1257413 玖、發明說明： 【發明所屬之技術領域】 本發明是屬於一種金屬表面奈米粉體溶膠處理法，立 係將奈米粉體溶膠均勾塗佈於被處理物表面，經設定的處 理私序後在破處理物表面形成吸附良好的薄膜的方法。亦 即，本發明是利用設定化學處理程序，將奈米粉體溶膠均 勻塗佈於被處理物表面，再經特定的物理或化學後處理程 序，使得奈轉體溶膠轉化成吸附良好而緻密的保護薄膜 ，可發揮表面光滑（不易積垢）、耐蝕、抗氧化等作用。 【先前技術】 從西元十八世紀開始，金屬表面處理即成為不管是研 發或應用上，均極受重視且應用廣泛的技術，其主要内容 為電鍍及陽極防蝕等技術，經長年研發改善，此類處理技 術已相^成熟’其成品功能往往能滿足客戶要求且品質良 好’但污染嚴重及基材限制始終是其最大瓶頸；此外，電 Μ或陽極防蝕處理後的成品，往往還需要作高溫燒結的處 理’造成成本提高及基材材質本身的傷害。 1960年後真空蒸鍍（包括化學蒸鍍（Chemical Vap〇r Deposition ; CVD)及物理蒸鍍（Physical Vapor Deposition) 等）技術開始推廣及導入生產，蒸鍍後的成品品質良好且適 用各種基材，但成本昂貴/品質會受基材形狀影響及存在 死角，始終成為技術的瓶頸及使用的限制。1980年後，化 學處理（主要為有機保護膜或有機金屬覆蓋層）的應用，可 有效改善成本、污染、形狀干擾、處理死角、高溫燒結、 5 1257413 基材傷宝擎P弓ΘΗ 、、但部有著不耐磨、不持久及不耐化學腐 观的問題。 基於上述問., 成7 碭，利用金屬氧化物作表面覆蓋的技術便 战了 1990年之；^ αα』 、技術開發主流。U· s· Patent 4,385,097 所揭示的作法，A * 入1 、忪、氮、硫等鹽基的水溶性樹脂中，加 1〜3〇%鈦或鍅的有機金屬錯化物，經覆蓋處理後可在 y表面形成抗腐餘薄膜，以代替高污染的鑛絡處理，·此 古处方式$ &的保言蒦膜耐# &好，但樹脂的物料成本甚 P 、”工濟效盈有限。u s Patent 6,656 6〇7則以辞一有機 (Silane)樹脂在金屬表面形成抗腐蝕薄膜，一樣存在 、蝕良好仁物料成本甚高的問題：此外，鋅的耐酸性較差 也是問題所在。英國專㈣M2U91號在料中加入叙 及銳的衍生合金，並配合適當胺類，形成保護膜，亦存在 相同的問題。歐洲專利第〇 595 341 A2號是在含二氧化欽 的塗料中加人1〜10%辞的金屬粉末，經覆蓋處理後可在 金屬表面形成抗腐蝕薄膜，但因塗料的耐熱性問題，造成 使用上的限制。 類似的作法亦在中華民國專利公告第539732號及 554017號（“防蝕金屬粉末塗料，，）中可見，其專利内容 為在塗料中添加含鋁的鋅粉，配合黏著劑、添加劑、塑劑 及溶劑’即可形成防蝕塗料；但此一作法，同樣存在塗料 耐熱性問題，造成使用上的限制。中華民國專利公告第 245733號“抑制金屬基材腐蝕之塗料組合物，，之專利案， 係以有機硫氮化物為基礎，合成可耐腐蝕的塗料配方，作 1257413 其耐溫性及财磨性均差。中華民國 八 “全屬声而夕狀廢為忐 ” A 口弟357196號 材料卢❹居主二 ㈣案則以含有機矽的複合 材科處理金屬表面，以達到防㈣目的 成品品質，耐磨性及耐㈣ &理方式的 依然存在。 仁物科成本甚高的問題 綜合上述，目前的金屬表 萄衣曲耐腐蝕處理雖各 但分別存在關鍵缺失，其内容如下： 一 ··真空蒸鍍··成本昂貴、口晳4、☆甘u P貝口口貝會文基材形狀影響 、存在處理死角。 < 二··電鍍：二次污染嚴重。 三：有機保護膜：不耐磨、不持久、不耐化學腐蝕 〇 四··金屬塗料··耐熱性不佳。 五：有機矽複合材料：物料成本甚高。 根據上述’目前的金屬表面耐腐蝕處理效果皆有待改 二，而技術開發部份，並無任何涉及利用奈米粉體溶膠覆 蓋技術’進行金屬表面耐腐蝕處理的技術開發或應用。 【發明内容】 本發明疋利用一系列的製程設定，將奈米粉體溶膠均 勻塗佈於已經過“清潔”及“前處理，，的金屬或合金表面 ，並經設定條件的“後處理，，程序，形成吸附良好而緻密 、保《蒦薄膜’可發揮表面光滑（不易積垢）、耐餘、抗氧 化等作用。 本發明包括以下程序： 1257413 別㈣^潔程序：將金屬或合金置人以依材料不同而分 一“人 液中’在設定條件下作處理，以達到金屬 s σ金表面清潔、抗氧化的目的； 、’ 需要二Γ理程序：將經過清潔處理的金屬或合金，依 及材科性質置入個別的前處理液中，以形成表面改質 幫助表面塗佈及後處理的進行； 三、表面塗佈程序：將選定的奈轉體溶膠溶液以選 具均句塗佈於已經過前處理程序的金屬或合金表面 ’並經過水洗、烘乾的步驟，在金屬或合金表面形成 而均勻的塗佈層； / 四後處理程序··將塗佈完成的金屬或合金，以設定 的溫度程序烘烤，使得塗佈層轉化成均句、緻密而吸附良 好的薄膜保護層，可發揮表面光滑（不易積垢）、耐钱^ 抗氧化等作用。 藉此，本發明可使金屬表面在耐酸、耐蝕的性能上 明顯的改善。 【實施方式】 本發明是運用一序列設定的化工處理程序，將被處理 的金屬或合金經清潔、前處理、表面塗佈及後處理等程序 ’使奈米粉體溶膠在金屬或合金表面形成均勻、緻密而吸 附良好的薄膜保護層，使具有表面光滑（不易積垢 L 蝕、抗氧化等作用。 其中清潔程序主要為以清潔劑在設定的溫度、時間進 行反應，其中清潔劑的選定是依被處理的金屬或合金材質 1257413 特性、表面清潔度及後製程（前處理程序或表面塗佈程序 )的需求而定，主要作用為在金屬或合金表面清潔、抗氧 化的目的。清潔劑依材質、表面污染類別及後製程特性分 成^性及鹼性兩大類，成份主要為潤濕劑、pH調整劑及金 屬保護劑；其中金屬保護劑依金屬或合金材質不同而異， 銅材貝以笨並***（Benzotriazole，BTA )及其衍生物為 金屬保羞劑的主成份，鐵金屬或其合金則以草酸、磷酸為 金屬保護劑的主成份。 ' 前處理程序主要是在被處理的金屬或合金表面形成表 面改質以幫助表面塗佈及後處理的進行；所使用的前處 理劑以含二氧化鈦、二氧化矽的奈米粉體溶膠溶液為主體 ，加入適當的有機矽化合物，並依需要添加潤濕劑及分散 劑；以塗抹、浸泡或喷灑等方式將前處理劑均勻附著於表 面清潔完成的金屬或合金，經水洗、烘烤後，配合適當的 焚燒處理形成薄膜，即完成前處理程序。其中所使用的奈 米粉體溶膠，粒徑分佈為2〇〜4〇〇nm;所使用的分散劑視 需要加入，種類以聚乙二醇（pEG )或聚丙二醇（ppG ) 或壬基紛（NP)或天然醇為主，分子量在200〜1000之間 ’添加罝為10〜5000ppm為宜；潤濕劑則以辛酚（〇ctyl Phen〇1，OP)或油醯醇（Oleyl Alcohol)或綿羊油為主， 为子1在200〜3 500之間，添加量為5〜l〇〇〇ppm為宜。 焚燒處理的條件依奈米粉體溶膠及有機矽化合物的種類不 同，溫度範圍自150°C〜400°C，焚燒時間為1〇分鐘〜4 小時。 1257413 表面塗佈所使用的處理劑為以含二氧化鈦、二氧化石夕 、氧化鋁的奈米粉體溶膠溶液，其粒徑分佈為3〜4〇nm， 並依需要添加潤濕劑及分散劑，其中潤濕劑及分散劑的選 用依奈米粉體種類而變，其成份及用量同前處理劑；處理 方式是以塗抹'浸泡或喷灑等方式將處理劑均勻附著於金 屬或合金的表面，經水洗、烘乾後進行後處理程序（ treatment)。後處理程序係依奈米粉體種類、顆粒大小及 基材性質而變，可分高溫焚燒及低溫熟化兩種方式；其中 高溫焚燒溫度範圍自20(rc〜7〇(rc，焚燒時間為3〇 鐘1 〜24小時；低溫熟化則在常溫條件下靜置1〜14天即成。 經過上述處理的的金屬或合金，表面會形成均勻、緻 密而吸附良好的薄膜保護層，不但表面光滑，丨易積垢， 而且在耐蝕、抗氧化等等特性上有明顯的改良。 [實施例]: 以下便舉出實施例以說明本發明内容，但本發明之範 圍並不只限於此等的實施例·· 實施例一： 將銅製水管之管件浸泡在以硫酸（3%)、雙氧水（ 10%)及BTA(100ppm)所組成的微姓劑中三分鐘（溫度 ).盈水洗、烘乾後，以二氧化石夕的奈米粉體溶膠溶 液塗佈其表面，經戰烘、烤1小時，再浸泡於二氧化鈦 、二乳切、氧化銘的奈米粉體溶膠溶液―分鐘（溫度25 C)，然後在3帆的條件下燒結，時間2小時，即為成 10 1257413 品。