201111554 六、發明說明： 【發明所屬之技術領域】 深入待處理 以及經由該 本發明係一種將奈米材料植入待處理物並 物之表層，以形成陶瓷強化皮膜的製造方法， 方法所獲得之奈米陶瓷強化皮膜。 ' 【先前技術】 目前在業界使用的各式m為滿足其❹時須且 備之各種特性，必須在工件的表層進行加工處理，以增加其 抗磨損、抗腐蝕、抗氧化以及增加其堅硬度、減少其ς度& 能力，以及可對抗熱脹冷縮、或對抗其他因物理或用 引起的破損或變形之因素；此外’各產品的零組件，為了避 免老化所導致的疲勞、堅韌度減損等問題，也常常需要進行 一些加工程序，例如：形成具耐受性材料之被覆層、應力消 除之加工、或定期檢查、維修及更換等作業。 而對於產業界所使用的各種大小型機具而言，其中構件 之抗腐钱、抗磨損的能力’是維護產品使用安全的必要條 件’其耐受度不足的問題，廣受各界重視。 曰例如，機器故障的原因中，與引擎主機的傳動軸、連接 杯、離合器、啟動馬達處所發生的構建材質發生龜裂或損壞 最為有關，因此，對於其對抗變形或磨耗、抗侵蝕的耐受能 力要求很高。 另，產業所使用的模具及加工用器具，其使用壽命對於 業者的成本影響很大。模具需要對抗模内的化學損傷、磨損 及腐餘以及熱疲勞損裂等情況。解決這些問題的技術手段， 可藉由增加模具的硬度，及以特殊表面處理，來達到各種耐 201111554 受能力的需求。 此外，為了解決各種零構件耐受度不足的問題，產業及 研究單位廣泛地尋找各種增加構件抵抗物理及化學耗損的 方法。除了構件本身以純度更高的材料鍛轉，一般已經製作 完成的產品，業界最常採用的方式，就是針對該物品加工， 以各種物理或化㈣方歧行表喊理，· 1由被覆或 各種鍍膜方式，在工件表面形成皮膜或覆蓋層，以增加其 腐餘、對抗變形或财磨耗等功能。 • 在構件表面被覆（coati呢）材質，固然已為廣泛使用的 方法’但是其抗腐蝕及耐磨耗的能力，已經無法達到「陶瓷 覆層技術」所製成的表面薄膜，其所能達到之對抗外在 的能，六。 M于201111554 VI. Description of the invention: [Technical field to which the invention pertains] The method for manufacturing a ceramic reinforced film by the method of the present invention, which is obtained by implanting a nanomaterial into the surface layer of the object to be treated, by the method Nano ceramic reinforced film. [Prior Art] The various types of m currently used in the industry are designed to meet the requirements of the time and must be processed on the surface of the workpiece to increase its resistance to wear, corrosion, oxidation and increase its hardness. , reducing its enthalpy & ability, and can resist thermal expansion and contraction, or against other physical or service-induced damage or deformation; in addition, 'components of each product, in order to avoid fatigue caused by fatigue, toughness For problems such as derogation, it is often necessary to carry out some processing procedures, such as forming a coating of a tolerant material, processing a stress relief, or performing regular inspections, repairs, and replacements. For all kinds of large and small-sized machines used in the industry, the ability of the components to resist money and wear is 'the necessary condition for maintaining the safety of the product', and the tolerance is insufficient. For example, the cause of the machine failure is most related to the cracking or damage of the construction material occurring at the engine main shaft, the connecting cup, the clutch, and the starting motor. Therefore, it is resistant to deformation or wear and erosion. The ability is very high. In addition, the service life of molds and processing tools used in the industry has a great impact on the cost of the operators. The mold needs to be resistant to chemical damage, wear and corrosion in the mold, and thermal fatigue damage. The technical means to solve these problems can be achieved by increasing the hardness of the mold and special surface treatment to meet various requirements for resistance to 201111554. In addition, in order to solve the problem of insufficient tolerance of various components, the industry and research institutes have extensively sought ways to increase the resistance of components to physical and chemical wear and tear. In addition to the fact that the component itself is forged with higher purity materials, the products that have already been produced are generally used. The most commonly used method in the industry is to process the article, and use various physical or chemical (4) square-shaped lines to scream, 1 by coating or various coatings. In a way, a film or a cover layer is formed on the surface of the workpiece to increase its rot, resist deformation or wear and tear. • The surface of the component is coated (coati), although it has been widely used, but its ability to resist corrosion and wear and tear has not been able to achieve the surface film made by "ceramic coating technology". Against the external energy, six. M
