TWI395791B - A preparation method of polymer membrane containing nano iron particles by chemical reduction method - Google Patents

Description

以化學還原法製備含奈米金屬顆粒複合薄膜之製備方法Preparation method of preparing nanometer metal particle composite film by chemical reduction method

本發明係關於一種以化學還原法製備含奈米金屬顆粒複合薄膜之製備方法。The invention relates to a preparation method for preparing a nanometer-containing metal particle composite film by a chemical reduction method.

按，近年來科技快速發展，工業日益蓬勃，但也產生出許多工業污染問題，有機廢液即是工業快速發展所產生的問題之一，因其對人類健康和生態環境都有嚴重危害，故需加以管制和處理。有機廢液中化學物質的分離、濃縮及純化是化學工業的主要製程之一，而且是非常重要的一個環節，加上近年來環保意識抬頭以及資源日趨減少，致使分離技術越來越受重視，也因此化學工業對於分離程序的要求持續朝著操作簡便、節約能源、提高分離物品質以及降低化學污染等方面積極發展，而薄膜分離程序的分離特性正好符合上述的發展趨勢。薄膜分離程序不只是在化學工業上有廣大的功能外，近幾年來各種薄膜分離程序已經成功地在工業程序上被大量應用，像是工業廢水處理、海水淡化、飲用水製備、超過濾、微過濾、逆滲透、食品及製藥產品之濃縮純化、血液透析、有價物質之回收、氣體分離、油氣回收分離、揮發性有機化合物(VOCs)之回收、食品及水中所含有機物之分離與純化、藥物釋放、氣體/液體的純化、液體混合物的增濃與分餾、製備電子工業所需的超純水等技術之研究開發，顯示薄膜分離技術具效率性、迅速性以及經濟性；不僅如此，薄膜分離技術更突破傳統分離技術的瓶頸，進行共沸物、同分異構物、熱敏感性及沸點相近混合物的分離，實有頗具發展之趨勢。According to the rapid development of science and technology in recent years, the industry is booming, but there are also many industrial pollution problems. Organic waste liquid is one of the problems caused by the rapid development of industry. Because it has serious harm to human health and ecological environment, It needs to be regulated and handled. The separation, concentration and purification of chemical substances in organic waste liquid is one of the main processes of the chemical industry, and it is a very important link. In addition, with the rising awareness of environmental protection and the decreasing resources in recent years, the separation technology has received more and more attention. Therefore, the chemical industry's requirements for separation procedures continue to be positively developed in terms of ease of operation, energy conservation, improved separation quality, and reduction of chemical contamination, and the separation characteristics of the membrane separation process coincide with the above-mentioned development trend. The membrane separation process is not only widely used in the chemical industry. In recent years, various membrane separation procedures have been successfully applied in industrial processes, such as industrial wastewater treatment, seawater desalination, drinking water preparation, ultrafiltration, micro Filtration, reverse osmosis, concentration and purification of food and pharmaceutical products, hemodialysis, recovery of valuable substances, gas separation, separation of oil and gas, recovery of volatile organic compounds (VOCs), separation and purification of substances contained in food and water, drugs Research and development of release, purification of gas/liquid, enrichment and fractionation of liquid mixtures, preparation of ultrapure water required for the electronics industry, etc., showing that membrane separation technology is efficient, rapid and economical; The technology has broken through the bottleneck of the traditional separation technology, and the separation of azeotropes, isomers, heat sensitivity and similar boiling points has a tendency to develop.

薄膜分離程序相較於其他分離程序的特色就是在於它的操作簡單、模組簡單、分離效率高、分離成本低、節省能源、佔地面積小、不會產生二次污染、處理後品質較好、及能夠回收有價值之物質等優點，因此具有相當高的經濟價值。由於薄膜分離程序深具發展潛力，且成功的應用在各種工業用途及產品上，以致於各種薄膜分離程序相繼被發展。Compared with other separation programs, the membrane separation program is characterized by simple operation, simple module, high separation efficiency, low separation cost, energy saving, small floor space, no secondary pollution, and good quality after treatment. And the ability to recover valuable substances, so it has a very high economic value. Since the membrane separation process has great potential and has been successfully applied in various industrial applications and products, various membrane separation procedures have been developed.

薄膜依據其操作原理及應用範圍可概略區分為：微過濾(microfiltration)、超過濾(ultrafiltration)、逆滲透(reverse osmosis)、透析/電透析(dialysis/electrodialysis)、氣體分離(gas permeation)與滲透蒸發(pervaporation)等，經由選擇適當的薄膜，可因其分離的特性，適用於各種不同的分離程序。薄膜在分離程序中可視為進料與出料端之透過選擇阻礙層，而分離程序皆屬於被動傳遞(passive transport)，其驅動力(driving force)主要區分為壓力梯度(△P)、濃度梯度(△C)、電位梯度(△E)、及溫度梯度(△T)，其相關作用示意如第一圖所示。According to its operating principle and application range, thin films can be roughly divided into: microfiltration, ultrafiltration, reverse osmosis, dialysis/electrodialysis, gas permeation and infiltration. Pervaporation or the like can be applied to various separation procedures depending on the characteristics of separation by selecting an appropriate film. The film can be regarded as the barrier layer through the separation of the feed and the discharge end in the separation process, and the separation process belongs to the passive transport, and the driving force is mainly divided into the pressure gradient (ΔP) and the concentration gradient. (ΔC), potential gradient (ΔE), and temperature gradient (ΔT), the related actions are shown in the first figure.

薄膜在分離程序上的定義是它屬於一種界面相(inter phase)，藉以隔開兩相之間的阻隔層，而且能控制兩相內部的質量之輸送速率，因此，特定兩種或兩種以上的物質，在通過薄膜(Membrane)時，可以造成篩選物質效應，或是物質在薄膜內部運動時，經由通過物質與薄膜分子間的交互作用，產生不同的運動速率，而造成分離通過物質的效果。一般可以作為薄膜用的材質，都具有一共同的特性，就是能夠以特殊的方式，限制各種化學物質通過薄膜，達到所需的分離效果。一般利用薄膜材質本身具有的特性，像是以親水性(hydrophilic)或疏水性(hydrophobic)官能基來控制兩相間的質傳現象、薄膜本身結構上的孔洞大小、官能基型態、兩相中不同分子之形狀，大小，親和力….等等方式來限制各種化學物質通過薄膜。The separation process of a film is defined as an interphase, which separates the barrier between the two phases and controls the rate of mass transfer within the two phases. Therefore, two or more specific types are specified. The substance, when passing through a membrane (Membrane), can cause a screening effect, or when the substance moves inside the film, through the interaction between the substance and the film molecule, different movement rates are generated, resulting in separation of the substance. . Generally, it can be used as a material for a film, and all have a common characteristic, that is, it is possible to restrict various chemicals through a film in a special manner to achieve a desired separation effect. Generally, the characteristics of the film material itself are used, such as hydrophilic or hydrophobic functional groups to control the mass transfer phenomenon between the two phases, the pore size on the structure of the film itself, the functional group type, and the two phases. The shape, size, affinity, etc. of different molecules are used to limit the passage of various chemicals through the film.