將原管件、處理後 Λ ^ (未&尨）、燒結後，分別以蹄酸 u蝕劑、氯化銅蝕刿 ~ 風0夂 • x ’夜’文泡，觀察銅面變色時間如表一1257413 玖, the invention description: [Technical field of the invention] The invention belongs to a metal surface nano powder sol treatment method, and the nano powder sol is uniformly coated on the surface of the object to be treated, and the processing is performed in a private order. A method of forming a well-adsorbed film on the surface of the treated material. That is, the present invention utilizes a set chemical processing procedure to uniformly apply a nano-powder sol to the surface of the object to be treated, and then undergoes a specific physical or chemical post-treatment procedure to convert the nano-rotate sol into a well-adsorbed and dense protection. The film can exert a smooth surface (not easy to scale), corrosion resistance, oxidation resistance and the like. [Prior Art] Since the eighteenth century AD, metal surface treatment has become a technology that is highly valued and widely used in research and development or application. Its main content is electroplating and anode anti-corrosion technology, which has been developed and improved over many years. The class processing technology has been matured. 'The finished product function can often meet the customer's requirements and the quality is good'. However, the pollution is serious and the substrate limitation is always the biggest bottleneck. In addition, the finished product after the electric or anode anti-corrosion treatment often needs high temperature. Sintering treatment 'causes cost increases and damage to the substrate material itself. After 1960, vacuum evaporation (including chemical vapor deposition (CVD) and physical vapor deposition (Physical Vapor Deposition)) technology was introduced and introduced into production. The finished product after evaporation was of good quality and suitable for various substrates. However, the cost/quality is affected by the shape of the substrate and the dead angle, which has always become a technical bottleneck and a limitation of use. After 1980, the application of chemical treatment (mainly organic protective film or organic metal coating) can effectively improve cost, pollution, shape interference, treatment of dead angles, high temperature sintering, 5 1257413 substrate damage Baoqing P bow, but The Ministry has problems of not wearing, not lasting and not resistant to chemical rot. Based on the above question, the technology of using metal oxides as surface covering was in 1990; ^αα』, the mainstream of technology development. U.S. Patent 4,385,097 discloses a method in which A* is added to a water-soluble resin having a base such as 1, ruthenium, nitrogen, or sulfur, and an organic metal complex of 1 to 3% by weight of titanium or ruthenium is added. An anti-corrosion film is formed on the surface of y to replace the highly polluted mineral processing. This ancient method is safe and good, but the material cost of the resin is very high. Limited.us Patent 6,656 6〇7 The problem is that the organic resin (Silane) resin forms a corrosion-resistant film on the metal surface, which has the same problem of high corrosion and good material cost: in addition, the acid resistance of zinc is also a problem. Special (4) M2U91 added the derivative alloy of Syria and sharp in the material, and combined with the appropriate amines to form a protective film, the same problem exists. European