目前金屬鋼材，對於外在環境影響所引發酸性、鹼性、 防鏽、導熱、散熱、耐熱、耐磨、抗壓縮等阻抗要求，而盔 法達到預期的使用壽命；現今熱處理界為了達到上述要東 大多利用表面處理進而改善，例如氮化處理、複合滲(im 法、物理氣相沉積（PVD)法、化學氣相沉積（CVD)&°、二 層等；但是’又因作用溫度過高，造成底材硬度下降及^ 或鍍層剝落之狀況發生。 乂 金屬表面陶瓷膜層製作技術，常見的有：利用化取 膜、複合電刷鍍膜、複合電鍍、熱喷烊噴塗、離子注入:蟪 理氣相沉積等方法，而將含有碳、氮、硼、矽和氧等 物 兗材料鑛於工件表面。這樣即可在玉件表面上形成緻密氧= 物陶瓷膜層，而使基質構體具有高性能的表層。 乳化 然而即使是一般的陶瓷薄膜技術，業界所採用的方 舊存在著：加工溫度過高、膜層過薄（陶竟皮膜層未能到達= 201111554 處理物的深層）'廢品及汙染過多等瓶頸，此外，有些硬質 基材不易被液態或流態金屬/_材料植人，以致無法有效 製作膜層’或是在外界環境有水分的情形下，會汗染或導致 膜層產生缺陷，這類問題都有待解決。 為滿足上述之針對工業構件製成陶瓷膜層的需求，本發 明土基於多年從事研發與諸多實務經驗，經多方研究設計與 測试探討，遂提出一種奈米陶究強化皮膜之製造方法及其 製成之強化皮膜’以作為前述課題之實現方式與依據。本發 拳 明之製造方法及其產出物具有新穎性，可提供產業上利用，且確 實具有增進功效的能力，確實具備產業價值而符合業界所需。 【發明内容】 有鑑於上述課題，本發明之主要目的為··提供一種奈米 陶瓷強化皮膜之製造方法及其製成之強化皮膜，以增強習 知技術的功效，達到有效製造工件及模具之奈米陶瓷皮 膜、增強構件強度、防止形變、抗磨耗、利用表面改質而 增加可處理的基材品目、使用符合環保的材料及機具、提 • 高奈米陶瓷深入構件的厚度、加工溫度較低、抵抗模具損 傷、抗磨損及耐腐钕、抗溫度震盪（temperature shock)之 熱疲勞損裂等目的。 作用時在常溫下（Room Temperature)，利用酸驗電位差 比’將奈米陶瓷（Nano Ceramic)進入金屬鋼鐵中，藉由界面 (Interface)轉換置入基材（Substratum)内，再利用溫度差 異變化進行熟化（Ripening)，將奈米陶瓷封孔，其金鋼皮膜 符合歐盟環保（R〇HS)標準。 201111554 本』之是二皮膜的主要目的，依 種不水陶瓷強化皮膜之製 耵依 -將不米陶£微粒植入待處理物以形成陶瓷至少包含： 及-將陶瓷皮膜往待處理物深m層：程序；以 且，為達上述製造可增加膜曰=5=，。 的又一目的，依本發明之一種夺曰又強丁 =陶竞強化皮膜 法，其中包含:-將奈米陶二之製造方 ;層之程序；以及-將陶曼皮膜以渗氮加工往：；形成陶 層擴散之高溫熟化程序。 工在待處理物深 層的再又」目為=發免:之些另材質::高温無法達成製作膜 將奈米陶㈣植入待處理物以ΐ 深層擴二=之;;:在低溫下㈣皮膜往待處理物 再者，為達上述使強化皮膜更具功效的另—目的，依 =發明之另-種奈米陶£強化皮膜之製造方法其中包 ^具有水分、酸成分或鹼成分的前處理程序；一將奈 米陶瓷微粒植入待處理物以形成陶瓷層之程序；以及一二 陶瓷皮膜往待處理物深層擴散之熟化程序。 承上所述’依據本發明之奈米陶瓷強化皮膜之製造方 法’其為可在常溫（Room Temperature)或特定之溫度下， 寿J用酉文驗電位差比（化學鐘或無電鍛electroless plating 或利用電鍍）’將奈米陶曼（Nano Ceramic)材料植入 (implant)待處理物之中，藉由界面（interface)轉換植入 基材（Substratum)内，再利用溫度差異變化進行熟化 Ripening)，將奈米陶瓷更深層的推入基材中，產生結締 201111554 組織（CormectiveTissue;其中含晶質層及非晶質層），形 成奈米陶莞強化皮膜。其所產生的強化皮膜可提⑽處理 之基材^孔、提升财磨耗、耐高溫、高導熱能力、高散熱 能力、高導電能力、抗酸鹼能力、抗生鏽及增加抗壓縮之 強度等性能及功效。又因加工程序中，可視基材選擇高溫 或低溫程序，而可適用於各種的工件基材。 茲為使貴審查委員對本發明之技術特徵，及其所達成 之功效能更進一步地瞭解與認識，以下文提供各較佳之實施 泰 例及相關圖式，並以詳細之說明文字配合說明如後。 【實施方式】 請參閱第-圖’係為本發明之奈米陶变強化皮膜之製造流 程圖； 本發明之「奈米陶瓷強化皮膜之製造方法及其製成之強 化皮膜」之第一較佳實施例包括以下步驟： ,1 〇.〇、前處理程序（初步表面處理）： 1 1 0、首先進行脫脂步驟:將待處理物置於脫脂槽，透過選自符 • 合此耶環保規定的、無機或者有機溶劑類的脫脂劑（如：美國 LPS laboratories公司出產的鹼性水溶液脫脂劑，或者是碳氫 化合物類溶劑）等脫脂溶液之浸潰，進行金屬鋼材等基材之脫 脂、去鏽及去汙等處理，以恢復金屬等基材表面原有光澤； 1 2 0、使用水洗或以酸劑清洗··將待處理物置入水洗槽或酸洗槽 並進行超音波震盪，以去除附著於金屬鋼材表面殘留的藥劑及 氧化物雜質，如此可確保後續的處理程序中，不會有外界雜質 與待處理之基材間交互汗染的現象； 1 3 0、吹乾:去除金屬鋼材等基材表面之水分殘留，以利後續處 201111554 理程序作業； 1 4 0、綱_或翻洗舰—步清洗並财充分洗淨； 1 5 0、烘乾⑽〜5〇()。〇:進—步去除金屬表面的揮發性物質， 以利後續處理作業； 1 6 0、真空或表面清洗處理··將待處理物置人真空清洗槽，再進 -步去除金屬表面的非揮發性物f，以利後續處理； -2 0 0、植入（Implant)程序： 2 1 0、殊層活化（depassivati〇n)處理:將待處理物送入活化 > 處_，使職驗驗(本财用濃度極低之氫_册或石肖 酉义"磷魷、％酸、冰醋酸、酒石酸、氫氧化鈉、碳酸鈉、 亞石肖酸鈉、含树_、_納、氣仙或氣水等）將工 件表面的«職、熱喊其他域㈣去除並且進行表面到 深層的清理及活化； 2 2 0、奈米陶竟微粒溶液之表面洗注處理:將工件送入微粒溶液 (Nar^a-granule liquid)槽，注入奈米陶瓷微粒（直徑為1〇_6 〜10 9m)及分散劑和溶劑所形成的微粒溶液。利用酸鹼電位差比 .的特f生，使微粒〉谷液與待處理物表面進行粒子及離子的交換 (凊參考第二圖及第四圖所示之金屬待處理物之成分，如:鐵離 子、鉑粒子、鈦粒子、鉻離子、鉬成分、釩成分、鎢等成分）； 將金屬材質置換成含石夕的奈米陶变微粒溶液成分(本例中為At present, metal steel has the impedance requirements of acidity, alkalinity, rust prevention, heat conduction, heat dissipation, heat resistance, wear resistance and compression resistance caused by external environmental influences, and the helmet method achieves the expected service life; Most of the East is improved by surface treatment, such as nitriding treatment, composite infiltration (im method, physical vapor deposition (PVD) method, chemical vapor deposition (CVD) & °, two layers, etc.; but 'by temperature High, resulting in a decrease in the hardness of the substrate and the occurrence of peeling of the coating. The fabrication techniques of the ceramic layer on the surface of the base metal are: using the film, composite brush coating, composite plating, thermal spray coating, ion implantation: A method such as vapor deposition is used to deposit a material containing carbon, nitrogen, boron, antimony