薄膜依材料的來源可分為天然(natural)或合成(synthetic)；依結構可分為緻密性薄膜(Dense membrane)、多孔性薄膜(Porous membrane)以及複合薄膜(Composite membrane)。而多孔性薄膜又可再細分為對稱性薄膜(Symmetric membrane)及非對稱性薄膜(Asymmetric membrane)兩種。緻密性薄膜是指從薄膜的表面到內部均非常的緻密，沒有任何孔洞結構的存在；多孔性對稱膜則是指從薄膜的表面到內部，孔洞的分佈以及孔徑大小均非常一致；而從薄膜的表面到內部，孔洞的分佈以及孔徑大小均非常不一致則稱為多孔性非對稱膜；至於複合膜則是除了正基材膜(一般為多孔非對稱性薄膜)外，上方再塗佈一層高分子以形成一個緻密膜。The film may be classified into natural or synthetic depending on the material; according to the structure, it may be classified into a dense film (Dense membrane), a porous film (Porous membrane), and a composite film (Composite membrane). The porous film can be further subdivided into a symmetric film (Symmetric membrane) and an asymmetric membrane (Asymmetric membrane). The dense film means that it is very dense from the surface to the inside of the film without any pore structure; the porous symmetric film means that the distribution of the pores and the pore size are very consistent from the surface to the inside of the film; The surface to the inside, the distribution of the pores and the pore size are very inconsistent, which is called a porous asymmetric membrane; as for the composite membrane, in addition to the positive substrate film (generally a porous asymmetric film), the upper layer is coated with a higher layer. Molecules to form a dense film.

一般對稱型薄膜的厚度大約介於10-200μm之間，其質傳的阻力是由薄膜厚度控制，即滲透通量隨薄膜厚度增加而下降，但選擇比會上升；雖說分離效果不錯，但是用來處理現今工業所產生的大量有機廢液，可能需要分批處理才能將所有廢液處理，所以現今工業上的應用上以非對稱型薄膜所具有的高透過量及能維持一定選擇比的優勢，而被著重於發展與應用。非對稱薄膜兼具緻密性薄膜(dense membrane)之高選擇性與超薄型薄膜(ultra-thin membrane)之高滲透通過量，而其結構由上層大約厚度0.1-1μm的皮層(skin layer)及次層大約厚度50-150μm的多孔性支撐層(porous sublayer)所組成。另一種複合薄膜(composite membrane)也是屬於非對稱型薄膜之一種，其緻密性皮層與非對稱支撐層之材質不同，常利用浸泡-塗佈法(dip-coating)，界面聚合法(interfacial polymerization)或電漿聚合法(plasma polymerization)等方法製備，於多孔性支撐層披覆上另一種不同材質polymer形成一層緻密層，多為現代工業界非對稱型薄膜之應用主流。Generally, the thickness of the symmetric film is between about 10-200 μm, and the resistance of the mass transfer is controlled by the thickness of the film, that is, the permeation flux decreases as the thickness of the film increases, but the selection ratio increases; although the separation effect is good, but To deal with the large amount of organic waste liquid produced by today's industry, it may be necessary to process all waste liquids in batches. Therefore, the current industrial applications have the high permeability of asymmetric membranes and the advantage of maintaining a certain selection ratio. And is focused on development and application. The asymmetric film combines the high selectivity of the dense membrane with the high permeation throughput of the ultra-thin membrane, and the structure consists of a skin layer having an upper thickness of about 0.1 to 1 μm and The sublayer consists of a porous sublayer having a thickness of about 50-150 μm. Another composite membrane is also a kind of asymmetric membrane. The dense cortex is different from the asymmetric support layer, and often uses dip-coating and interfacial polymerization. Or plasma polymerization method (plasma polymerization) and other methods, the porous support layer is coated with another different material polymer to form a dense layer, mostly for the mainstream application of modern industrial asymmetric film.

在薄膜分離程序依所使用膜材本身的性質與膜結構決定其分離性能之優劣。在膜材方面可區分為親水性膜材(hydrophilic membrane)與疏水性膜材(hydrophobic membrane)。親水性膜材通常具有氫鍵或是極性-極性的高子；此類膜材對水會有較強的親和力，因此被廣泛的應用在脫水程序(dehydration)，常見的膜材有poly(vinyl alcohol)、poly(acrylic acid)、纖維素(cellulose)…等等。疏水性膜材則是不具有與水有親和力的官能基或者是與水之間的作用力較小，對水有排斥性，常見的膜材有poly(ethylene)、poly(propylene)…等等。In the membrane separation process, the separation performance is determined depending on the nature of the membrane itself and the membrane structure. The membrane can be distinguished as a hydrophilic membrane and a hydrophobic membrane. Hydrophilic membranes usually have hydrogen bonds or polar-polar highs; such membranes have a strong affinity for water and are therefore widely used in dehydration processes. Common membranes have poly(vinyl). Alcohol), poly(acrylic acid), cellulose (cellulose), etc. Hydrophobic membranes are functional groups that do not have affinity for water or have less force with water and are repellent to water. Common membranes include poly(ethylene), poly(propylene), etc. .

薄膜結構可區分為具有孔洞性(pore)的多孔性薄膜或是為緻密性(dense)薄膜，當薄膜分離程序中本身是否會對於所接觸的溶劑而產生膨潤(swelling)現象；此外，膜材本身的結晶度(crystallinity)、親水性(hydrophilic)或是疏水性(hydrophobic)都可能會影響分離程序的結果，還有分離物質本身的分子結構、形狀、大小與分離薄膜之間的作用力均是影響分離效果因素之一，故可因其所分離物質特性選擇適用所需薄膜材料，以適當製程製成適當的薄膜。The film structure can be distinguished as a porous film having a pore or a dense film, which itself swells in the film separation process; in addition, the film Its crystallinity, hydrophilicity or hydrophobicity may affect the results of the separation procedure, as well as the molecular structure, shape, size of the separated material itself and the interaction between the separation membranes. It is one of the factors affecting the separation effect, so it is possible to select a suitable film material for the characteristics of the material to be separated, and to form a suitable film by a suitable process.

薄膜之製備方法有燒結法(sintering method)、拉伸法(stretched method)、軌跡蝕刻法(tracked-etched method)、及相轉換法(phase inversion method)等多種，其中以相轉換法為一般較常用之薄膜製備方法。相轉換法就是將均勻之液相高分子溶液轉變成固相之高分子薄膜。相轉換法又可分為下列幾種方法：The preparation method of the film includes a sintering method, a stretched method, a tracked-etched method, and a phase inversion method, and the phase conversion method is generally used. A commonly used film preparation method. The phase inversion method is a polymer film that converts a homogeneous liquid phase polymer solution into a solid phase. The phase conversion method can be divided into the following methods:

1.熱誘導式相轉換法(Thermal induced phase separation；TIPS)：乃是藉由溫度的變化來降低均相高分子溶液之溶解度，控制相分離行為的產生，促使高分子沉澱而形成凝膠(gel)，最後形成一層薄膜，再藉由萃取(extraction)、揮發(evaporation)或冷凍乾燥(freeze drying)等方法，以去除殘存之溶劑，最後乾燥成膜。因此，熱誘導式相轉換法是鑄膜後控制其降溫速率及溫度變化，調整其相分離行為，藉此改變薄膜形成不同結構。1. Thermal induced phase separation (TIPS): It is to reduce the solubility of homogeneous polymer solution by temperature change, control the generation of phase separation behavior, and promote the precipitation of polymer to form a gel ( Finally, a film is formed, and the remaining solvent is removed by extraction, evaporation, or freeze drying, and finally dried to form a film. Therefore, the heat-induced phase inversion method controls the temperature drop rate and temperature change after casting, and adjusts the phase separation behavior, thereby changing the film to form different structures.

