C-type clamp with DC and AC overlap, using a higher current density. To change the growth rate of the industrial C-type sandwich oxide film; and control the temperature of the acidic electrolyte, thereby increasing the density of the anode coating. The invention relates to an aluminum anode treatment method for industrial C-clamps, comprising: A. Establishing a temperature-controlled acidic electrolysis environment: dissolving the acidic electrolyte in water to form an acidic electrolysis environment and controlling the temperature thereof; 200928004 Β·Configure anode workpiece and cathode material: In the above-mentioned temperature-controlled acidic electrolysis environment, the aluminum alloy C-clamp is used as the anode and a conductive material is used as the cathode; C. A voltage is applied: at the anode and cathode The voltage alternating between the alternating current and the alternating current is applied, and the generated current causes the electrolyte to react with the 〇-shaped clip of the anode, and an oxide film is formed on the surface of the c-clip; D·sealing treatment. The c-type with the oxide film is formed. The clip is taken out from the acidic electrolytic environment of the temperature control and then sealed, and an anode coating is formed on the c-clamp. The acidic electrolyte of the above step is selected from any one or a combination of sulfuric acid, oxalic acid, chromic acid, nitric acid, a dish acid, and a hydrazine-based organic acid. Step A above is controlled by a refrigeration cycle machine. In the above step B, the C-clip must be cleaned before being configured. The invention has the following advantages: 1. The invention adopts an anode coating of an aluminum alloy on the surface to form a dense oxide film on the surface, and after sealing treatment, a more anti-corrosive anode coating is formed, which is applied to In the semiconductor industry, it is more resistant to chemical corrosive gases and atmospheric erosion, reducing the probability of c-clip replacement and the cost of use. 2. The present invention uses a hard anodized c-clamp for DC and AC overlap, using a higher current density to change the growth rate of the anode coating and adjusting the thickness of the C-type sandwich oxide film depending on the situation. 3. The present invention controls the temperature of the acidic electrolyte by a refrigeration cycle machine, thereby increasing the density of the anode coating. 7 200928004 ·- 4. The method of the present invention can be widely applied to components required in the semiconductor industry, such as dry-etched wafer carrier, reaction chamber liner, and plasma-induced chemical vapor deposition (PECVD) heating plate, etc. Appropriate aluminum anode treatment can be carried out according to different aluminum alloy workpieces. [Embodiment] Embodiments of the present invention, please refer to the method flow chart of the first figure, which provides an aluminum anode treatment method for industrial C-clamps, including: ❹ A· Establishing a temperature-controllable acidic electrolysis environment·· Dissolving the acidic electrolyte in water to form an acidic electrolytic environment, and controlling the temperature thereof, the acidic electrolyte is selected from any one or a combination of sulfuric acid, oxalic acid, chromic acid, citric acid, acid and organic acid. The temperature of the acidic electrolyte is controlled by a refrigerating cycle machine, and sulfuric acid is used as the acidic electrolyte in this embodiment. B. Configuring the anode workpiece and the cathode material: in the above-mentioned temperature-controlled acidic electrolysis environment, the crucible c-type clamp is used as the anode, and a conductive material is used as the cathode, and the c-clamp of step B must be cleaned before being disposed. In order to remove the accumulated sources of pollution on the surface of the C-clip, such as: the remaining carbonaceous deposits, the traces left by the oil as the main slip agent and the oil molecules (4) left behind by the body material molecules and heat treatment Oxidized film, etc. C. Applying a voltage: a constant current alternating current is supplied between the anode and the cathode. The electrolyte is reacted with the anode of the anode to form an oxide film on the surface of the C-clamp. D. Sealing treatment · The G ^ Shuang formed by the oxide film is taken out from the acidic electrolytic environment of the controllable temperature and then sealed, and the c-type cool produces an anode coating. 200928004 When the c-clip is placed in a In the acidic electrolysis environment where sulfuric acid is the electrolyte, the c-type clamp is used as the anode. At this time, the sulfuric acid suitable for the current to pass through begins to decompose, and the hydrogen gas is generated at the cathode, and the sulfate ion generated at the anode is attracted to the aluminum anode to be 'on the anode surface. On the 'aluminum ion combined with oxygen cations to form an oxide film to cause an oxide film' and excess aluminum ions can not be dissolved in the electrolyte in combination with oxygen ions, sulfate ions sometimes also have a role, 12-15% on the oxide film It is a sulfate which can assist the positive charge to pass through the activity of the oxide film. Once a certain thickness is reached, the acid will begin to decompose the oxide film, causing a dynamic balance between the film growth process and the film decomposition process, and formation on the oxide film. Many small "holes" that are saved once they are created, because each hole has a junction that makes each hole tend to be equally spaced Oxidized to form a wall or cell. The oxide film is filled with pores and may contain a large amount of water, which must be sealed. The operation of the plugging method is to soak the k time in the near boiling water, so that the anode coating of the oxide film becomes a more chemically stable hydrated hydrate appearance, in fact, the alumina becomes a stable hydroxide. During this change, the coating will expand and the small holes will be closed. As such, a more chemically resistant, resistant anode coating is formed. The sealing treatment, in addition to being carried out in water, can also be carried out in a dichromic acid solution (e.g., & As shown in the first figure, the effect of the concentration of sulfuric acid electrolyte can be seen. When the sulfuric acid wave is 30%, the best conductivity is 〇7, and the applied voltage will form a characteristic current density. It is said that it will decrease with the increase of the concentration of electrolyte 200928004. It will also increase the temperature of the electrolyte, and the degree of erosion of the outer portion of the anodized oxide film will increase. As shown in the third figure, 'the relationship between the thickness of the oxide film and the hardness and the electrolyte temperature' is below a certain film thickness. The temperature of the sulfuric acid electrolyte will seriously affect the hardness of the oxide film formed by the hard anode treatment. At the same thickness, The electrolyte temperature is 25 when it is 0 °C. (The thickness of the oxide film formed at the time of the film is better. Therefore, the present invention controls the temperature rise effect of the electrolyte by a refrigeration cycle machine to control the temperature rise of the electrolyte. As shown in the attached article, the anode treatment is known. The relationship between voltage and current density 'In the anode treatment, the voltage will affect the porosity of the anodic oxide coating and the hardness of the anode coating. At the same time, it will also affect the heat of the electrolyte in the anode treatment system and the required cooling system. The capacity, as seen from the attachment, at the same voltage, has a larger current density at -3 (TC than at -37.5 〇c. As shown in the fourth figure, the effect of current density on thickness, oxide ◎The thickness of the anode coating will decrease with the increase of current density, but the current density will continue to increase until the anode coating is coked, which will make the anode coating close to a certain thickness. [Simplified illustration] The first figure The flow chart of the method of the present invention is a graph showing the relationship between the concentration of the sulfuric acid electrolyte and the conductivity of the present invention. The relationship between the thickness of the film of the present invention and the hardness of the electrolyte. Fourth FIG current density based on the relationship between the thickness of the present invention FIG 200928004-- voltage and current density relationship based anodized FIG attachment of the present invention The main element REFERENCE NUMERALS no.
1111