200927994 九、發明說明： 【發明所屬之技術領域】 本發明涉及-觀合朗形成方法及其裝置，尤其是一種具有 多孔塗層之複合膜的形成方法及其裝置。 【先前技術】 薄臈分離為-省能源且又輯之分離技術，因此薄膜分離程序 已經逐誠為化學4、水處理、食品加卫、生醫科技及電子產業 等方面的重要分離齡。在_分_序中，細蝴料可分為有 機薄膜、無機義和有無機混合_，其中，無機材料的熱穩定 性、機械穩定性和化學敎性_#好，因此無機賴在分離程序 上有相當廣泛的_，不論是在微過濾、超過_氣體分離技術甚 至疋薄联反應器上都扮演重要角色。 夕無機薄膜依其表面層的形態可大致分為緻密膜和多孔膜兩種， 夕孔膜由於其树量較緻贿高，因此紅業上的使用比較廣泛， 夕孔,、、、機相制上的功能亦較多，例如氣體分離，固液分離中 的微過;慮超猶’甚至是奈来職、，都是其應用賴。 在多孔無機薄_製備方法中，—般常見的有轉·凝膠法 (S〇1调、固態粒子燒結法、化學氣相沉積法(chemical vapor deposition， CVD)等’但上述製程之鱗繁複、製備_冗長、職_受限等 缺點，限制盆-φ- 1 . "第上之應用。有鑑於此，仍有必要開發新的薄膜 200927994 裝置與製程’以製造具有多孔塗層之複合膜，並降低生產成本。 【發明内容】 鑒於上述之發明背景中’為了符合產業上之需求，本發明提供 一種具有多孔塗層之複合膜的形成方法及其裝置，可用以解決上述 傳統技術未能達成之標的。 本發明之一目的在於藉由液體受熱汽化之原理，以製備多孔無 ❹機薄膜。首先，將熔融液滴喷塗至充填有液體之多孔基板表面，藉 由液滴之高溫氣化多孔基板孔隙中之液體並形成蒸汽，蒸汽貫穿液 滴，使液滴濺射成不同的區塊，冷卻固化後形成不規則且分散狀的 扁平粒子，持續形成與堆疊扁平粒子，藉此形成一具有多孔塗層之 複合膜。 本發明之另一目的在於使用有機高分子原料且/或無機原料以形 ❹成有機/無機塗層，傳統技術如溶膠-凝膠法、固態粒子燒結法與化學 氣相沉積法，僅能製備無機多孔薄膜，並不適用於有機多孔薄膜或 有機/無機複合多孔薄膜之形成。據此，本發明可符合經濟上之效益 與產業上的利用性。 【實施方式】 本發明在此所探討的方向為一種具有多孔塗層之複合膜的形成 方法及其裝置。為了能徹底地瞭解本發明，將在下列的描述中提出 200927994 滅本置及其步驟。顯然地’本發明的施行並未限定於該領域之 二_習的特殊㈣m眾所周知的步驟或裝置並未 描述於細節中，以避免造成本發明不必要之限制。本發明的較佳實 .施例會詳細描述如下，然嫌了這些詳細描述之外，本發明還可以 廣泛地施行在其他的實施财，且本發日__不受限定，其以之 後的專利範圍為準。 ❽ 之第實施例揭露一種具有多孔塗層之複合膜的形成方 、，首先提供多孔基板，此多孔基板係為孔徑小於或等於微 米之陶兜或金屬多孔基板，對多孔基板進行填充程序使一液體充 滿於多孔基板⑽巾。其巾，上狀㈣可為水、_、_或其 組合，此填充程序可為加壓式填充、喷淋式填充、真空吸引式填充 或浸入式填充。接著，進行一熔融程序，利用一熱源（例如：火焰、 ❾電弧或電漿）將-原料轉換成熔融或半溶融液滴，再將液滴喷塗於 充滿有紐之乡孔基板的表面，並完成—喷塗料。於上述喷塗程 序中，液滴撞擊於多孔基板表面後向四周擴散並形成平坦化之液 滴’藉由㈣之高溫（即大於該紐之軸溫度）氣化該多孔基板 孔隙中的液體並形成蒸汽，蒸汽貫穿平坦化之液滴的較薄處，使液 滴濺射成不同的區塊，冷卻固化後形成不規則且分散狀的扁平粒 子，重複進行數次喷塗程序，以持續形成與堆疊扁平粒子，藉此形 成一具有多孔塗層之複合膜。於多孔塗層之複合膜製程後，若欲增 8 200927994 加塗層厚度’可重新進行填充、溶融與喷塗程序。除此之外，上述 之無機材料麵下雜群中之—錢其組合：驗金屬、驗土金屬、 混合驗金屬及駐金射酸_、械鋪、魏鋪、經水合 的石夕酸鹽類、紹酸鹽類、氧化物類、氮化物類、氧氣化物類、碳化 物類、氧碳化物類、碰鹽、鈦酸鹽、填酸鹽、齒素化合物，及其 行生物於本實施例之一較佳範例，係為將炼融程序與喷塗程序合 ^ 併為熱熔射製程或大氣電漿熔射製程。 本發明之第二實施例揭露—細⑽成具有乡孔㈣之複合膜 的裝置’其包含-熱源產生裝置，—原料輸送裝置…充填裝置與 一噴塗裝置。上述之原料輸送裝置係用以將一原料送入熱源產生裝 置中，並藉由-熱源（例如：火焰、電弧或電聚）使原料轉換成熔 融或半熔融狀液滴；另外，充填裝置用以使一多孔基板之孔隙充填 一液體，此多孔基板之材質可為陶瓷或金屬，液體可為水、醇類、 ® 酮類或其混合物；喷塗裝置用以將液滴喷塗至充填有液體之多孔基 板表面。藉由液滴之高溫（即大於液體之沸點溫度）氣化多孔基板 孔隙中之液體並形成蒸汽，蒸汽貫穿液滴，使液滴濺射成不同的區 塊，冷卻固化後形成不規則且分散狀的扁平粒子，持續形成與堆疊 扁平粒子，藉此形成一具有多孔塗層之複合膜。其中，上述之充填 裝置可為加壓式充填裝置、噴淋式充填裝置、真空吸引式充填裝置 或浸入式充填裝置。除此之外，上述之熱源產生裝置依據一第一訊 9 200927994 號調整電此供應與熱源溫度’原料輸送裝置依據一第二訊號調整原 料輸送速4噴塗裝置依據—第三訊號調整喷塗速度，第一訊號、 第二訊號與第三訊號係由一控制裝置所產生。 本發露—種用以形成具有多孔塗層之複合膜 的大氣電漿溶射製程裝置，其包含一電源產生器，一高頻產生器， -電漿喷搶送粉機與-充填裝置。上述之高頻產生關用電源 ❹產生騎提供之電能產生高敝花並引燃電弧，而電弧能量則由電 漿喷搶利用’並用以離子化-惰性氣體，且在槍體内產生一電聚射 流，送粉機則將一粉體送入該電漿嘴搶中，利用電漿射流的溫度將 粉體轉換成熔融或半熔融液滴，充填裝置係用以使一多孔基板之孔 隙充填-液體，其中’電漿射流將液滴喷塗至充填有液體之多孔基 板表面，並藉由電漿射流與液滴之高溫（即大於液體之沸點溫度） 軋化多孔基板孔隙中之液體並形成蒸汽，蒸汽貫穿液滴，使得液滴 ® 濺射成不同的區塊，冷卻固化後形成不規則且分散狀的扁平粒子， 持續形成與堆疊扁平粒子，藉此形成一具有多孔塗層之複合膜。上 述之多孔基板材質、液體種類與充填裝置類型以第二實施例所提及 者為主。除此之外，電源產生器依據一第一訊號調整電源供應，高 頻產生器依據·一第一訊號調整起動點火，電聚喷搶依據^__第=訊辦· 調整喷槍速度’送粉機依據一第四訊號調整粉體輸送速度，第一訊 號、第二訊號、第三訊號與第四訊號係由一控制器所產生。 200927994 熱熔射法是近年來最新的製膜技術，目前常用以製備緻密無機 薄膜，而傳統的大氣電漿熔射技術是指在大氣環境下進行熔射製 程，所形成的塗層孔隙率較高，所以對於利用電漿熔射喷塗保護表 層的應用者來說，大氣電漿熔射的緻密度是不足的，因此才陸續研 發出不同製程的電漿熔射技術。長久以來，傳統大氣電漿熔射技術 所製造出之高孔隙率塗層被認定為失敗的技術參數，並沒有使用者 》將此-特性應用於多孔無機薄膜的製備方法中。本發明克服該所屬 技術領域巾具有通常知識者長久絲根雜固之技術偏見，而採用 因技術偏見而被捨棄之技術，並加以改良以符合高孔隙度，佐證本 發明並非能輕易完成。 麵地，依社的施财_述，本㈣可财料的修正 與差異。因此需要在其附加的權利要求項之範圍内加以理解，除了 》上述詳細的描述外，本發明還可以廣泛地在其他的實施例中施行。 上述僅為本發明之較佳實施例而已，並非用以限定本發明之申嗜專 利範圍；凡其妹_本發明所揭故騎下所完成料效改贱 修飾，均應包含在下述申請專利範圍内。 【圖式簡單說明】 【主要元件符號說明】 11BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method and apparatus for forming a composite film, and more particularly to a method and apparatus for forming a composite film having a porous coating. [Prior Art] Separation of thin crucibles is an energy-saving and comprehensive separation technique. Therefore, the membrane separation process has been an important separation age for chemical 4, water treatment, food hygiene, biomedical technology, and electronics industry. In the _ minute_order, the fine material can be