經濟部中央標準局貝工消費合作社印製 ^υ8ΐ87 a? ____Β7 五、發明説明（1 ) 本案清求1998年3月6日提出申請之美國臨時申請案第 60/077,062號之權益。 本發明係關於陽極電火花鍍敷（ASC)方法，可用於此 種方法之電解質浴，及利用此種方法產生之鍍層a特別本 發明係關於陽極電火花鍍敷方法其利用含低濃度磷酸鹽之 電解質浴生產薄且光滑及主要為氧化物鍍層於金屬基材特 別鋁及鋁合金製成的基材上之鍍層。 ASC方法為業界已知》—般而言多種此等方法曾經用 於金屬基材改善表面特徵例如外觀（如著色）、耐久性（如 防蝕性、耐磨性）及改良黏著性（例如黏著於清漆或環氧樹 脂鍍層）。先前技術中’ ASC方法曾經稱做陽極電火花沈 積（ASD)、電解沈積、電火花陽極鍍敷（SA)、微電漿方法 等。 ASC方法典型係將待鍍敷為陽極之金屬基材置於電解 溶液（通常為水溶液）》電解溶液常稱電解質「浴」。陰極 也置於浴中’跨越陽極與陰極施加電壓，使電流流經陽極 舆陰極。 任電流流動至陽極獲得預定鍍層厚度為止。電流典型 控制為可維持陽極與陰極間之穩定電流，或控制為跨越陽 極與陰極之恆定電壓。鍍敷陽極過程中，通常於陽極可見 火花。 先前技術曾經嘗試多種不同電解質浴组合物而成功度 不等。曾經使用之電解質浴含有鋁酸鹽，矽酸鹽，鎢酸鹽 ，鉬酸鹽，鉻酸鹽，磷酸鹽，氟化物，釩酸鹽，鈦酸鹽， 本紙張尺度遑用中國國家標準（CNS > Μ規格（2丨0X297公釐） 4Printed by the Central Standards Bureau of the Ministry of Economic Affairs, Shellfish Consumer Cooperative ^ υ8ΐ87 a? ____ Β7 V. Description of Invention (1) This case seeks the rights and interests of US Provisional Application No. 60 / 077,062 filed on March 6, 1998. The present invention relates to an anode electric spark plating (ASC) method, an electrolyte bath that can be used in this method, and a plating layer produced by this method. In particular, the present invention relates to an anode electric spark plating method, which uses a low concentration of phosphate The electrolyte bath produces a thin, smooth and mainly oxide coating on metal substrates, especially substrates made of aluminum and aluminum alloys. The ASC method is known in the industry "—In general, a variety of these methods have been used on metal substrates to improve surface characteristics such as appearance (such as color), durability (such as corrosion resistance, abrasion resistance), and improved adhesion (such as adhesion to Varnish or epoxy coating). In the prior art, the 'ASC method' has been referred to as anode spark deposition (ASD), electrolytic deposition, spark anode plating (SA), micro-plasma method, and the like. The ASC method typically involves placing the metal substrate to be plated as an anode in an electrolytic solution (usually an aqueous solution). The electrolytic solution is often referred to as an electrolyte "bath". The cathode is also placed in the bath. A voltage is applied across the anode and the cathode to cause a current to flow through the anode and the cathode. The current is allowed to flow until the anode obtains a predetermined coating thickness. The current is typically controlled to maintain a stable current between the anode and cathode, or to a constant voltage across the anode and cathode. During anode plating, sparks are usually visible on the anode. The prior art has tried several different electrolyte bath compositions with varying degrees of success. The used electrolyte bath contains aluminates, silicates, tungstates, molybdates, chromates, phosphates, fluorides, vanadates, titanates. This paper uses the Chinese National Standard (CNS) > Μ specifications (2 丨 0X297 mm) 4