and oxygen on the surface of the workpiece, so that a dense oxygen-ceramic film layer can be formed on the surface of the jade piece, and the matrix structure can be formed. High-performance surface layer. Emulsification However, even the general ceramic film technology, the industry has used the old: the processing temperature is too high, the film is too thin (the ceramic film layer failed to reach = 201111554 Deep in the treatment) Bottlenecks such as waste and excessive contamination. In addition, some hard substrates are not easily implanted by liquid or fluid metal/materials, so that they cannot be effectively formed or have moisture in the external environment. Under the influence of sweating or causing defects in the film layer, such problems have to be solved. In order to meet the above requirements for the production of ceramic film layers for industrial components, the invention is based on years of research and development and many practical experiences, and has been designed and researched by many parties. In connection with the test, a method for producing a nano-ceramic reinforced film and a reinforced film made thereof are proposed as a realization method and basis of the above-mentioned problems. The manufacturing method and the output of the present invention are novel. It is industrially usable, and it has the ability to improve the efficiency, and it has the industrial value and meets the needs of the industry. SUMMARY OF THE INVENTION In view of the above problems, the main object of the present invention is to provide a nano-ceramic reinforced film. The method and the reinforced film made thereof are used to enhance the efficiency of the conventional technology and to effectively manufacture the workpiece and the mold Ceramic film, reinforcing member strength, deformation prevention, abrasion resistance, surface modification to increase the number of substrates that can be processed, use of environmentally-friendly materials and implements, thickness of G-nano ceramics, deep processing, low processing temperature Resisting mold damage, anti-wear and anti-corrosion, thermal shock resistance against temperature shock, etc. At room temperature, using the acid potential difference ratio 'Nano Ceramic' Into the metal and steel, through the interface (Interface) conversion into the substrate (Substratum), and then use the temperature difference change for ripening (Ripening), the nano-ceramic sealed, the steel film is in line with the EU environmental protection (R〇HS The standard. 201111554 This is the main purpose of the two membranes, according to the system of non-aqueous ceramic reinforced membranes - the implantation of the granules into the material to be treated to form ceramics at least: and - the ceramic membrane Treatment of the deep m layer: the program; and, in order to achieve the above manufacturing can increase the film 曰 = 5 =,. A further object, according to the invention, is a sturdy and strong Ding = Tao Jing reinforced film method, which comprises: - a process for manufacturing nano-Taoji; a layer; and - processing the taman film with nitriding :; Forming a high temperature curing process for the diffusion of ceramic layers. In the deeper layers of the work to be treated, the purpose is again: the other materials:: high temperature can not be achieved to make the film, nano-potassy (four) is implanted into the object to be treated to deepen the second layer;;: at low temperature (4) The film is treated to the object to be treated, in order to achieve the above-mentioned effect of making the reinforced film more effective, according to the invention of the invention, the method for producing the reinforced film of the nano-potato has a moisture, an