divided into organic film, inorganic meaning and inorganic mixed _, wherein the thermal stability, mechanical stability and chemical enthalpy of the inorganic material _# is good, so the inorganic reliance on the separation procedure There is a wide range of _, both in microfiltration, over-gas separation technology and even thin-film reactors play an important role. According to the shape of the surface layer, the inorganic film can be roughly divided into two types: dense film and porous film. Because the amount of the tree is higher than that of the tree, the use of the red hole is relatively extensive, and the use of the hole is relatively wide. There are many functions on the system, such as gas separation, micro-liquid separation, and the use of ultra-Jude or even Nailai. In the porous inorganic thin_preparation method, there are commonly used rotary gel methods (S〇1 modulation, solid particle sintering, chemical vapor deposition (CVD), etc.] but the scale of the above process is complicated. , preparation _ lengthy, job _ limited and other shortcomings, limit the basin - φ - 1 . " the first application. In view of this, it is still necessary to develop a new film 200927994 device and process 'to make a composite with a porous coating The present invention provides a method for forming a composite film having a porous coating layer and a device thereof, which can be used to solve the above-mentioned conventional techniques, in view of the above-mentioned background of the invention. One of the objects of the present invention is to prepare a porous ruthenium-free film by the principle of liquid vaporization by liquid. First, the molten droplets are sprayed onto the surface of the porous substrate filled with liquid by the high temperature of the droplets. Gasifying the liquid in the pores of the porous substrate and forming steam. The steam penetrates the droplets, causing the droplets to be sputtered into different blocks, and formed into irregular and dispersed flat after cooling and solidification. The particles continuously form and stack the flat particles, thereby forming a composite film having a porous coating layer. Another object of the present invention is to use an organic polymer raw material and/or an inorganic raw material to form an organic/inorganic coating, conventional techniques For example, the sol-gel method, the solid particle sintering method and the chemical vapor deposition method can only prepare an inorganic porous film, and are not suitable for the formation of an organic porous film or an organic/inorganic composite porous film. Accordingly, the present invention can be economical. Advantages and Industrial Applicability [Embodiment] The present invention is directed to a method for forming a composite film having a porous coating layer and an apparatus therefor. In order to thoroughly understand the present invention, the following will be In the description, the present invention and its steps are presented. It is obvious that the implementation of the present invention is not limited to the special (four) m well-known steps or devices in the field, which are not described in detail to avoid making the invention unnecessary. The invention will be described in detail below, but the invention may be widely applied in addition to the detailed description. Other implementations, and the present invention is not limited, which is based on the scope of the following patents. 