2.乾式相轉換法(Precipitation by solvent evaporation)：即藉由高分子與揮發性溶劑配製成之鑄膜溶液，在某固定溫度之下為均相的高分子溶液，在恆溫程序中溶劑逐漸揮發，至完全揮發後，由於高分子溶液之溶解度降低，因此發生相分離而形成多孔性薄膜結構。2. Precipitation by solvent evaporation: a solution solution prepared by mixing a polymer with a volatile solvent, a homogeneous polymer solution at a fixed temperature, and gradually evaporating the solvent in a constant temperature program. After volatilization, after complete volatilization, since the solubility of the polymer solution is lowered, phase separation occurs to form a porous film structure.

3.濕式相轉換法(Wet-phase inversion)：其製造方法係將高分子溶液鑄膜後浸入凝聚劑(非溶劑)中，此時溶劑和凝聚劑間進行擴散交換作用，利用非溶劑將鑄膜液中之所添加的溶劑萃取出來，同時凝聚劑也可進入鑄膜液中，導致高分子溶解度降低，使鑄膜液固化成膜。如此所製得之薄膜通常具有一多孔性結構型態，而且膜結構具可變性及可調整性；此法常用以製造非對稱性薄膜。3. Wet-phase inversion: The method is as follows: the polymer solution is cast into a film and then immersed in a coagulant (non-solvent). At this time, the solvent and the coagulant are diffusion-exchanged, and the non-solvent is used. The solvent added in the casting solution is extracted, and the coagulant can also enter the casting solution, resulting in a decrease in the solubility of the polymer and solidification of the casting solution into a film. The film thus obtained usually has a porous structure and the film structure has variability and adjustability; this method is commonly used to produce an asymmetric film.

4.乾/濕式混合製程(Dry/Wet process)：簡單來說就是乾式相轉換法及濕式相轉換法搭配使用；係鑄膜溶液在鑄膜後在某固定溫度下先讓溶劑揮發一段時間，再浸入凝聚劑中使高分子固化成膜，其中溶劑揮發性、揮發時間是影響薄膜緻密層形成之重要因素。4. Dry/Wet process: In simple terms, the dry phase conversion method and the wet phase conversion method are used together; the casting solution is allowed to volatilize the solvent at a fixed temperature after casting the film. Time, and then immersed in the coagulant to solidify the polymer into a film, wherein the solvent volatility and volatilization time are important factors affecting the formation of the dense layer of the film.

優良之薄膜得具備高透過量及高選擇比之分離效能，但兩者通常無法同時兼顧，當薄膜的透過量較大時，其選擇比會降低；相反的，選擇性提升時，往往會使其透過量下降；在以往許多研究中指出，高分子薄膜與進料溶液間的氫鍵效應(hydrogen-bonding effect)對於薄膜的選擇性上具有舉足輕重的關鍵，所以若是只有單一高分子材質製成之滲透蒸發分離薄膜是很難能夠完全兼具一優良薄膜所具有的要求如：高機械強度，高滲透通量(P)及高選擇性(α)，但若能以結合兩種或兩種以上材料之優點來改質做成複合薄膜，以求得薄膜性能上之突破，則可達到較佳的分離效果。一般習知所知的研究上所採取將兩種以上材料加以結合的結合方法有：An excellent film has high separation efficiency and high selectivity. However, the two cannot usually be considered at the same time. When the amount of the film is large, the selection ratio is lowered. Conversely, when the selectivity is increased, it tends to Its permeability has decreased; in many previous studies, it has been pointed out that the hydrogen-bonding effect between the polymer film and the feed solution is critical to the selectivity of the film, so if it is made of only a single polymer material. The pervaporation separation membrane is difficult to completely combine the requirements of an excellent membrane such as high mechanical strength, high permeation flux (P) and high selectivity (α), but if two or two types can be combined The advantages of the above materials are modified to form a composite film, in order to achieve a breakthrough in film performance, a better separation effect can be achieved. The combination of two or more materials adopted in the conventionally known research is as follows:

1.摻合(blending)：聚合物之摻合是利用物理的方法來混合，將聚合物與聚合物之間藉由彼此間互溶性(miscibility)的關係，來改良兩邊界區(boundary)之相分離(phase separation)的現象，通常是在兩聚合物的溶解參數值間選擇一最佳值以作為二聚合物的共同溶劑亦是取兩聚合物的優點以適當的比例混合以達較佳之透過率分離係數及機械強度。為達到改質的目的，最需要注意的是，以摻合改質材料時必須考慮到材料之間的相容性，因只有兩聚合物在最適當的混合比例下才可達到較佳的透過率、分離係數和機械強度。摻合法的缺點就是所選擇的兩聚合物必須有一定的相容性才行、須依一適當之比例摻合、摻合膜通常其透過性質都介於原材質之間。1. Blending: The blending of polymers is done by physical means, and the relationship between the polymer and the polymer is improved by the mutual miscibility. The phenomenon of phase separation, usually by selecting an optimum value between the solubility parameters of the two polymers as a common solvent for the dipolymer, or mixing the advantages of the two polymers in an appropriate ratio to achieve better Transmission separation factor and mechanical strength. In order to achieve the purpose of upgrading, the most important thing to note is that the compatibility between the materials must be taken into consideration when blending the modified materials, because only the two polymers can achieve better penetration at the most appropriate mixing ratio. Rate, separation factor and mechanical strength. The disadvantage of the blending method is that the selected two polymers must have a certain compatibility, and must be blended in an appropriate ratio. The blended film usually has a permeability property between the original materials.

2.化學接枝：接枝聚合是改良高分子材料的物理與化學性質最常使用的方法，利用起始劑引發聚合反應而將單體接上高分子的主鏈，接枝的產生必先形成自由基(free radical)，這些自由基一端以游離基狀態捕捉高分子而發生聚合，另一端則與氧作用而生成過氧化物。其優點為可依不同的需求接枝上不同特性的單體，然而最大的缺點就是可能在接枝的過程中會受到起始劑、溫度、濃度、接枝的程度等變數影響，還有接之後所產生的一些殘餘廢液會造成污染。2. Chemical grafting: Graft polymerization is the most commonly used method to improve the physical and chemical properties of polymer materials. The initiator is used to initiate the polymerization reaction and the monomer is attached to the main chain of the polymer. Free radicals are formed, and one of these radicals is polymerized in a free radical state to polymerize, and the other end is activated by oxygen to form a peroxide. The advantage is that monomers with different characteristics can be grafted according to different requirements, but the biggest disadvantage is that it may be affected by variables such as initiator, temperature, concentration, degree of grafting, etc. during the grafting process, and Some residual waste liquid produced afterwards can cause pollution.

3.電漿改質：電漿的能量及活性較一般物質之氣態還高，一般氣體分子呈電中性之絕緣狀態，但在強大的能量及電場中，可將中性分子激發或解離成電子、離子、自由基等活性物質，稱之為電漿狀態。利用電漿改質具有以下優點：在基材表面形成一均勻無針孔的超薄膜、對基材有良好的附著性、形成的物質具有化學穩定性及物理耐久性、僅對基材表面改質而不影響其整體性質。3. Plasma modification: The energy and activity of plasma are higher than the gaseous state of general materials. Generally, gas molecules are electrically neutral, but in strong energy and electric field, neutral molecules can be excited or dissociated into Active substances such as electrons, ions, and radicals are called plasma states. The use of plasma modification has the following advantages: forming a uniform pinhole-free ultra-thin film on the surface of the substrate, good adhesion to the substrate, chemical stability and physical durability of the formed material, and only changing the surface of the substrate Quality does not affect its overall nature.