acid component or an alkali component. Pre-treatment procedure; a procedure for implanting nano ceramic particles into a material to be treated to form a ceramic layer; and a curing process for deep diffusion of the ceramic film to the object to be treated. According to the 'manufacturing method of the nano-ceramic reinforced film according to the present invention', it is possible to check the potential difference ratio (chemical clock or electroless plating or electroless plating at room temperature or specific temperature). Using electroplating) 'Nano Ceramic' material is implanted into the object to be treated, and the substrate is converted into a substrate (Substratum), and then the temperature difference is used to mature Ripreing) The nano ceramic is pushed deeper into the substrate to form a connective 201111554 tissue (CormectiveTissue; which contains a crystalline layer and an amorphous layer) to form a nano-pottery strengthening film. The reinforced film produced by the invention can provide (10) processing of the substrate hole, increase the wear and tear, high temperature resistance, high thermal conductivity, high heat dissipation capability, high electrical conductivity, acid and alkali resistance, rust resistance and strength of compression resistance. Performance and efficacy. In addition, it is applicable to various workpiece substrates in the processing program by selecting a high temperature or low temperature program for the substrate. In order to enable the reviewing committee to further understand and understand the technical features of the present invention and the effects achieved by the present invention, the preferred embodiments of the Thai and related drawings are provided below, and the detailed explanations are followed by a description. . [Embodiment] Please refer to the figure - Figure ' is a flow chart for manufacturing a nano-ceramic reinforced film of the present invention; the first method of "the method for producing a nano-ceramic reinforced film and the reinforced film made thereof" of the present invention The preferred embodiment comprises the following steps: , 1 〇.〇, pre-treatment procedure (preliminary surface treatment): 1 1 0, first degreasing step: placing the object to be treated in a degreasing tank, through the selection of the environmental protection regulations Degreasing of a degreasing agent such as an inorganic or organic solvent degreaser (such as an alkaline aqueous degreasing agent produced by LPS Laboratories, Inc., or a hydrocarbon solvent), and degreasing and derusting a substrate such as a metal steel. And decontamination and other treatments to restore the original luster surface of the substrate such as metal; 1 20, using water or acid cleaning · Place the object to be treated in a washing tank or pickling tank and perform ultrasonic vibration to remove the adhesion The residual chemical and oxide impurities on the surface of the metal steel ensure that there is no interaction between the external impurities and the substrate to be treated in the subsequent processing procedure; 1 30 Dry: remove the moisture residue on the surface of the substrate such as metal steel, in order to facilitate the subsequent operation of 201111554; 1 40, _ or retreading ship - step cleaning and fully clean; 1 50, drying (10) ~ 5 〇(). 