第 The first embodiment discloses the formation of a composite film having a porous coating, first providing a porous substrate, The porous substrate is a ceramic pocket or a metal porous substrate having a pore diameter of less than or equal to a micrometer, and the filling process of the porous substrate is such that a liquid is filled in the porous substrate (10). The towel, the upper shape (4) may be water, _, _ or a combination thereof. The filling procedure can be a pressurized filling, a spray filling, a vacuum suction filling or an immersion filling. Next, a melting process is performed to convert the raw material using a heat source (for example, flame, helium arc or plasma) Melting or semi-melting the droplets, spraying the droplets on the surface of the hole-filled substrate of the New Zealand, and completing the spray coating. In the above spraying process, the droplets impinge on the surface of the porous substrate and then spread to the periphery and Forming a flattened droplet' to vaporize the liquid in the pores of the porous substrate by steam at a high temperature (ie, greater than the axis temperature of the button) and form a vapor that passes through the thinner portion of the planarized droplet Sputtering dropwise into different blocks, and irregular-shaped flat particle dispersion solidifies on cooling, spraying process was repeated several times, to form a continuous stack of flat particles, thereby forming a composite film having the porous coating layer. After the porous coating composite film process, if you want to increase the thickness of 200927994 plus coating thickness, you can refill, melt and spray the process. In addition, the combination of the above-mentioned inorganic materials in the sub-population - money combination: metal test, soil test metal, mixed metal test and resident gold acid _, equipment shop, Wei Pu, hydrated stone Classes, salts, oxides, nitrides, oxygenates, carbides, oxycarbides, salt, titanates, acidates, dentate compounds, and their biology A preferred example of the example is to combine the smelting process with the spraying process and to be a thermal spray process or an atmospheric plasma spray process. A second embodiment of the present invention discloses a device (10) which is a composite film having a town hole (four), which comprises a heat source generating device, a material conveying device, a filling device and a spraying device. The above-mentioned raw material conveying device is used for feeding a raw material into a heat source generating device, and converting the raw material into a molten or semi-molten liquid droplet by a heat source (for example, flame, arc or electropolymerization); In order to fill a porous substrate with a liquid, the porous substrate may be made of ceramic or metal, the liquid may be water, alcohol, ketone or a mixture thereof; the spraying device is used to spray the droplets to A porous substrate surface filled with a liquid. The liquid in the pores of the porous substrate is vaporized by the high temperature of the liquid droplets (ie, greater than the boiling temperature of the liquid) and vapor is formed, and the vapor penetrates the liquid droplets to cause the liquid droplets to be sputtered into different blocks, which are formed into irregular and dispersed after cooling and solidification. The flattened particles continue to form and stack the flat particles, thereby forming a composite film having a porous coating. The above filling device may be a pressurized filling device, a spray filling device, a vacuum suction filling device or an immersion filling device. In addition, the heat source generating device adjusts the supply and the heat source temperature according to a first message 9 200927994. The raw material conveying device adjusts the material conveying speed according to a second signal. 