Patent No. 595 341 A2 is added to the coating containing Dioxin 1 ~10% of the metal powder can form a corrosion-resistant film on the metal surface after being covered, but it is limited by the heat resistance of the coating. Similar practices are also found in the Republic of China Patent Bulletin Nos. 539732 and 554017 ("Protection It can be seen in the metal powder coating, the patent content is that the aluminum powder containing aluminum is added to the coating, and the anti-corrosive coating can be formed by using the adhesive, the additive, the plastic agent and the solvent; but in this way, the heat resistance of the coating is also present. The problem is caused by restrictions on use. The Republic of China Patent Publication No. 245733 "Painting composition for inhibiting corrosion of metal substrates, the patent case, based on organic sulfur nitrides, synthesizes a corrosion-resistant coating formulation for 1257413, its temperature resistance and robustness. The mean difference. The Republic of China eight "all sounds and the eve of the waste" A A mouth brother 357196 material Lu Hao owner two (four) case to deal with the metal surface with a composite material containing the machine to achieve (four) purpose of finished product quality , wear resistance and resistance (4) & the way of management still exists. The problem of high cost of Renkeke is comprehensive. As mentioned above, there are key defects in the current corrosion resistance treatment of metal-coated clothing. The contents are as follows: ·Vacuum evaporation · expensive, clear 4, ☆ 甘 P P 贝 贝 基材 基材 基材 基材 基材 基材 基材 基材 基材 基材 基材 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 二 二 二 二 二 二Not wear-resistant, not durable, not resistant to chemical corrosion 〇 4. Metal coatings · Poor heat resistance. 5: Organic bismuth composite materials: material costs are very high. According to the above-mentioned 'metal surface corrosion resistance treatment To be reworked, and in the technology development part, there is no technology development or application involving the use of nano-powder sol coating technology to perform metal surface corrosion-resistant treatment. [Invention] The present invention utilizes a series of process settings to The rice powder sol is evenly applied to the surface of the metal or alloy which has been "cleaned" and "pretreated", and after the set conditions, "post-treatment, procedures, formation of good adsorption and compact, "蒦 film" can play the surface Smooth (not easy to foul), durable, anti-oxidation, etc. The present invention includes the following procedures: 1257413 (4) ^ cleaning procedures: the metal or alloy is placed in accordance with the material and divided into a "human liquid" under the set conditions It is treated to achieve the purpose of cleaning and anti-oxidation of metal s σ gold surface; 'Requires two treatment procedures: the cleaned metal or alloy is placed into individual pretreatment liquid according to the material properties to form Surface modification helps surface coating and post-treatment; 3. Surface coating procedure: Apply the selected nematic transfer sol solution to the selected ones before it has passed The metal or alloy surface of the process is 'washed and dried, and a uniform coating layer is formed on the surface of the metal or alloy; / Four post-treatment procedures · The finished metal or alloy is set to a temperature The program is