〇: Step-by-step removal of volatile substances on the metal surface for subsequent processing; 1 60, vacuum or surface cleaning treatment · Place the object to be treated in a vacuum cleaning bath, and then step-by-step to remove non-volatile metal surface Substituting f for subsequent processing; -200, Implant procedure: 2 1 0, depassivati〇n treatment: sending the object to be treated to activation > (This hydrogen is very low concentration of hydrogen _ book or Shi Xiaoyiyi " phosphonium, % acid, glacial acetic acid, tartaric acid, sodium hydroxide, sodium carbonate, sodium succinate, containing trees _, _ nano, gas fairy or Gas, water, etc.) removes the surface of the workpiece, heats up other fields (4) and performs surface to deep cleaning and activation; 2 2 0, surface treatment of nano ceramics particle solution: feeding the workpiece into the particle solution ( The Nar^a-granule liquid tank is filled with nano-ceramic particles (having a diameter of 1〇_6 to 10 9m) and a fine particle solution formed by a dispersant and a solvent. The particle and the surface of the object to be treated are exchanged for particles and ions by using the specificity of the acid-base potential difference ratio (refer to the components of the metal to be treated shown in the second and fourth figures, such as iron). Ions, platinum particles, titanium particles, chromium ions, molybdenum components, vanadium components, tungsten, etc.); replacing the metal material with a nano-ceramic particle solution containing Shishixi (in this case
SiC、SiN、CK、SiK、PtM、MoL、VK、CrK、FeK、及WC，按照 待處理工件的材質，分別調整溶液成分比例），而將奈米陶兗 植入待處理物表面或於埋入其孔隙中； 2 3 0、再進行高溫固化成型/低溫燒結。產生結締組織 (C〇nnective Tissue ;其中含晶質層及非晶質層），形 成奈米陶瓷強化皮膜。 201111554 3 〇 Q.、熟化(Ripening)程序： 3 1 0、進行高溫熟化處理(適用的基材係選自各式耐高溫材質如 金屬、合金及鋼鐵等）； 311、將待處理之基材及承载基材的容器以天車送人高溫處理 槽（本例中使用真空爐）巾；為了增加能被奈米材質植入基材 表層，以及達成將奈__人基材深層+的目的，'所以二對 待處理物進行表面滲氮處理，及奈米喊滲人處理程序； 3 12將氮化處理槽/爐以泵抽為真空(爐内約達到 ，小HTinbaK毫巴）壓力）’將一般空氣及其十的雜質抽除； 3 13、接著，逐漸注入高壓氮或氣態氮(注入速度為 將待處理轉進行表面淨化(purging)，此時爐中達到正壓（以 閥門排氣維持爐内壓力為丨· 5kg/平方公尺）； 314、接著開始均勻地加熱，並以氣體對流，進行熱傳導 後達到300〜500 〇C並維持定溫持續12〜36小時。經過熟化處理 的奈米陶竟薄膜可深入基材達仙卯以上(請參閱第二圖之第 -實施例的金相攝影’可測得膜層深度達4〇卵以上，而未經 . 熟化處理的陶瓷層僅能達到約2/zm深度）。 、、 本發明之「奈米喊強Μ狀製造方法及其製成之 化皮膜」之弟二較佳實施例包括以下步驟.· 將工件基材先麵復〇_之祕财序及之植 後再進行以下步驟： 序 -S-Q 〇、熟化(Ripening)程序： 3 低溫熟化處理(適用的基材為較不適於高溫處理材質 或谷易變形者，如選自鋁系合金材質的工件）； 、 3 2理1 梓之基材及承載該基材的容器以天車送入低溫處 理槽（本例中使用超深冷槽）中，為了增加能被奈米材質植入 201111554 達成將奈米陶細推入基材深層中的目的， ’、（處⑯進行表面渗氮處難序，及奈米_渗入程 序， 3 2 2、將低溫處理槽抽為真空(5χ1(Γΐ小的㈤）； 3 2度3 以速度如每分瓣低2.5°c的速 ’且在適當條件下，可進行回收該冷卻 L付口^即能的製程），將待處理工件自環境溫度以2.5SiC, SiN, CK, SiK, PtM, MoL, VK, CrK, FeK, and WC, according to the material of the workpiece to be processed, respectively, adjust the proportion of the solution component), and implant the nano-ceramics on the surface of the object to be treated or buried Into the pores; 2 3 0, then high temperature curing molding / low temperature sintering. Connected tissue (C〇nnective Tissue; which contains a crystalline layer and an amorphous layer) forms a nano-ceramic reinforced membrane. 201111554 3 〇Q., Ripening procedure: 3 1 0, high temperature curing treatment (suitable substrate is selected from various high temperature resistant materials such as metals, alloys and steel); 311, the substrate to be treated And the container carrying the substrate is sent to the high temperature treatment tank (in this case, a vacuum furnace) towel; in order to increase the surface layer of the substrate which can be implanted by the nano material, and to achieve the purpose of deep layering of the substrate. , 'So the second treatment of the surface of the treatment with nitriding, and the nano-shock infiltration process; 3 12 nitriding treatment tank / furnace pumping vacuum (in the furnace about reached, small HTinbaK mbar pressure) ' The general air and its ten impurities are removed; 3 13, and then, high pressure nitrogen or gaseous nitrogen is gradually injected (the injection speed is to purify the surface to be treated, at which time the furnace reaches a positive pressure (with valve exhaust) Maintain the pressure in the furnace is 丨·5kg/m2); 314, then start to heat evenly, and conduct gas conduction, heat conduction to reach 300~500 