滲透蒸發(pervaporation)於近二十年之發展，已成功地應用於各項化學工業之分離程序，由於滲透蒸發程序常應用於液相混合物之分離與純化，尤其對於生產超高純度之有機溶劑更佔優勢，因此對於分離乙醇(ethanol)、異丙醇(iso-propanol)、乙烯醇(ethylene glycol)等有機溶劑分離具優勢，並已有許多商品化之滲透蒸發程序進行商業運轉，滲透蒸發乃結合了滲透(permeation)和蒸發(vaporization)兩種不同的程序，由於滲透蒸發之穿透介質乃依循溶解-擴散(solution-diffusion)模式，即溶液溶解進入薄膜並且溶液中各成份以一定分配比溶入並膨潤表層薄膜，依分配比差異形成不同濃度梯度，溶液中各成份以持續擴散至薄膜非膨潤層，溶液中各成份擴散至薄膜下游表面進行脫附，如第二圖所示。而溶質經由滲透蒸發之過程透過薄膜，通常因為下游皆處於低壓狀態，一旦溶液中各成份擴散於薄膜中擴散，溶質通常容易於擴散過程由液相轉變成氣相，薄膜因此膨潤程度迅速降低，而發生阻力增加之現象，因此穿透介質於此高阻力階段會因質傳過程越長則致其薄膜之溶質透過量越小，當穿透介質到達薄膜下游表面時則介質進行脫附離開薄膜，此一脫附步驟發生迅速且其脫附過程只與下游壓力有關。由以上分析可知穿透介質於薄膜中之質傳行為決定於兩因素：The development of pervaporation in the past two decades has been successfully applied to the separation process of various chemical industries. The pervaporation process is often applied to the separation and purification of liquid mixtures, especially for the production of ultra-high purity organic solvents. It is more dominant, so it is advantageous for separating organic solvents such as ethanol, iso-propanol, and ethylene glycol. There are many commercial pervaporation procedures for commercial operation and pervaporation. It combines two different procedures of permeation and vaporization. The penetrating medium of pervaporation follows the solution-diffusion mode, that is, the solution dissolves into the film and the components in the solution are distributed. Compared with the dissolution and swelling of the surface film, different concentration gradients are formed according to the difference of the distribution ratio, and the components in the solution continuously diffuse to the non-swelling layer of the film, and the components in the solution diffuse to the downstream surface of the film for desorption, as shown in the second figure. The solute passes through the membrane through the process of pervaporation, usually because the downstream is in a low pressure state. Once the components in the solution diffuse into the membrane, the solute is usually easily converted from the liquid phase to the gas phase during the diffusion process, and the swelling degree of the film is rapidly reduced. However, the phenomenon of increased resistance occurs. Therefore, the longer the mass transfer process, the smaller the solute permeability of the film is, and the medium is desorbed away from the film when the penetrating medium reaches the downstream surface of the film. This desorption step occurs rapidly and its desorption process is only related to downstream pressure. From the above analysis, it is known that the mass transfer behavior of the penetrating medium in the film is determined by two factors:

1.穿透介質於薄膜非澎潤層中之活性梯度大小。通常活性梯度大小取決於薄膜表層溶入穿透介質濃度之大小，一般而言較易溶入薄膜表層之穿透物質較易建立較高之濃度梯度，此一梯度可藉由塑化效應及溶劑之偶合效應之影響而達到較高濃度梯度之建立。就一般高分子薄膜而言，較易溶入薄膜之穿透介質在膜中質傳速度亦較快，因此大部分滲透蒸發分離膜皆選擇與欲穿透介質溶解性相似者。1. The magnitude of the activity gradient of the penetrating medium in the non-smooth layer of the film. Generally, the size of the active gradient depends on the concentration of the surface layer of the film dissolved in the penetrating medium. Generally, the penetrating substance which is more soluble in the surface layer of the film is easier to establish a higher concentration gradient. The gradient can be plasticized and solvent. The effect of the coupling effect is reached to achieve the establishment of a higher concentration gradient. In the case of a general polymer film, the penetrating medium which is more soluble in the film is also faster in the film, so most of the pervaporation separation membranes are selected to have similar solubility to the medium to be penetrated.

2.薄膜非膨潤層中溶液成份之擴散行為差異及溶液成份於薄膜中之擴散行為決定於穿透分子與薄膜孔隙之相對大小及穿透分子與薄膜高分子官能基分子間作用力之強弱，假使穿透分子與薄膜之作用力顯著則穿透分子之擴散行為較不受穿透分子與薄膜之相對大小影響，而由分子間作用力決定穿透介質之質傳阻力。2. The difference in the diffusion behavior of the solution components in the non-swelling layer of the film and the diffusion behavior of the solution components in the film are determined by the relative size of the penetrating molecules and the pores of the film and the strength of the interaction between the penetrating molecules and the functional groups of the film polymer. If the interaction between the penetrating molecule and the film is significant, the diffusion behavior of the penetrating molecule is less affected by the relative size of the penetrating molecule and the film, and the intermolecular force determines the mass transfer resistance of the penetrating medium.

薄膜的分離效能在各種分離程序中扮演著重要的角色，分離效能主要是指透過量及對各待分離物種之選擇性。一個好的薄膜必須具備的條件就是優越之分離效能，也就是有高之透過量與優異之選擇性，但兩者往往無法同時兼顧。一般而言，透過量較大的膜，其選擇性會較低；相反的，選擇性提升時，往往會使其透過量下降。所以就有許多的方法被研發出來，可以克服這樣難題。例如化學接枝與輻射接枝就可以成功的將薄膜改質，但是接枝層並無法有完全一致的接枝程度或是完全無缺陷的合成薄膜；又如摻合與披覆技術可以成功製備出一無缺陷的合成薄膜，但是摻合技術的最大缺失就是必須找出所要摻合聚合物的可溶性；由於上述各種改質方法均有各其缺失，無法製備出一個薄且無缺陷的合成膜。The separation efficiency of the membrane plays an important role in various separation procedures. The separation efficiency mainly refers to the amount of permeation and the selectivity to each species to be separated. A good film must have the conditions of superior separation performance, that is, high transmission and excellent selectivity, but the two can not always take care of both. In general, a membrane with a large amount of permeation will have a lower selectivity; conversely, when the selectivity is increased, the amount of permeation will tend to decrease. So there are many ways to develop it that can overcome this problem. For example, chemical grafting and radiation grafting can successfully modify the film, but the grafted layer cannot have a completely uniform grafting degree or a completely defect-free synthetic film; and can be successfully prepared by blending and coating techniques. A defect-free synthetic film is produced, but the biggest drawback of the blending technique is that it is necessary to find out the solubility of the polymer to be blended; due to the various modifications described above, it is impossible to prepare a thin and defect-free synthetic film. .

因此尋找一種更佳的製備方法，以製備出具良好滲透蒸發分離效能之非對稱薄膜，顯為迫切需要。而針對此等需求，本發明人即深入研究發明，而終有本發明完成。Therefore, it is urgent to find a better preparation method to prepare an asymmetric film with good pervaporation separation efficiency. In view of these needs, the inventors have intensively studied the invention, and the invention has been completed.

緣是，本發明之主要目的即在提供一種以化學還原法製備含奈米金屬顆粒複合薄膜之製備方法，以達到具良好滲透蒸發分離效能之要求。The main purpose of the present invention is to provide a preparation method for preparing a nanometer-containing metal particle composite film by a chemical reduction method to achieve a good pervaporation separation efficiency.