;—：---¢------------ii . ' ' , (請先聞讀背面之注意事項再填寫本頁J 經濟部中央揉準局貝工消費合作杜印製 408187 A7 _ B7五、發明説明（2 ) 鈮酸鹽，碳酸鹽，硼酸鹽等》也已知分散粒子如氧化物陶 瓷、顏料及金屬硫化物也可存在於電解質浴。 多種先前技術ASC方法中，目標係由電解質浴沈積離 子（經常為金屬離子）或氧化物於待鍍敷基材表面上《典型 此乃先前技術稱做ASD或電沈積目的。 ASC方法涉及許多不同參數，包括基材組成、浴組成 、浴pH、浴溫、使用電壓、使用電流及施加電流時間， 先前技術教示多種不同ASC方法其曾經嘗試經由改變其中 一或多種參數來改良錢層。 雖然先前技術教示多種不同ASC方法，但先前技術教 示之方法及鍍層仍有缺點。例如通常觀察到藉先前技術 ASC方法生產的較厚鍍層不如較薄鍵層光滑且常有裂開傾 向。因此鍍敷業界仍然需要比先前技術ASC方法製造之同 等厚度鍍層更為光滑的鍍層。較光滑鍍層對某些產業特別 黏合用途較佳。鍍敷業界也仍需要提高用於物件例如主制 動機筒之較高耐磨性、防蝕性及較低表面粗度》 一具體例中，本發明為一種新穎ASC方法。另一具體 例中本發明為ASC方法有用的電解質浴之新穎組成。又另 一具體例中本發明為新穎金屬基材鍍層。 本發明之電解質浴通常無毒、生產價廉、製造容易且 容易維持。本發明之電解質浴可用於ASC方法於寬廣製程 參數（例如電流密度、浴溫及電流施加時間）公差下，於寬 廣範圍之鋁合金上生產高品質一致鍍層》 本發明之電解質浴包含低濃度磷酸根陰離子於鹼性溶 ----------裝------一訂--------練 . ' . - (請先閲讀背面之注意事項再填寫本頁) 本紙張尺度適用中國國家標準（CNS ) Α4規格（210Χ297公釐） A7 B7 408187 五、發明説明（3 ) 液。鹼性表示本發明之電解質浴之pH高於或等於7。較佳 本發明之電解質浴之pH高於約8。 本發明之浴須含足量磷酸鹽來消除因浴導電率低造成 的燒灼。本發明之浴含有至少約0.01莫耳濃度磷酸根陰離 本發明浴含有不多於約0.1莫耳濃度磷酸陰離子。較 佳本發明之浴含有不多於約0.06莫耳濃度磷酸根陰離子。 本發明之較佳具體例中，電解質浴包含約等濃度正磷 酸鹽及焦破酸鹽。本發明之特佳具趙例中，電解質浴包含 约0.03莫耳濃度正磷酸鹽及约〇.〇3莫耳濃度焦磷酸鹽。 其它陰離子也可存在於本發明之電解質浴a但此等陰 離子之存在濃度須夠低而不會顯著改變利用浴於ASC方法 所得銀層。例如若碎酸鹽係存在於本發明之電解質浴，則 其存在濃度須夠低而大致並無二氧化矽於ASC過程沈積於 基材表面上◊ 本發明之鍍層為主要為由氧化鋁組成之薄而緊密的鍍 層。雖然鍵層主要由氧化銘組成，但小量鱗偶_出現於鍵 層。若磷存在於鍍層，則通常接近鍍層外表面。本發明之 鍍層厚約0.5微米至10微米9此外本發明之鍍層表面粗度 比先則技術等厚度之錄層更低。發現本發明之銀層可提高 經鍍敷基材面之防蝕性及耐磨性。本發明進而提供出乎意 外地用於陽極配置之優點包括深鏜孔及窄管内側其存在於 澆鑄鋁部件用於汽車例如用於主制動機筒。本發明也提供 金屬基材至其它材料例如另一種金屬或塑膠使用黏著劑接 本紙張尺度適用中國國家標準（CNS ) A4坑格（210χ297公董） i . 裝 —訂------線 (請先閱讀背面之注意事項再填寫本頁) 經濟部中央標準局貝工消费合作社印裝 6 Α7 Β7 408187 五、發明説明（4 ) 合的改良。本發明之鍍層可用作鋁面之表面處理俾充分接 合或塗漆β 一般而言，本發明方法係經由設置待鍍敷金屬基材於 電解質浴作為陽極進行。陰極也設置於浴中，電壓施加跨 越陽極及陰極，使電流流經陽極與陰極間。也使電流流動 至於陽極獲得預定鍍層厚度為止。電流典型係經由維持陽 極與陰極間之恆定電流控制或經由維持跨越陽極與陰極之 怪定電壓控制。鍍敷陽極過程中，通常於陽極觀察得電火 花。用於本發明之目的，首次觀察得火花使測得之電壓稱 做V電火花。 須注意當使用本發明之電解質浴時，本發明方法驗證 對特定施加電流密度顯著不敏感。換言之本發明方法中， 電流密度之顯著改變不會顯著改變所得鍍層性質（例如表 面粗度）。顯然鍍敷性質更佳依賴電流密度與操作時間的 乘積（亦即總電荷）。相反地，先前技術鍵層之表面粗度似 乎與鍍層生產過程使用電流密度有較密切關聯。 本發明之電解質浴包含低濃度磷酸根陰離子於鹼性水 溶液。鹼性一詞表示本發明之電解質浴具有？11大於或等 於7 β若浴之pH過低，則陽極基材受到某些「燒灼」。「燒 灼」發生於陽極基材局部區域電話放電過度密集，結果導 致品質不良且不一致的艘層。較佳本發明之電解質浴具有 pH高於約8。本發明之鍍層可成功地使用就pH高達約11之 浴生產。可利用pH高於11之浴β 浴中較低濃度陰離子使浴具有較低導電率，因此效率 本紙張尺度適用中國國家榡準（CNS ) Α4規格（210X297公釐） -----------裝-------訂------線 , . - . (請先聞ί面之注$項再填寫本頁) 經濟部中央梯準局負工消费合作社印製 經濟部中央梯準局貝工消費合作社印裝 A7 B7 五、發明説明（5 ) 較低。若磷酸根濃度過低，則容易因導電率降低產生較高 燒灼傾向。如此本發明之浴較佳含足量磷酸鹽來消除因浴 導電率低造成的燒灼。本發明浴含有至少约莫耳丨農度 磷酸根陰離子。 若填酸根浪度超過約0.1莫耳濃度，則形成較厚且較 不一致的鍍層。濃度高於約0.1莫耳濃度，要求電壓較低 ，鍍層之形成速率較高。發現使用包含磷酸根濃度大於約 〇_1莫耳濃度之浴產生之鍍層較厚、較不均句且比使用較 低濃度磷酸鹽與產生之鍍層更粗糙。此等較厚且較不均勻 的鑛層於許多用途較為不具利用性例如黏著接合之前處理 、塗漆或鍵敷主制動機筒β較佳本發明浴含有不高於約 0.06莫耳濃度磷酸根陰離子β 本發明之較佳具體例甲，電解質浴包含約等濃度正磷 酸鹽及焦磷酸鹽《觀察得包含約略等濃度正磷酸鹽及焦磷 酸鹽之電解質浴比較不含約略等濃度正磷酸鹽及焦磷酸鹽 之浴可獲得更寬廣之有用製程參數範圍（例如電流密度、 浴溫及電流施加時間）^本發明之特佳具體例中，電解質 浴包含約0.03莫耳濃度正磷酸根及約0·03莫耳濃度焦磷酸 根。 其它陰離子可存在於本發明之電解質浴。但此等陰離 子僅以夠低濃度存在因而不會顯著改變由於利用浴於ASc 方法所得錄層。 特別當某些陰離子以充分高濃度存在於電解質浴時， 此等陰離子之氧化物可能於ASC過程中沈積於陽極基材上 本紙張適用中家標準（CNS ) ( 21Gx297公着） ^ ^ 裝------，訂-------線 • * . · (請先W讀背面之注意事項再填寫本頁) 408187 A7 B7 五、發明説明（6 。用於本說明書之用途，此等陰離子將稱做「可沈積陰離 子可沈積陰離子為含氧陰離子也稱做二元氧陰離子相 。可沈積陰離子包括例如矽酸鹽、釩酸鹽、鉬酸鹽、鎢酸 鹽' 鋁酸鹽、硼酸鹽及磷酸鹽。 例如若矽酸鹽存在於本發明之電解質浴，則其存在濃 度須夠低因此於ASC過程大致並無二氧化矽沈積於基材表 面上°當二氧化矽沈積於基材表面時，表面粗度高於當無 二氧化矽沈積於基材表面時之粗度。當然小量二氧化矽沈 積物可忍受，取決於表面鍍層之預定用途β 相信可沈積陰離子氧化物係於ASC方法可見電火花該 期形成。電火花較為緻密產生由可沈積陰離子衍生而得之 氧化物沈積物較大。 可沈積陰離子濃度上限屬於使用之特定陰離子、電火 花強度、浴pH、浴溫等改變。任何用於其它參數之特定 陰離子濃度上限無須經過不當的實驗即可測定。此種可沈 積陰離子上限觀察得約〇.〇4莫耳濃度。較佳本發明之電解 質浴未存在有可沈積陰離子。 經濟部中央棣準局貝工消费合作社印製 (請先閱讀背面之注意事項再填寫本貫〕 用於本說明書之用途「非可沈積陰離子」表示並無相 關之眾所周知的穩定二元結晶氧化物相。非可沈積陰離子 包括例如碳酸鹽，硫酸鹽及氟化物。 非可沈積陰離子可以比較可沈積陰離子於本發明浴令 忍受較高濃度。通常本發明之電解質浴含有至多約〇1莫 耳濃度非可沈積陰離子。較佳並無非可沈積陰離子存在於 本發明浴。 L紙張尺度通用中國困家樣準（CNS ) A4规格（210X297公釐） 9 . 經濟部中央揉準局*:工消费合作社印製 408187 A7 _ B7 五'發明説明（7) 一旦已知預疋陰離子濃度，本發明之電解質浴之製法 並無特殊限制。設預定陰離子濃度於浴t業界人士容易了 解如何生產浴。 本發明之電解質浴溫並無特殊規定。典型浴溫於本發 明過程中略升。使用15°C至35。(：浴溫生產絕佳鍍層。如前 述，當電解質浴含有约略等濃度正磷酸鹽及焦磷酸鹽時， 可接受之浴溫範圍顯著更高。預期浴溫通常維持1〇〇c至40〇c。 本發明之鑛層於銘基材上接受顯微碳針分析》分析顯 示鐘層含氧化鋁。如此本發明錄層為薄且緻密之主要為氧 化鋁之鍍層。雖然此等鍵層主要由氡化鋁組成，但小量碟 偶爾而出現於链層。若碟存在於鍍層，則通常接近鍵層外 表面。 本發明鍍層厚約0.5微米至1〇微米.若二鍍層係使用 相同浴生產’則較厚鍍層之表面粗度較高。