〇C and maintain the constant temperature for 12~36 hours. After curing Nano-Tao film can penetrate the substrate Above the immortal (see the metallographic photography of the second embodiment - the embodiment can measure the depth of the film up to 4 eggs, while the ceramic layer without the ripening can only reach about 2 / zm depth). The preferred embodiment of the "nano shouting method and the film made thereof" of the present invention includes the following steps: · re-recovering the workpiece substrate _ the secret recipe and planting Then proceed to the following steps: Order-SQ 〇, Ripening (Ripening) procedure: 3 Low temperature curing treatment (applicable substrate is less suitable for high temperature processing materials or valley deformable, such as workpieces selected from aluminum alloy materials); , 3 2 1 1 梓 基材 基材 及 及 及 及 及 及 基材 基材 基材 基材 基材 基材 基材 基材 基材 基材 基材 基材 基材 基材 基材 基材 基材 基材 基材 基材 基材 基材 基材 基材 基材 基材 基材 基材 基材 基材 基材 基材 基材 基材 基材 基材 基材 基材 基材 基材The purpose of pushing the ceramic into the deep layer of the substrate, ', (the 16 is difficult to sequence the surface nitriding, and the nano-infiltration procedure, 3 2 2. The low-temperature treatment tank is vacuumed (5χ1 (Γΐ小(五)) ; 3 2 degrees 3 at a speed of 2.5 ° C per minute, and can be recycled under appropriate conditions Cooling L ^ port that can pay for the process), since the workpiece to be processed at ambient temperature 2.5
處二^降ί ;持續降低溫度到零下120〜職，持續低溫 處理12〜48小時； 枝—接著開始均勻地升溫，最後達到環境溫度（室溫)並維 ^溫。經過此一步驟後，奈米陶細b皮膜層可以深入基材 達l〇//m以上。 請參閱第三圖及第四圖所示，將加工後的基材切出試片樣本， ，過本發明之熟化處理後，以胍技術(χ射線散射光譜儀;En卿 ispei*sive Χ’）測試樣本中的元素成分（定性及定量分析）。苴 中^本，例所得基材中央（芯部)及邊緣(表層）各取之試片了 其疋1(重量百分比)及定性(分舰原子相量碳、⑦、翻、翻、 飢、。鉻、?、鶴)結果為:含碳量由基材中央處所取出之試片的 3. 38/0(重1百刀比），上升到基材邊緣處所取出之試片的 14. 5挪（4日量百分比）；切量由基材中央處所取出之試片的 1/7/。(重量百分比）’上升到基材邊緣處所取出之刻的5.挪(重 量百刀比）’含i自量由基材巾央處所取出之則的5.順重量百分 比)曰’上升到基材邊緣處所取出之試片的9·概重量百分比）；含 錮董由基材中央處所取出之試㈣4 71%(重量百分比），上升到基 材邊緣處所取$之試>;的13·64%(重量百分比）·，含縫由基材中 央處所取iti之制的1鹰(重量百分比），上升到基材邊緣處所取 201111554 片出==重7分比);含路量由基材中央處所取出之試 片^7(U(重$百分比），到基材邊緣 析出含鉻；含鐵量由基材中央處 出之忒片中則未此刀 H其If處所取出之試片的说⑽(重量百分比）•’含 編㈣，刪 請m五圖、第六圖、第蝴及第八圖本發明之作用過程 中’…T *陶倾粒溶液之塗佈及植人係在常溫下一 ΤΖ ' 5 ^ =(N咖GeramiG)進人金屬峨中，料界面（&㈣⑽） 、.入基材（Substratum)内，再利用溫度差異變化進行熟 卿㈣，將奈米陶究封孔，其金鋼皮膜符合歐盟環保 〇心準’且無論其奈米材料、設備、藥劑及製程都符合 歐盟有關於環保的規範。在第五圖中，本發明之強化皮膜(金 鋼皮膜）的鍍層特性與其他基材表面處理的效果進行比較，可發現 其具有:硬度猶低而膜層厚度極高的現象。第六圖中，本發明之全 陶曼銑刀使用壽命與日本銑刀使用壽命之比較，本發明可增加銳 刀之使用寿命。第七圖中，本發明之實驗針孔測試，以硫酸銅試 液（90%水加上1〇%硫酸銅）浸泡處理及未處理過的工件，則未處理 的工件，因為其表層具有許多微細孔洞，故很快即會沾染上銅著 色；而經過本發明處理的工件，並未呈現銅著色，證明其表面微 細孔洞均以奈米陶瓷封孔。第八圖中，為本發明經過水液等流體 喷灑，因表面陶瓷化，故外部流體不易黏滯於其表面。 另外，本發明能夠處理製作螺絲的模具如：牙板(screw rolling die)，使其壽命提升loo〜300%，·且如前段内容所述，可提升封孔 的效果；以及可提升工件耐受極端環境的能力，例如：經本發明處 201111554 =過之剎車盤，當交通工具由時速200公里瞬間剎車達到時速70 么里時，本刹車盤可耐受共達七次以上的操作，而未發生變形， 相，較之下，未經處理的剎車盤，以同樣條件僅運作一次該種減 U車之動作’就會發生變形而無法使用；此外運用在刀具的處 理上時，如第八圖所示，可以抗沾黏也可以防止指紋等痕跡，而 保持工件的表面潔淨。 . c綜上所述，本發明人基於多年從事研究與諸多實務經驗， 么多方研九6又计與專題探討，遂於本發明提出一種「奈米陶 • 瓷強化皮膜之製造方法及其製成之強化皮膜」。經過該等程 序所製成的奈米陶瓷強化皮膜，將可達到具備耐磨耗、導 熱、散熱、耐高溫、抗腐蝕、導電、導磁、消除磁性以及 不易變形等特性。 ，本發明無論就目的、手段及功效，在在均顯示其迥異於習知技 術之特徵，因此本發明具有新穎性，能提供產業上利用，且確實 具有增進功效的能力，爰依法申請發明專利。惟應注意的是，上 述諸多實施例僅係為了便於說明而舉例而已，本發明所主張之權 餐利範圍自應以申請專利範圍所述為準，而非僅限於上述實施例。 【圖式簡單說明】 第一圖：本發明之奈米陶瓷強化皮膜之製造流程圖。 第二圖：本發明之較佳實施例的金相攝影圖。 第二圖.本發明之強化皮膜的腿技術(X射線散射光譜 儀；Energy Dispersive X-ray)測試之圖譜(基材中 央試片）。 第四圖：本發明之強化皮膜的腿技術(X射線散射光譜 12 201111554 儀；Energy Dispersive X-ray)測試之圖譜(基材邊 緣表面試片）。 第五圖：本發明之活化皮膜的鐘層特性比較圖。 第六圖：本發明之全陶竟銳刀使用壽命比較圖。 第七圖：本發明之實驗針孔測試圖(銅著色試液浸泡圖）。 第八圖：本發明之喷漆沾黏性質圖。 