本發明為達成上述目的，即研發一種以化學還原法製備含奈米金屬顆粒複合薄膜之製備方法，主要先以化學還原法配置鑄膜溶液，其過程係將氯化鐵(Iron(III)Chloride，FeCl₃ )溶入N-甲基2-四吡咯酮(N-methyl-2-pyrrolidnone，NMP)溶劑混合攪拌均勻，另將硼氫化鈉(Sodium borohydride，NaBH₄ )溶解於蒸餾水中，配製成硼氫化鈉水溶液，然後將硼氫化納水溶液加入上述氯化鐵NMP溶液中進行化學還原反應，反應完全後形成含奈米鐵之N-甲基2-四吡咯酮(NMP)溶液，接著取聚嗍碸(polysulfone，PSF)高分子顆粒溶於上述奈米鐵溶液中，於室溫下經過混合攪拌完全溶解後，靜置待鑄膜溶液中氣泡完全去除，即完成鑄膜溶液之配置；接著即利用上述鑄膜溶液以濕式相轉換法製備出含奈米金屬顆粒複合薄膜。The invention aims to achieve the above object, that is, to prepare a preparation method for preparing a nanometer-containing metal particle composite film by a chemical reduction method, which firstly configures a casting film solution by a chemical reduction method, and the process is iron (Iron (III) Chloride , FeCl ₃ ) dissolved in N-methyl-2-pyrrolidnone (NMP) solvent mixed and stirred uniformly, and dissolved sodium borohydride (Sodium borohydride, NaBH ₄ ) in distilled water, prepared The aqueous solution of sodium borohydride is added, and then the aqueous solution of sodium borohydride is added to the above-mentioned iron chloride NMP solution for chemical reduction reaction, and after completion of the reaction, a solution of N-methyl 2-tetrapyrrolidone (NMP) containing nano iron is formed, followed by taking The polysulfone (PSF) polymer particles are dissolved in the above-mentioned nano iron solution, and after being completely dissolved by mixing and stirring at room temperature, the bubbles in the solution to be cast are completely removed, that is, the configuration of the casting solution is completed; Next, a composite film containing a nano metal particle was prepared by the wet phase conversion method using the above casting solution.

在上述發明中，奈米金屬鐵濃度為4wt%所製備之含奈米金屬顆粒複合薄膜，其滲透蒸發分離指標(PSI)為最佳。In the above invention, the nano-particle-containing composite film prepared by the nano metal iron concentration of 4% by weight has the best pervaporation separation index (PSI).

在上述發明中，硼氫化鈉溶液之添加量為0.18mL時所製備之含奈米金屬顆粒複合薄膜，其滲透蒸發分離指標(PSI)為最佳。In the above invention, the nano-particle-containing composite film prepared by adding the sodium borohydride solution to 0.18 mL has the best pervaporation separation index (PSI).

本發明為達成上述之目的，所採用之技術手段及所達致之功效效果，茲舉以下較佳可行實施例配合附圖詳述說明於后，俾利完全瞭解。In order to achieve the above objects, the technical means and the effects achieved, the following preferred embodiments are described in detail with reference to the accompanying drawings, which are fully understood.

本發明實施例先以化學還原法配置鑄膜溶液，其過程係稱取不同比例之氯化鐵(Iron(III)Chloride，FeCl₃ )，溶入N-甲基2-四吡咯酮(N-methyl-2-pyrrolidnone，NMP)溶劑中，置於50mL血清瓶中，於室溫下以磁力攪拌機充分攪拌至完全溶解，接著將硼氫化鈉(Sodium borohydride，NaBH₄ )以適量水溶解至完全溶解，然後加入上述氯化鐵NMP溶液中進行化學還原反應，反應完全後形成含奈米鐵之N-甲基2-四吡咯酮(NMP)溶液，接著稱取聚嗍碸(polysulfone，PSF)高分子顆粒溶於上述奈米鐵溶液中，於室溫下以磁力攪拌機充分攪拌24小時完全溶解後，靜置兩小時待鑄膜溶液中氣泡完全去除，即完成鑄膜溶液之配置。接著，本發明實施例即利用上述鑄膜溶液進一步製備出含奈米金屬顆粒複合薄膜，其過程係以濕式相轉換法製備，刮膜前，先將平板玻璃用去離子水洗淨並沖洗，烘乾後，將靜置完成之澄清鑄膜液適量倒置於玻璃板上，以刮刀塗佈一層均勻且不同厚度於支撐物(玻璃)上後，將其浸入凝聚劑(去離子水)中，過程中聚嗍碸高分子因溶劑和凝聚劑交換而固化成膜，即其脫離支撐物而懸浮於凝聚槽中，藉此判定已經成膜，然後置於去離子水中靜置一天，以去除薄膜上多餘的溶劑，再取出置於空氣中乾燥，最後將薄膜置於真空烘箱中於室溫下乾燥24小時，即完成含奈米金屬顆粒複合薄膜之製備程序。In the embodiment of the invention, the casting solution is firstly arranged by a chemical reduction method, and the process is to weigh different proportions of ferric chloride (Iron (III) Chloride, FeCl ₃ ) and dissolve into N-methyl 2-tetrapyrrolidone (N- Methyl-2-pyrrolidnone, NMP) solvent, placed in a 50mL serum bottle, stirred thoroughly at room temperature with a magnetic stirrer until completely dissolved, then sodium borohydride (Sodium borohydride, NaBH ₄ ) dissolved in an appropriate amount of water to completely dissolve Then, the above-mentioned iron chloride NMP solution is added to carry out a chemical reduction reaction, and after completion of the reaction, a solution of N-methyl 2-tetrapyrrolidone (NMP) containing nano iron is formed, and then polysulfone (PSF) is high. The molecular particles are dissolved in the above-mentioned nano-iron solution, and after completely stirring at room temperature for 24 hours in a magnetic stirrer, the bubbles are completely removed after standing for two hours, that is, the configuration of the casting solution is completed. Next, in the embodiment of the present invention, the nanometer-containing metal particle composite film is further prepared by using the above casting solution, and the process is prepared by a wet phase conversion method. Before the film is scraped, the flat glass is washed and rinsed with deionized water. After drying, the clarified casting solution liquid which is left to stand is poured on a glass plate, and a uniform layer of different thickness on the support (glass) is applied by a doctor blade, and then immersed in a coagulant (deionized water). During the process, the polyfluorene polymer is solidified into a film by solvent and coagulant exchange, that is, it is suspended from the support and suspended in the coagulation tank, thereby determining that the film has been formed, and then standing in deionized water for one day to remove The excess solvent on the film is removed and dried in air. Finally, the film is dried in a vacuum oven at room temperature for 24 hours to complete the preparation process of the nano-particle-containing composite film.

本發明實施例以化學還原法製備含奈米金屬顆粒複合薄膜時，即進行以下各種實驗，藉以探討以化學還原法所製得之含奈米顆粒複合薄膜之各種性能。In the embodiment of the present invention, when the nano-particle-containing composite film is prepared by the chemical reduction method, the following various experiments are carried out to investigate various properties of the nanoparticle-containing composite film obtained by the chemical reduction method.