baked to convert the coating layer into a uniform, dense and well-adsorbed film protective layer, which can exert a smooth surface (not easy to scale), and is resistant to money and oxidation. Thereby, the present invention can significantly improve the metal surface in acid resistance and corrosion resistance. [Embodiment] The present invention uses a sequence of chemical processing procedures to clean, pretreat, surface coat and post-treat the treated metal or alloy to make the nano-powder sol uniform on the surface of the metal or alloy. The dense and well-adsorbed film protective layer makes the surface smooth (not easy to foul, corrosion, anti-oxidation, etc.) The cleaning procedure is mainly to react with the cleaning agent at a set temperature and time, wherein the cleaning agent is selected The metal or alloy material to be processed 1257413, surface cleanliness and post-process (pre-treatment procedures or surface coating procedures) requirements, the main role is to clean the metal or alloy surface, anti-oxidation purposes. The surface contamination category and the post-process characteristics are divided into two categories: ^2 and alkaline. The components are mainly wetting agents, pH adjusters and metal protectants. The metal protectants vary depending on the metal or alloy material. Benzotriazole (BTA) and its derivatives are the main components of metal stinking agents, and iron metal or its alloys are oxalic acid. Phosphoric acid is the main component of the metal protective agent. ' The pretreatment process mainly forms surface modification on the surface of the treated metal or alloy to help surface coating and post treatment; the pretreatment agent used contains titanium dioxide and dioxide. The ruthenium nano-powder sol solution is mainly composed of a suitable organic cerium compound, and a wetting agent and a dispersing agent are added as needed; the pre-treatment agent is uniformly attached to the surface-cleaned metal by painting, soaking or spraying, or The alloy is washed and baked, and then formed into a film by appropriate incineration treatment, that is, the pretreatment process is completed. The nano powder sol used therein has a particle size distribution of 2 〇 4 4 nm; the dispersant used is regarded as Need to be added, the type is mainly polyethylene glycol (pEG) or polypropylene glycol (ppG) or sulfhydryl (NP) or natural alcohol, the molecular weight is between 200~1000', adding 罝 is 10~5000ppm; The agent is mainly composed of octylphenol (〇ctyl Phen〇1, OP) or oil sterol (Oleyl Alcohol) or lanolin, and the amount of the agent 1 is between 200 and 3 500, and the amount is 5 to l 〇〇〇 ppm. Suitable conditions for incineration There are different types of enamel powder sol and organic bismuth compound, the temperature range is from 150 ° C to 400 ° C, and the incineration time is from 1 〜 to 4 hours. 1257413 The surface treatment is treated with titanium dioxide and dioxide. Shixi, alumina nano-powder sol solution, the particle size distribution is 3~4〇nm, and adding wetting agent and dispersing agent as needed, wherein the wetting agent and dispersing agent are selected according to the type of insulin powder The composition and dosage are the same as the pretreatment agent; the treatment method is to uniformly adhere the treatment agent to the surface of the metal or alloy by applying the method of soaking or spraying, and after washing and drying, the