【主要元件符號說明】 • 10 0、前處理程序 1 10、脫脂步驟 1 2 0、水洗/酸洗 1 3 0、吹乾 14 0、臉類或酸類洗劑清洗 15 0、烘乾 1 6 0、真空/表面清洗處理 Φ 2 0 0、植入（Implant)程序 210、深層活化處理 2 2 0、微粒溶液表面澆注處理 2 3 0、固化/燒結 3 0 0、熟化(Ripening)程序 310、 高溫熟化處理 311、 置入高溫處理槽 201111554 312、抽真空 3 1 3、’主入而壓氮 3 1 4、加熱至300〜500°C維持12〜36小時 3 2 0、低溫熟化處理 3 21、置入低溫處理槽 3 2 2、抽真空 3 2 3、注入冷卻劑並冷卻至一120〜一190°C持續12〜48小時 Λ 3 2 4、升溫至室溫At the same time, the temperature is lowered to minus 120%, and the low temperature treatment is continued for 12 to 48 hours; the branching - then begins to uniformly heat up, and finally reaches the ambient temperature (room temperature) and maintains the temperature. After this step, the nano-ceramic b-film layer can penetrate the substrate up to l〇//m or more. Referring to the third and fourth figures, the processed substrate is cut out of the test piece sample, and after the ripening treatment of the present invention, the enthalpy technique (χ 散射 scattering spectrometer; Enqing ispei*sive Χ') Test the elemental composition (qualitative and quantitative analysis) in the sample. In the middle of the sample, the center (core) and the edge (surface) of the obtained substrate were taken from the test piece (疋%) and qualitative (the atomic phasor of carbon, 7, turn, turn, hunger, The result of the test piece taken out from the center of the substrate is 3. 38/0 (weight 1 knives ratio), and the test piece taken up at the edge of the substrate is 14. 5 Move (4% percent); cut 1/7/ of the test piece taken from the center of the substrate. (% by weight) '5. (100% of the weight ratio) that is taken out at the edge of the substrate. The percentage of the weight contained in the substrate is taken from the center of the substrate. The percentage of the weight of the test piece taken out at the edge of the material); the test taken by the center of the substrate (4) 4 71% (by weight), and the rise of the sample taken at the edge of the substrate is 13.64% (% by weight) ·, the eagle (weight percentage) of the joint made from the center of the substrate, rising to the edge of the substrate taken 201111554 piece == weight 7 points); the path is from the center of the substrate The test piece taken out at the place ^7 (U (weight: %), the chromium is precipitated to the edge of the substrate; the test piece of the test piece taken out from the If) where the iron content is from the center of the substrate (10) (% by weight) • 'Including (4), delete m, 5, 6, and 8 in the process of the invention '...T * potting solution and implanting at room temperature The next ΤΖ ' 5 ^ = (N Cafe GeramiG) into the metal enamel, the material interface (& (4) (10)), into the substrate (Substratum), reuse The change in temperature difference is carried out by Shuqing (4), and the nano-ceramics are sealed, and the gold-steel film conforms to the EU environmental protection standards and the nano-materials, equipment, chemicals and processes are in line with the EU's environmental protection regulations. In the fifth figure, the coating properties of the reinforced film (gold steel film) of the present invention are compared with those of other substrate surface treatments, and it is found that the hardness is low and the film thickness is extremely high. In the sixth figure, Compared with the service life of the Japanese milling cutter of the present invention, the present invention can increase the service life of the sharp knife. In the seventh figure, the experimental pinhole test of the present invention uses a copper sulfate test solution (90% water plus 1〇% copper sulphate) soaked and untreated workpieces, untreated workpieces, because the surface layer has many fine holes, it will soon be stained with copper; while the workpiece processed by the present invention is not presented The coloration of copper proves that the micropores on the surface are sealed by nano ceramics. In the eighth figure, the invention is sprayed with a fluid such as water and liquid, and the external fluid is not easily adhered to the surface due to surface ceramization. In addition, the present invention is capable of processing a mold for making a screw such as a scrap rolling