但本發明之鍍 層比較先前技術具有相等厚度之鍍層表面粗度較低。 下表資料進一步示例說明本發明之若干具體例。下表 資料之全部鍍層係使用直流電源生產。 表1資料係有關於鋁5052製造之1呎（30.48厘米）xl呎 (30.48厘米）板生產的鍍層。表2資料係有關於鋁11〇〇製成 的2.5吋（6.35厘米）x3吋（7.62厘米）板上生產的錢層·» 其它铭基材也曾經根據本發明成功地鑛敷。例如由 1000 ' 2000 ' 3000、5000及6000系列加工紹合金製造的銘 基材曾經成功地鍍敷，以及鋁澆鑄合金如356合金製造的 基材亦如此。 本紙張尺度適用中國圉家標準（CNS > A4規格（210X297公釐} 10 ------：--.---裝-- . . - (請先閲讀背面之注意事項再填寫本頁} 訂 線 A7 B7 408187 五、發明説明（8 ) 表1 經濟部中央樣準局舅工消費合作社印策 浴組成 浴pH 電流密度 操作時間 V電夂花 觀察 0.03M Κ2ΗΡ04 0.03MN34PA 10.3 30毫安/平方厘米 4分鐘 360伏 均勻嗶嘰色嫂層 0.03MK2HPO4 O.CQMNa^O, O.OlMNaF 9.9 30毫安/平方厘米 4分鐘 360伏 均勻嗶嘰色鐘層 0·03ΜΚ2ΗΡ04 0.03MNa,P207 O.OlMNaF O.CWMNHiVOs 0.04MNaOH 9,4 30毫安/平方厘米 4分鐘 240伏 比電火花樣式更 為燒灼的暗色沈 積物 0.03MK2HP04 0.03MN34PA O.OlMNaF 0,04MNH<V〇3 0.05M Si02 9.7 30毫安/平方厘米 4分鐘 250伏 比電火花樣式更 為燒灼的暗色沈 積物 0.018MK2HP04 0.018MNa4P207 0.006MNaF 0.024MNH,V〇3 0.03M Si02 10.3 30毫安/平方厘米 4分鐘 320伏 均勻褐嘩嘰色鍍 層，接近角隅有 小的黑色沈積物 0.06M K2HP04 0.01MNa,P207 11.7 30毫安/平方厘米 4分鐘 200伏 邊緣及角隅有重 質痂皮狀沈積物 (請先閲讀背面之注意事項再填寫本頁) 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 11 經濟部中央標準局員工消费合作社印製 408187 A7 __- B7 I _ 五、發明説明（9) 表2 浴組成 浴pH 電流密度 操作時間 觀察 0.02M K2HP04 O.tQMNa^A 9.9 3〇毫安/平方厘米 4.5分鐘 380伏均勻嗶嘰色錢層 0.03M Κ2ΗΡ04 0.03MNa4P207 9.9 30毫安/平方厘米 4.1分鐘 345伏均勻嗶嘰色鍍層 0.03MK2HP〇4 0.03MNa4P2〇7 O.OlMNaF 9.9 30毫安/平方厘米 4.0分鐘 360伏均勻嗶嘰色鑛層 0.04MK2HP04 O.tMMNaJPA 10.0 30毫安/平方厘米 4.0分鐘 300伏均勻嗶嘰色錄層 0.045MK2HP〇4 0.045MNaJ>207 10,0 30毫安/平方厘米 4.0分鐘 300伏均勻嗶嘰色鍍層 0.05MK2HP〇4 0.05MNa,P207 HU 30毫安/平方厘米 4.0分鐘 300伏均勻嗶嘰色链屠 0,055MK2HP04 0.055MNa4P207 10.2 30毫安/平方厘米 4.0分鐘 300伏局部燒灼起點 0.03MK2HP04 0·03ΜΝ〜ΡΑ 10.3 40毫安/平方厘米 3.0分鐘 300伏均勻嗶嘰色鍍廣 0.018MK2HP〇4 Ο.ΟΙδΜΝ^ΡΑ 0.04MNH4V03 0.030M Si02 40毫安/平方厘米 4分鐘 250伏比電火花-fractal樣 式更為燒灼的暗色 沈積物 0.019MK2HP04 〇.〇鹽琴2〇7 0.144ΜΝΗ,ν〇ϊ O.OSMSiC^ 30毫安/平方厘米 4分鐘 320伏均勻褐嗶嘰色嫂層 I in —Μ n I I 裝 n ^ ~^ n I t [線 (請先閱1^面之注f項再填寫本頁) 本紙張尺度適用中國國家棣準（〇呢）八4規格（2〖0乂297公釐> -12 -; —: --- ¢ ------------ ii. '', (Please read the notes on the back before filling out this page. 408187 A7 _ B7 V. Description of the invention (2) Niobate, carbonate, borate, etc. "It is also known that dispersed particles such as oxide ceramics, pigments and metal sulfides can also be present in the electrolyte bath. A variety of prior art ASC methods The goal is to deposit ions (often metal ions) or oxides from the electrolyte bath on the surface of the substrate to be plated. This is typically referred to as ASD or electrodeposition in the prior art. The ASC method involves many different parameters, including the substrate Composition, bath composition, bath pH, bath temperature, applied voltage, applied current, and applied current time, the prior art teaches a variety of different ASC methods that it has tried to improve the money layer by changing one or more of the parameters. Although the prior art teaches a variety of different ASC Methods, but the methods and coatings taught in the prior art still have disadvantages. For example, it is generally observed that thicker coatings produced by the prior art ASC method are not as smooth as thinner bond layers and tend to crack. Therefore, the plating industry is still Requires a smoother coating than the equivalent thickness coating produced by the prior art ASC method. A smoother coating is better for special bonding applications in some industries. The plating industry also needs to improve the higher wear resistance of objects such as the main brake cylinder In one specific