post-treatment is performed. The program is based on the type of nano-nano powder, particle size and substrate properties. It can be divided into high temperature incineration and low temperature curing. The high temperature incineration temperature ranges from 20 (rc~7〇(rc, incineration time is 3 〇1) ~24 hours; low temperature curing is allowed to stand at room temperature for 1 to 14 days. After the above treatment of the metal or alloy, the surface will form a uniform, dense and well-adsorbed film protective layer, which not only has a smooth surface, but also tends to foul, and has obvious improvement in corrosion resistance, oxidation resistance and the like. [Examples] The following examples are given to illustrate the contents of the present invention, but the scope of the present invention is not limited to the examples. First Embodiment: The tube of the copper water pipe is immersed in sulfuric acid (3%), Three minutes (temperature) in a micro-suricue consisting of hydrogen peroxide (10%) and BTA (100 ppm). After washing and drying, the surface is coated with a nano-solute sol solution of cerium dioxide. Bake for 1 hour, then soak in titanium dioxide, diced milk, oxidized rice nano-sol sol solution - minute (temperature 25 C), and then sinter under the conditions of 3 sails, 2 hours, that is 10 1257413 products. After the original pipe fittings, after treatment, Λ ^ (not & 尨), after sintering, respectively, with the humic acid etchant, copper chloride etched ~ wind 0 夂 • x 'night' bubble, observe the copper surface color time as shown One
由表一可知，本奈米粉體溶膠溶液處理的銅材管件在 耐酸、耐蝕的性能上有明顯的改善。 實施: 將不鏽鋼一 304以磷酸（3〇mi / l)、草酸（i〇g/L) 及潤濕劑配成的清潔劑浸泡後，以二氧化矽的奈米粉體溶 膠溶液喷灑其表面，經250。(：烘烤丨小時後，再浸泡於二 氧化鈦、二氧化石夕、氧化紹的奈米粉體溶膠溶液一分鐘（ 溫度25°C )，取出後經水洗、烘乾，然後在55〇。(：的條件 下燒結，時間2小時，即為成品。將原材料、處理後（未 1257413 燒結）、燒結後，分別以鹽酸、硝酸、氯化鐵蝕刻液浸泡 ，觀察銅面變色時間如下表（附表二）： 才篆品 原材料 處理後 (未燒 結） 燒結後 鹽酸 (18% ) 5分鐘 6小時 72小時 硝酸（ 10M) 40秒 20分鐘 2.5小時 氯化鐵 餘刻液 5秒 3分鐘 40分鐘 表二：不同處理方式鐵材耐蝕測試 由表二可知，本奈米粉體溶膠溶液處理的鐵材在耐酸_ 、耐蝕的性能上有明顯的改善。 【圖式簡單說明】 無 12It can be seen from Table 1 that the copper pipe fittings treated by the nano-powder sol solution have a significant improvement in acid resistance and corrosion resistance. Implementation: After soaking stainless steel-304 with a cleaning agent composed of phosphoric acid (3〇mi / l), oxalic acid (i〇g / L) and a wetting agent, spray the surface with a cerium oxide nano-sol sol solution. , after 250. (: After baking for a few hours, immerse in the titanium dioxide, sulphur dioxide, and oxidized nano-powder sol solution for one minute (temperature 25 ° C), take it out, wash it with water, dry it, then at 55 〇. Under the conditions of sintering, the time is 2 hours, that is the finished product. After the raw materials, after treatment (not 1257413 sintering), after sintering, respectively, soaked with hydrochloric acid, nitric acid, ferric chloride etching solution, observe the copper surface discoloration time as shown below (attached table 2): After the raw materials are processed (unsintered), hydrochloric acid after hydrolysis (18%) 5 minutes 6 hours 72 hours nitric acid (10M) 40 seconds 20 minutes 2.5 hours ferric chloride residual solution 5 seconds 3 minutes 40 minutes Table 2 : Corrosion resistance test of iron in different treatment methods As shown in Table 2, the iron material treated by the nano-powder sol solution has obvious improvement in acid resistance and corrosion resistance. [Simple description] No 12