4 the spraying device adjusts the spraying speed according to the third signal. The first signal, the second signal and the third signal are generated by a control device. The present invention relates to an atmospheric plasma spray process apparatus for forming a composite film having a porous coating, comprising a power generator, a high frequency generator, a plasma spray powder feeder and a filling device. The above-mentioned high frequency generates a power supply, generates electric energy provided by the rider to generate high spurs and ignites the arc, and the arc energy is utilized by the plasma spray and uses ionization-inert gas to generate electricity in the gun body. The poly-jet, the powder feeder sends a powder into the nozzle, and uses the temperature of the plasma jet to convert the powder into molten or semi-molten droplets, and the filling device is used to make the pores of a porous substrate Fill-liquid, wherein the 'plasma jet sprays droplets onto the surface of the porous substrate filled with liquid, and rolls the liquid in the pores of the porous substrate by the high temperature of the plasma jet and the droplets (ie, greater than the boiling temperature of the liquid) And forming steam, the steam penetrates the droplets, so that the droplets are sputtered into different blocks, and after cooling and solidification, irregular particles are formed and dispersed, and the flat particles are continuously formed and stacked, thereby forming a porous coating layer. Composite film. The porous substrate material, liquid type and filling device type described above are mainly as mentioned in the second embodiment. In addition, the power generator adjusts the power supply according to a first signal, and the high frequency generator adjusts the starting ignition according to the first signal, and the electric squirting is based on the ^__ The powder machine adjusts the powder conveying speed according to a fourth signal, and the first signal, the second signal, the third signal and the fourth signal are generated by a controller. 200927994 Hot melt spraying method is the latest film forming technology in recent years. It is commonly used to prepare dense inorganic film. The traditional atmospheric plasma spraying technology refers to the spraying process in the atmosphere, and the porosity of the formed coating is better. High, so for the application of plasma spray coating to protect the surface layer, the density of atmospheric plasma spray is insufficient, so the plasma spray technology of different processes has been developed. High-porosity coatings produced by conventional atmospheric plasma spray technology have long been recognized as technical parameters of failure, and no user has applied this feature to the preparation of porous inorganic thin films. SUMMARY OF THE INVENTION The present invention overcomes the technical prejudice of the prior art in which the prior art has a long history of stalking, and employs techniques that have been discarded due to technical biases and has been modified to conform to high porosity, supporting the invention to be not readily accomplished. In the face, according to the company's financial management _, this (four) can be corrected and differences in the financial materials. It is therefore to be understood that within the scope of the appended claims, the invention may be The above is only the preferred embodiment of the present invention, and is not intended to limit the scope of the patent application of the present invention; the modification of the material effect modified by the sister of the present invention should be included in the following patent application. Within the scope. [Simple description of the diagram] [Explanation of main component symbols] 11