example, the present invention is a novel ASC method. In another specific example, the present invention is a novel composition of an electrolyte bath that is useful for the ASC method. In another specific example, the present invention is The coating is a novel metal substrate. The electrolyte bath of the present invention is generally non-toxic, inexpensive to produce, easy to manufacture and easy to maintain. The electrolyte bath of the present invention can be used in the ASC method for a wide range of process parameters (such as current density, bath temperature, and current application time) Production of high-quality consistent coatings on a wide range of aluminum alloys within tolerances "The electrolyte bath of the present invention contains a low concentration of phosphate anions in an alkaline solution. -------- Exercise. '.-(Please read the notes on the back before filling this page) This paper size applies to Chinese National Standard (CNS) A4 specification (210 × 297 mm) A7 B7 408187 5. Explanation (3) Liquid. Alkaline means that the pH of the electrolyte bath of the present invention is higher than or equal to 7. Preferably, the pH of the electrolyte bath of the present invention is higher than about 8. The bath of the present invention must contain a sufficient amount of phosphate to eliminate the bath. Burning caused by low electrical conductivity. The bath of the present invention contains at least about 0.01 moles of phosphate anions. The bath of the present invention contains no more than about 0.1 moles of phosphate anions. Preferably the bath of the present invention contains no more than about 0.06 moles Ear concentration phosphate anion. In a preferred embodiment of the present invention, the electrolyte bath contains approximately equal concentrations of orthophosphate and pyrogenate. In a particularly preferred embodiment of the present invention, the electrolyte bath contains approximately 0.03 mole of orthophosphate Salt and pyrophosphate at a molar concentration of about 0.03. Other anions may also be present in the electrolyte batha of the present invention, but the concentration of these anions must be low enough without significantly altering the silver layer obtained by using the bath in the ASC method. For example, if the salty acid salt is present in the electrolyte bath of the present invention, its concentration must be low enough so that no silicon dioxide is deposited on the surface of the substrate in the ASC process. The coating of the present invention is mainly composed of alumina. Thin and tight plating. Although the bond layer is mainly composed of oxide layers, a small amount of scale couples appear in the bond layer. If phosphorus is present in the coating, it is usually close to the outer surface of the coating. The thickness of the plating layer of the present invention is about 0.5 micrometer to 10 micrometers9 In addition, the surface roughness of the plating layer of the present invention is lower than that of the recording layer of the prior art. It was found that the silver layer of the present invention can improve the corrosion resistance and abrasion resistance of the plated substrate surface. The invention further provides unexpected advantages for anode configurations including deep boring and narrow tube insides which are