本發明實施例為了解含奈米金屬顆粒複合薄膜在成膜過程中成膜時間對緻密層厚度之影響，故稱取不同濃度之氯化鐵(Iron(III)Chloride，FeCl₃ )，分別為2wt%、4wt%、6wt%、8wt%、10wt%，將之與25mL之N-甲基2-四吡咯酮(N-methyl-2-pyrrolidnone，NMP)溶劑混合攪拌均勻，另將2.5g硼氫化鈉(Sodium borohydride，NaBH₄ )溶解於5mL之蒸餾水中，配製成硼氫化鈉水溶液，再依等比例(FeCl₃ /NaBH₄ ，0.14g/0.06mL、0.28g/0.12mL、0.42g/0.18mL、0.56g/0.24mL、0.7g/0.30mL)添加入氯化鐵NMP溶液中，使反應成含奈米鐵之N-甲基2-四吡咯酮(NMP)溶液，再加入適量之22wt%聚嗍碸(polysulfone，PSF)高分子顆粒於上述含奈米鐵之N-甲基2-四吡咯酮(NMP)溶液中，經過混合攪拌溶解後，製備成含奈米金屬鐵顆粒之鑄膜液。In the embodiment of the present invention, in order to understand the influence of the film formation time on the thickness of the dense layer during the film formation process, the different concentrations of iron chloride (Iron (III) Chloride, FeCl ₃ ) are weighed. 2wt%, 4wt%, 6wt%, 8wt%, 10wt%, mixed with 25mL of N-methyl-2-pyrrolidnone (NMP) solvent and stirred evenly, and 2.5g of boron Sodium borohydride (NaBH ₄ ) was dissolved in 5 mL of distilled water to prepare an aqueous solution of sodium borohydride in an equal ratio (FeCl ₃ /NaBH ₄ , 0.14 g / 0.06 mL, 0.28 g / 0.12 mL, 0.42 g / 0.18mL, 0.56g/0.24mL, 0.7g/0.30mL) was added to the ferric chloride NMP solution to form a N-methyl 2-tetrapyrrolidone (NMP) solution containing nano iron, and then added in an appropriate amount. 22wt% polysulfone (PSF) polymer particles are prepared by dissolving in a solution of the above-mentioned nano-iron-containing N-methyl-2-tetrapyrrolidone (NMP), and preparing nano-containing iron particles. Casting solution.

由於高分子鑄膜液中奈米粒子有助於高分子鏈與鏈間之作用力，因此高分子膜形成之過程中，其分子鏈堆疊亦受奈米顆粒影響，此種影響於濕式成膜法中對於成型之皮層厚度更是明顯。第三圖為成膜定型時間對光穿透率之影響關係圖，由圖顯示出奈米金屬鐵濃度增加，其成膜時間會有變慢之情形，此表示當奈米金屬鐵含量增加時，分子鏈與奈米粒子之交互作用延遲了皮層定型之時間，而會拉長成膜時間，因而增加奈米複合薄膜緻密層之厚度。此結果印證鑄膜液中高分子鏈糾纏作用力會受奈米粒子濃度多寡影響，高分子鑄膜液中有奈米金屬顆粒存在時，確實可以影響其成膜時間。Since the nanoparticle in the polymer casting solution contributes to the interaction between the polymer chain and the chain, the molecular chain stack is also affected by the nanoparticle during the formation of the polymer film, and the effect is on the wet formation. The thickness of the formed skin layer is more pronounced in the film method. The third graph is the relationship between the film formation time and the light transmittance. The graph shows that the nano-metal iron concentration increases, and the film formation time will slow down. This indicates that when the nano-metal iron content increases. The interaction between the molecular chain and the nanoparticle delays the time of cortical shaping, and the filming time is elongated, thereby increasing the thickness of the dense layer of the nanocomposite film. This result confirms that the entanglement force of the polymer chain in the casting solution is affected by the concentration of the nanoparticle, and the presence of the nano metal particles in the polymer casting solution can actually affect the film formation time.

接著，本發明實施例添加不同含量之硼氫化鈉，藉以觀察不同添加量之硼氫化鈉在成膜過程中，其成膜時間對光穿透率之影響。由第四圖可以看出，當硼氫化鈉添加量較少時，其成膜時間較慢，故其複合薄膜之緻密層較厚。當硼氫化鈉添加量為0.18mL時則明顯發現，成膜定型之時間顯著縮小。因此可推論出鑄膜液中過量之還原劑無益於延長成膜定型時間，相反地，未反應完全之硼氫化鈉會以鹽之形式於濕式成型系統中加快凝聚劑(水)由皮層快速流出，而縮短了成膜時間。由此可知，硼氫化鈉之含量於還原反應中對於成膜時間有所影響，過多之還原劑無助於成膜時獲得良好結構之薄膜。Next, the present invention adds different amounts of sodium borohydride to observe the effect of different filming time on the light transmittance of sodium borohydride in the film formation process. As can be seen from the fourth figure, when the amount of sodium borohydride added is small, the film formation time is slow, so the dense layer of the composite film is thick. When the amount of sodium borohydride added was 0.18 mL, it was apparent that the time for film formation was significantly reduced. Therefore, it can be inferred that the excess reducing agent in the casting solution is not beneficial for prolonging the film forming time. Conversely, the unreacted sodium borohydride will accelerate the coagulant (water) in the wet molding system in the form of salt. Flow out, shortening the film formation time. From this, it is understood that the content of sodium borohydride has an influence on the film formation time in the reduction reaction, and an excessive amount of the reducing agent does not contribute to a film having a good structure at the time of film formation.

由於過多還原劑無益於獲致良好結構之薄膜，因此爲了解高分子溶液中氯化鐵含量對於複合膜成膜時間之影響，本發明實施例將不同量之氯化鐵及N-甲基2-四吡咯酮添加入聚嗍碸溶解攪拌，製備出含氯化鐵離子之鑄膜液，藉以探討成膜過程對光穿透之影響。此部份係稱取不同濃度之氯化鐵，分別為2wt%、4wt%、6wt%、8wt%、10wt%，將之與25mL之N-甲基2-四吡咯酮混合攪拌均勻，製備成含氯化鐵離子之鑄膜液。第五圖即為以該等氯化鐵離子濃度製備薄膜之成膜時間對光穿透率之影響關係圖，由圖可知，添加不同濃度氯化鐵離子之高分子鑄膜液於凝聚槽中逐漸定型成膜之過程中，並不會因氯化鐵濃度之增加而改變其光穿透率之大小，所以單純添加氯化鐵離子無法顯著改變其薄膜緻密層之厚度。Since too much reducing agent is not beneficial to obtain a film having a good structure, in order to understand the influence of the content of ferric chloride in the polymer solution on the film formation time of the composite film, the embodiments of the present invention will have different amounts of ferric chloride and N-methyl 2- Tetrapyrrolone was added to the polyfluorene to dissolve and stir to prepare a casting solution containing ferric chloride ions, thereby exploring the effect of the film formation process on light penetration. This part is weighed to different concentrations of ferric chloride, respectively 2wt%, 4wt%, 6wt%, 8wt%, 10wt%, and mixed with 25mL of N-methyl-2-tetrapyrone, and prepared into Casting solution containing ferric chloride ions. The fifth figure is the relationship between the film formation time and the light transmittance of the film prepared by the concentration of the ferric chloride ions. It can be seen from the figure that the polymer casting solution with different concentrations of ferric chloride ions is added to the coagulation tank. In the process of gradually forming the film, the light transmittance is not changed by the increase of the concentration of ferric chloride, so the simple addition of ferric chloride ions can not significantly change the thickness of the dense layer of the film.