die, and has a life improvement of loo~300%, and as described in the foregoing paragraph, the sealing effect can be improved; and the workpiece can be lifted. The ability to withstand extreme environments, for example: through the brake disc of the 201111554 = 2011, when the vehicle is braked at a speed of 70 km/h and the speed is 70, the brake disc can withstand more than seven operations. No deformation, phase, or lower, untreated brake disc, only operate once in the same condition, the action of the U-reduction vehicle will be deformed and cannot be used; in addition, when used in the processing of the tool, As shown in Figure 8, it can resist sticking and prevent fingerprints and other traces while keeping the surface of the workpiece clean. c In summary, the inventor has been engaged in research and many practical experiences for many years, and has developed a method for manufacturing nano-ceramic porcelain reinforced film and its system. Intensive film." The nano-ceramic reinforced film made by these procedures can achieve wear resistance, heat conduction, heat dissipation, high temperature resistance, corrosion resistance, electrical conductivity, magnetic permeability, magnetic elimination and deformation resistance. The present invention, regardless of its purpose, means, and efficacy, exhibits characteristics that are different from conventional techniques, and thus the present invention is novel, can provide industrial use, and does have the ability to enhance efficacy, and applies for invention patents according to law. . It should be noted that the above-described embodiments are merely examples for convenience of description, and the scope of the claims of the present invention is determined by the scope of the patent application, and is not limited to the above embodiments. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a flow chart showing the manufacture of a nano-ceramic reinforced film of the present invention. Second Figure: A metallographic photograph of a preferred embodiment of the invention. Fig. 2 is a map of the leg technique (X-ray scattering spectrometer; Energy Dispersive X-ray) test of the reinforced film of the present invention (substrate central test piece). Figure 4: A map of the leg technique of the reinforced film of the present invention (X-ray scattering spectroscopy 12 201111554; Energy Dispersive X-ray) (substrate edge surface test piece). Fig. 5 is a graph showing a comparison of the bell layer characteristics of the activated film of the present invention. Figure 6: Comparison of the service life of the full ceramics sharp knife of the present invention. Figure 7: Experimental pinhole test chart of the present invention (copper coloring test solution soaking chart). Figure 8 is a graph showing the adhesion properties of the spray paint of the present invention. [Main component symbol description] • 10 0, pre-treatment program 1 10, degreasing step 1 2 0, washing/pickling 1 3 0, drying 14 0, face or acid lotion cleaning 15 0, drying 1 6 0 , vacuum / surface cleaning treatment Φ 200, implant (Implant) program 210, deep activation treatment 2 2 0, particle solution surface casting treatment 203, curing / sintering 300, ripening (Ripening) program 310, high temperature The aging treatment 311, placing the high temperature treatment tank 201111554 312, evacuating the vacuum 3 1 3, 'mainly entering the nitrogen pressure 3 1 4, heating to 300 to 500 ° C for 12 to 36 hours 3 2 0, low temperature curing treatment 3 21, Place the low temperature treatment tank 3 2 2. Drain the vacuum 3 2 3, inject the coolant and cool to a temperature of 120 to 190 ° C for 12 to 48 hours Λ 3 2 4, warm to room temperature
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