present in cast aluminum parts for automobiles such as for main brake cylinders. The present invention also provides a metal substrate to other materials, such as another metal or plastic. Adhesives are used to connect the paper. This paper applies the Chinese National Standard (CNS) A4 pit grid (210 × 297). I. (Please read the notes on the back before filling this page) Printed by the Central Standards Bureau of the Ministry of Economic Affairs, Shellfish Consumer Cooperatives 6 Α7 Β7 408187 V. Description of the invention (4) Improvement of the combination. The plating layer of the present invention can be used as a surface treatment of an aluminum surface. Fully bonded or painted. In general, the method of the present invention is performed by setting a metal substrate to be plated in an electrolyte bath as an anode. The cathode is also placed in the bath, and a voltage is applied across the anode and the cathode so that a current flows between the anode and the cathode. A current is also caused to flow until the anode obtains a predetermined plating thickness. The current is typically controlled by maintaining a constant current between the anode and the cathode or by maintaining a strange voltage across the anode and the cathode. During the anode plating process, sparks are usually observed on the anode. For the purposes of the present invention, the first observation of a spark causes the measured voltage to be referred to as a V-spark. It should be noted that when using the electrolyte bath of the present invention, the method of the present invention verifies that it is significantly insensitive to a specific applied current density. In other words, in the method of the present invention, a significant change in current density does not significantly change the properties of the resulting coating (such as surface roughness). Obviously, better plating properties depend on the product of current density and operating time (ie, total charge). In contrast, the surface roughness of the prior art bond layer seems to be more closely related to the current density used in the plating production process. The electrolyte bath of the present invention contains a low concentration of phosphate anions in an alkaline aqueous solution. The term alkaline means that the electrolyte bath of the present invention has? 11 is greater than or equal to 7 β If the pH of the bath is too low, the anode substrate is subject to some "burning". “Cauterization” occurred when the telephone discharge was too dense in a local area of the anode substrate, resulting in poor quality and inconsistent ship layers. Preferably, the electrolyte bath of the present invention has a pH above about 8. The coating of the present invention can be successfully produced using a bath having a pH of up to about 11. Can use the bath with a pH higher than 11 to lower the concentration of anions in the bath to make the bath have a lower conductivity, so the efficiency of this paper is applicable to China National Standard (CNS) A4 specification (210X297 mm) ------- ---- Install ------- Order ------ line,.