為更進一步印證光穿透試驗所得之結果，本發明實施例以聚嗍碸(分別為2g、3g、4g)及25mL之N一甲基2-四吡咯酮混合攪拌一天，使完全均勻溶解，然後將攪拌完成之高分子鑄膜液置於黏度計(型號為Rion Viscotester VT-03E)之槽體中，並於槽體下方放置磁石攪拌機，並配置2.5g NaBH₄ 、5mL H₂ O之硼氫化鈉溶液。首先以黏度計轉動10分鐘，觀察無添加硼氫化鈉溶液之高分子黏度，接下來加入0.5mL之硼氫化鈉溶液並開啟磁石攪拌機混合攪拌5分鐘，主要是希望硼氫化鈉溶液能與聚嗍碸混合均勻，此時黏度計關閉，避免磁石攪拌機與黏度計相互干擾，待攪拌5分鐘後，關閉磁石攪拌機，再開啟黏度計轉動10分鐘，並觀測其黏度變化，第六圖為未添加氯化鐵時硼氫化鈉溶液對高分子溶液黏度之影響關係圖，由圖可以看出，無添加氯化鐵之高分子溶液，當硼氫化鈉添加量增加時，其黏度並無明顯之變化，皆維持一定值，由此可知，單純添加硼氫化鈉溶液並無法影響其高分子之黏度。In order to further confirm the results obtained by the light penetrating test, the present invention is mixed and stirred for one day with polyfluorene (2 g, 3 g, 4 g, respectively) and 25 mL of N-methyl 2-tetrapyrrolone to completely dissolve completely. Then, the stirred polymer casting solution is placed in a tank of a viscometer (model Rion Viscotester VT-03E), and a magnet mixer is placed under the tank, and 2.5 g of NaBH ₄ and 5 mL of H ₂ O boron are disposed. Sodium hydride solution. Firstly, the viscosity was measured by a viscometer for 10 minutes, and the polymer viscosity of the sodium borohydride solution was not observed. Then, 0.5 mL of sodium borohydride solution was added and the magnet mixer was turned on for 5 minutes. It is mainly desired that the sodium borohydride solution can be mixed with polyfluorene. The mixture is evenly mixed. At this time, the viscometer is closed to avoid mutual interference between the magnet mixer and the viscometer. After stirring for 5 minutes, the magnet mixer is turned off, and then the viscometer is turned on for 10 minutes, and the viscosity change is observed. The sixth figure shows that no chlorine is added. The relationship between the effect of sodium borohydride solution on the viscosity of polymer solution in the case of iron, it can be seen from the figure that there is no significant change in the viscosity of the polymer solution without the addition of ferric chloride when the amount of sodium borohydride is increased. All of them maintain a certain value, and it can be seen that simply adding a sodium borohydride solution does not affect the viscosity of the polymer.

為了解奈米金屬顆粒於鑄膜液中對黏度之影響，本發明實施例將6wt%之氯化鐵添加入2g、3g、4g、5g、6g之高分子溶液中，其實驗步驟則與上述未添加氯化鐵之黏度測量相同。由第七圖明顯看出，含有氯化鐵之高分子溶液與硼氫化鈉溶液反應時，其黏度很明顯增加，原因為硼氫化鈉與氯化鐵混合時，生成之奈米金屬顆粒所產生之奈米效應影響高分子間之黏度；在高分子含量為2g、3g時，其黏度尚無明顯變化，原因為高分子含量較低，所生成之奈米金屬顆粒無法明顯的對黏度產生影響；高分子含量為5g、6g時，其黏度皆已超過黏度計所能側量之範圍；而高分子含量為4g時，比較第六、七圖得知，奈米金屬鐵粒子於高分子溶液中確實對高分子之黏度有顯著之變化。在成膜過程中，高分子黏度對薄膜緻密層有重要之影響，當黏度越高，其流動性較差，所形成之薄膜較厚，相對的其緻密層也會較厚，因此會有較高之分離性能；反之，黏度越低所形成之薄膜其分離性能也會越低。In order to understand the influence of the nano metal particles on the viscosity in the casting solution, in the embodiment of the present invention, 6 wt% of ferric chloride is added to the polymer solution of 2 g, 3 g, 4 g, 5 g, and 6 g, and the experimental steps are as follows. The viscosity measurement was the same without adding ferric chloride. It is apparent from the seventh figure that when the polymer solution containing ferric chloride is reacted with the sodium borohydride solution, the viscosity thereof is remarkably increased because the produced nano metal particles are produced when sodium borohydride is mixed with ferric chloride. The nano-effect affects the viscosity between the polymers; when the polymer content is 2g, 3g, the viscosity has not changed significantly, because the low molecular content, the generated nano metal particles can not significantly affect the viscosity. When the polymer content is 5g or 6g, the viscosity has exceeded the range of the side of the viscometer; when the polymer content is 4g, the sixth and seventh figures are compared, and the nano metal iron particles are in the polymer solution. There is a significant change in the viscosity of the polymer. In the film formation process, the viscosity of the polymer has an important influence on the dense layer of the film. When the viscosity is higher, the fluidity is poor, and the formed film is thicker, and the dense layer is thicker, so it will be higher. The separation performance; conversely, the lower the viscosity, the lower the separation performance of the film formed.

本發明實施例為了更清楚了解高分子黏度增加對緻密層厚度之影響，接著將未添加任何物質之高分子薄膜、添加硼氫化鈉之高分子薄膜及含有奈米金屬顆粒之高分子複合薄膜三種利用環境掃描式電子顯微鏡(E-SEM)觀察其緻密層之厚度。第八、九、十圖為未添加任何物質之高分子薄膜放大不同倍率之切面圖，由圖可以看出未添加任何物質之高分子薄膜，其緻密層厚度非常薄。第十一、十二、十三圖為添加硼氫化鈉之高分子薄膜放大不同倍率切面圖，由圖可以得知，添加硼氫化鈉於高分子溶液中所製備之高分子薄膜，與未添加任何物質之高分子薄膜其緻密層厚度並未有明顯之差別。由此也說明硼氫化鈉並無法改變高分子溶液之黏度，也無法有效改變緻密層之厚度。第十四、十五、十六圖則為含奈米金屬顆粒之高分子複合薄膜放大不同倍率切面圖，由圖中可以很明顯的看出，當高分子濃度為2g、3g時，因其高分子濃度較低，故緻密層厚度增加有限，但當高分子濃度為4g、5g時，比較第十、十三、十六圖(同在放大為12,000倍之倍率下)可以很清楚的看出，其緻密層厚度明顯的增厚約一倍，而且也更緊密，對照之前之黏度測試，可以很明確的知道，當高分子溶液中有奈米金屬顆粒存在時，會改變其高分子之黏度，也會影響其高分子薄膜緻密層之厚度。In order to more clearly understand the influence of the increase of the viscosity of the polymer on the thickness of the dense layer, the polymer film without any substance, the polymer film with sodium borohydride and the polymer composite film containing the nano metal particles are three kinds of materials. The thickness of the dense layer was observed using an environmental scanning electron microscope (E-SEM). The eighth, ninth and tenth figures are the cut-away views of the polymer film without any substance to enlarge the different magnifications. It can be seen from the figure that the polymer film without any substance has a very thin thickness. The eleventh, twelfth and thirteenth figures are the polymer films with sodium borohydride added to enlarge the different magnification cutaway views. It can be seen from the figure that the polymer film prepared by adding sodium borohydride in the polymer solution is not added. There is no significant difference in the thickness of the dense layer of the polymer film of any substance. This also shows that sodium borohydride does not change the viscosity of the polymer solution, nor can it effectively change the thickness of the dense layer. The fourteenth, fifteenth and sixteenth plans are for the magnification of different magnifications of the polymer composite film containing nano metal particles. It can be clearly seen from the figure that when the polymer concentration is 2g or 3g, The polymer concentration is low, so the thickness of the dense layer is limited, but when the polymer concentration is 4g, 5g, compare the tenth, thirteenth, and sixteenth figures (the magnification is 12,000 times the magnification) can be clearly seen The thickness of the dense layer is obviously doubled and doubled. Compared with the previous viscosity test, it can be clearly known that when there are nano metal particles in the polymer solution, the polymer is changed. Viscosity also affects the thickness of the dense layer of the polymer film.