-. (Please read the note above and fill in this page). Printed by A7 B7, Shellfish Consumer Cooperative of the Central Ladder Bureau of the Ministry of Economic Affairs 5. The description of the invention (5) is low. If the phosphate concentration is too low, a high burning tendency tends to occur due to a decrease in conductivity. Thus, the bath of the present invention preferably contains a sufficient amount of phosphate to eliminate the burning caused by the low bath conductivity. The baths of the present invention contain at least about Moore ' s fertility phosphate anions. A thicker and more inconsistent coating will be formed if the acid-filling wave intensity exceeds about 0.1 mole. Concentrations higher than about 0.1 Molar require lower voltages and higher plating formation rates. It was found that the use of a bath containing a phosphate concentration greater than about 0 to 1 moles resulted in a thicker, more uneven coating and a rougher coating than using a lower concentration of phosphate and the resulting coating. These thicker and more non-uniform mineral layers are less useful for many purposes, such as pre-adhesive processing, painting or keying the main brake cylinder β. The bath of the present invention contains no more than about 0.06 moles of phosphate Anion β A preferred embodiment of the present invention is that the electrolyte bath contains approximately equal concentrations of orthophosphate and pyrophosphate. "Observed electrolyte baths containing approximately equal concentrations of orthophosphate and pyrophosphate are relatively free of approximately equal concentrations of orthophosphate. And pyrophosphate baths can obtain a wider range of useful process parameters (such as current density, bath temperature, and current application time) ^ In a particularly preferred embodiment of the present invention, the electrolyte bath contains about 0.03 moles of orthophosphate and about 0.03 Molar concentration pyrophosphate. Other anions may be present in the electrolyte bath of the present invention. However, these anions are only present at a sufficiently low concentration and will not change significantly due to the recording layer obtained by using the ASc method. Especially when certain anions are present in the electrolyte bath at a sufficiently high concentration, the oxides of these anions may be deposited on the anode substrate during the ASC process. This paper applies the China Standard (CNS) (21Gx297) ^ ^ Pack- -----, order ------- line • *. · (Please read the precautions on the back before filling out this page) 408187 A7 B7 V. Description of the invention (6. For the purposes of this manual, These anions will be referred to as "depositionable anions. Depositionable anions are oxygen-containing anions and also known as binary oxyanion phases. Depositionable anions include, for example, silicates, vanadates, molybdates, tungstates' aluminates For example, if silicate is present in the electrolyte bath of the present invention, its concentration must be low enough so that during the ASC process, no silicon dioxide is deposited on the surface of the substrate. When silicon dioxide is deposited on The surface roughness of the substrate surface is higher than that when no silicon dioxide is deposited on the substrate surface. Of course, a small amount of silicon dioxide deposit can be tolerated, depending on the intended use of the surface coating. Β It is believed that anionic oxides can be deposited Based on the ASC method, electric fire can be seen It is formed in this period. The electric spark is more dense and produces larger oxide deposits derived from the depositable anions. The upper limit of the concentration of the depositable anions belongs to the specific anion used, electric spark strength, bath pH, bath temperature, etc. The upper limit of the specific anion concentration of other parameters can be determined without undue experimentation. The upper limit of this depositable anion is observed to be about 0.004 mole. The electrolyte bath of the present invention does not have a depositable anion. Central of the Ministry of Economic Affairs Printed by 棣 Junbei Shellfish Consumer Cooperative (please read the precautions on the back before filling in this document). The purpose of this manual "non-depositable anion" means that there is no related well-known stable binary crystalline oxide phase. Non Depositionable anions include, for example, carbonates, sulfates, and fluorides. Non-depositionable anions can tolerate higher concentrations than depositable anions in the baths of the present invention. Generally, the electrolyte baths of the present invention contain up to about 0.01 moles of non-depositionable Anions. It is preferred that no non-depositable anions be present in the bath of the present invention. China Standard for Household Standards (CNS) A4 (210X297 mm) 9. Central Bureau of Standards, Ministry of Economic Affairs *: Printed by the Industrial and Consumer Cooperatives 408187 A7 _ B7 Five 'Description of the Invention (7) Once the pre-anion concentration is known, this There is no special limitation on the method for producing the electrolyte bath of the invention. It is easy to understand how to produce a bath by setting a predetermined anion concentration in the bath. The electrolyte bath temperature of the invention has no special regulations. The typical bath temperature is slightly increased during the process of the invention. Use 15 ° C to 35. (: bath temperature produces an excellent coating. As mentioned earlier, when the electrolyte bath contains approximately equal concentrations of orthophosphate and pyrophosphate, the acceptable bath temperature range is significantly higher. It is expected that the bath temperature will generally be maintained at 100 c to 40 ° c. The ore layer of the present invention was subjected to microscopic carbon needle analysis on a substrate. Analysis showed that the bell layer contained alumina. Thus, the recording layer of the present invention is a thin and dense plating layer mainly composed of aluminum oxide. Although these bond layers are mainly composed of aluminum halide, a small number of dishes occasionally appear in the chain layer. If the dish is present on the plating, it is usually close to the outer surface of the key layer. The thickness of the coating of the present invention is about 0.5 micrometer to 10 micrometers. If the two plating layers are produced using the same bath ', the surface roughness of the thicker coating is higher. However, the surface roughness of the coating of the present invention is lower than that of the prior art coating having the same thickness. The following table further illustrates some specific examples of the present invention. All coatings in the table below are produced using DC power. The information in Table 1 refers to the coatings produced on 1-foot (30.48 cm) x 1-foot (30.48 cm) plates made of aluminum 5052. The data in Table 2 are about the layer of money produced on a 2.5-inch (6.35 cm) x 3-inch (7.62 cm) board made of aluminum 1 100. Other substrates have also been successfully deposited according to the present invention. For example, substrates made from 1000 '2000' 3000, 5000, and 6000 series processed alloys have been successfully plated, as are aluminum substrates such as 356 alloys. This paper size is in accordance with China's standard (CNS > A4 size (210X297mm) 10 ------: --.--- installed-..-(Please read the precautions on the back before filling in this Page} Ordering line A7 B7 408187 V. Description of the invention (8) Table 1 Composition of the bath of the printed policy bath of the Central Samples and Standards Bureau of the Ministry of Economic Affairs and Consumer Cooperatives, pH current density, operating time, V, electric observation, 0.03M, Κ2, PP04, 0.03MN34PA, 10.3 30 mA 360-degree uniform serge-colored sorrow layer 0.03MK2HPO4 O.CQMNa ^ O, O.OlMNaF 9.9 30 mA / cm2 4-minute 360-degree uniform serge-colored serge clock layer 0.03MΚ2ΗΡ04 0.03MNa, P207 O.OlMNaF O .CWMNHiVOs 0.04MNaOH 9,4 30mA / cm2 4 minutes 240V darker deposits that burn more than electric spark pattern 0.03MK2HP04 0.03MN34PA O.OlMNaF 0,04MNH < V〇3 0.05M Si02 9.7 30mA / 250 volts per square centimeter for 250 minutes Darker deposits that are more scorching than the electric spark pattern 0.018MK2HP04 0.018MNa4P207 0.006MNaF 0.024MNH, V〇3 0.03M Si02 10.3 30 mAh / cm2 320 volts uniform brown rust coating for 4 minutes There are small black deposits near the horned owl 0.06M K2HP0 4 0.01MNa, P207 11.7 30 mA / cm2 4 minutes 200 volts at the edges and corners with heavy pimple-like deposits (please read the precautions on the back before filling this page) This paper size applies to Chinese national standards (CNS ) A4 specification (210X297 mm) 11 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 408187 A7 __- B7 I _ V. Description of the invention (9) Table 2 Bath composition bath pH current density Operating time observation 0.02M K2HP04 O.tQMNa ^ A 9.9 30mAh / cm2 4.5 minutes 380V uniform serge color money layer 0.03M Κ2ΗΡ04 0.03MNa4P207 9.9 30mA / cm2 4.1 minutes 345V uniform serge color coating 0.03MK2HP〇4 0.03MNa4P2〇7 O.OlMNaF 9.9 30 mA / cm2 4.0 minutes 360 volts uniform serge color mineral layer 0.04MK2HP04 O.tMMNaJPA 10.0 30 mA / cm2 4.0 minutes 300 volts uniform serge color layer 0.045MK2HP〇4 0.045MNaJ > 207 10,0 30 millimeters Amp / cm2 4.0 minutes 300V uniform serge color coating 0.05MK2HP〇4 0.05MNa, P207 HU 30 mA / cm2 4.0 minutes 300V uniform serge color chain 0,055MK2HP04 0.055MNa4P207 10.2 30mA / cm2 4.0 minutes 300 volt local cauterization starting point 0.03MK2HP04 0.03 MN ~ PA 10.3 40 mA / cm2 3.0 minutes 300 volt uniform serge color plating 0.018MK2HP〇4 〇〇〇ΙΙΜΜ ^ ΡΑ 0.04MNH4V03 0.030M Si02 40 mA / cm2 250 Volts for 4 minutes is more scorching than the electric spark-fractal style. Dark deposits 0.019MK2HP04 〇〇〇 琴 2〇7 0.144ΜΝΗ, ν〇ϊ O.OSMSiC ^ 30mA / cm2 320V uniform brown serge for 4 minutes Color layer I in —Μ n II 装 n ^ ~ ^ n I t [Line (please read the note f of 1 ^ face before filling out this page) This paper size is applicable to China National Standard (〇 呢) 8 4 specifications (2 〖0 乂 297mm > -12-