本發明實施例為了解以化學還原法製備之含奈米金屬鐵顆粒複合薄膜對滲透蒸發性能之影響，故稱取不同濃度之氯化鐵(Iron(III)Chloride，FeCl₃ )，分別為2wt%、4wt%、6wt%、8wt%、10wt%，將之與25mL之N-甲基2-四吡咯酮(N-methyl-2-pyrrolidnone，NMP)混合攪拌均勻，另將2.5g硼氫化鈉(Sodium borohydride，NaBH4)溶解於5mL之蒸餾水中，配製成硼氫化鈉水溶液，再依等比例(添加量分別為0.06mL、0.12mL、0.18mL、0.24mL、0.30mL)添加入氯化鐵NMP溶液中，使反應成含奈米鐵之N-甲基2-四吡咯酮(NMP)溶液，再加入適量之22wt%聚嗍碸(polysulfone，PSF)高分子顆粒於上述含奈米鐵之N-甲基2-四吡咯酮(NMP)溶液中，經過混合攪拌溶解後，製備成含奈米金屬鐵顆粒之非對稱性薄膜。由第十七圖可以看出，添加不同濃度之奈米顆粒，其滲透蒸發分離性能確實有明顯之提升，在濃度4wt%時有最好之分離效能，之後隨著奈米鐵濃度之增加，其分離效能也逐漸降低，且透過量也隨著奈米鐵濃度之增加而逐漸升高，主要原因為奈米金屬鐵在高分子溶液中會因其奈米粒子與分子鏈糾纏效應，提高其高分子溶液之黏滯性，增加非對稱性薄膜之緻密層厚度，因而提高其分離性能；但過多之奈米金屬鐵卻容易在高分子溶液中形成團聚現象，造成奈米鐵金屬顆粒過大，且過多未完全反應之氯化鐵在成膜過程中會迅速穿透薄膜緻密層，增加薄膜之缺陷並降低非對稱性薄膜緻密層之緻密度，因此降低分離性能，且透過量也升高。In the embodiment of the present invention, in order to understand the influence of the nano-metal iron particle composite film prepared by the chemical reduction method on the pervaporation performance, different concentrations of ferric chloride (Iron (III) Chloride, FeCl ₃ ) are weighed, respectively, 2 wt. %, 4wt%, 6wt%, 8wt%, 10wt%, mix and mix with 25mL of N-methyl-2-pyrrolidnone (NMP), and add 2.5g of sodium borohydride (Sodium borohydride, NaBH4) was dissolved in 5 mL of distilled water to prepare an aqueous solution of sodium borohydride, and then added to ferric chloride in equal proportions (0.06 mL, 0.12 mL, 0.18 mL, 0.24 mL, 0.30 mL, respectively). In the NMP solution, the reaction is made into a solution of N-methyl 2-tetrapyrrolidone (NMP) containing nano iron, and an appropriate amount of 22% by weight of polysulfone (PSF) polymer particles is added to the above-mentioned nano-iron-containing In a solution of N-methyl-2-tetrapyrrolidone (NMP), after dissolution and dissolution, an asymmetric film containing nano metal iron particles is prepared. It can be seen from the seventeenth figure that the addition of different concentrations of nano-particles has a significant improvement in pervaporation separation performance, and the best separation efficiency at a concentration of 4 wt%, followed by an increase in the concentration of nano-iron. The separation efficiency is also gradually reduced, and the permeation amount is gradually increased with the increase of the concentration of nano-iron. The main reason is that the nano-metal iron is entangled in the polymer solution due to the entanglement effect of its nanoparticles and molecular chains. The viscosity of the polymer solution increases the thickness of the dense layer of the asymmetric film, thereby improving its separation performance; however, the excessive nano metal iron is liable to form agglomeration in the polymer solution, causing the nano-iron metal particles to be too large. And too much incompletely reacted ferric chloride rapidly penetrates the dense layer of the film during the film formation process, increasing the defects of the film and reducing the density of the asymmetric thin film dense layer, thereby lowering the separation performance and increasing the permeation amount.

第十八圖為奈米鐵濃度0~10wt%之滲透蒸發分離指標(Pervaporation separation index，PSI)值關係圖。由圖可知，當奈米鐵濃度為4wt%時之奈米複合薄膜，其滲透蒸發分離指標(PSI)值為最好。所以本研究就以含奈米鐵濃度為4wt%所製備之奈米複合薄膜來做進一步之研究，探討其滲透蒸發分離條件與分離性能之影響。The eighteenth figure shows the relationship between the pervaporation separation index (PSI) of the nano iron concentration of 0 to 10% by weight. As can be seen from the figure, the nano-composite film with a nano iron concentration of 4 wt% has the best pervaporation separation index (PSI) value. Therefore, in this study, a nanocomposite film prepared with a nano iron concentration of 4 wt% was used for further study to investigate the effects of pervaporation separation conditions and separation performance.

第十九、二十、二十一圖為不同奈米金屬鐵濃度之奈米複合薄膜之環境掃描式電子顯微鏡(SEM)切面圖，由圖中可以看出，添加不同濃度之奈米金屬顆粒，其奈米複合薄膜之緻密層會有明顯之增厚情形。由此可知，奈米金屬顆粒對於複合薄膜之緻密層可以有顯著之影響。The nineteenth, twenty-first and twenty-first graphs are environmental scanning electron microscopy (SEM) cut-away views of nanocomposite films with different nano-metal iron concentrations. It can be seen from the figure that different concentrations of nano-metal particles are added. The dense layer of the nanocomposite film will have a significant thickening. It can be seen that the nano metal particles can have a significant influence on the dense layer of the composite film.

本發明實施例為了更確定氯化鐵溶液在化學還原過程中是否完全反應成奈米金屬鐵，所以進一步改變硼氫化鈉之添加量來製備含奈米顆粒之複合薄膜，藉以了解硼氫化鈉不同添加量對滲透蒸發分離性能之影響，此實驗以氯化鐵含量為4wt%所製備之複合薄膜來進行。第二十二圖為不同硼氫化鈉添加量對複合薄膜滲透蒸發分離性能之影響關係圖，由圖可知硼氫化鈉添加量之變化確實對分離性能有明顯之影響，當添加較少量之硼氫化鈉溶液時，雖然氯化鐵離子並未完全反應成奈米鐵顆粒，但對奈米複合薄膜之分離性能已有明顯之提升，隨著硼氫化鈉溶液添加量增加為0.18mL時會有最高之分離性能，但隨著硼氫化鈉溶液添加量繼續增加，其分離性能迅速降低，甚至比未改良之高分子薄膜更低。其原因係添加過多之硼氫化鈉溶液時，溶液中會有過多之蒸餾水，導致在成膜過程中容易造成薄膜緻密層破洞，因而降低分離效能；另一個原因則是過多之硼氫化鈉溶液容易在高分子溶液中生成金屬鹽類，於成膜過程中金屬鹽類容易穿透薄膜表面，導致形成孔洞而降低分離性能。所以由第二十二圖可知，當硼氫化鈉溶液添加量為0.18mL時其分離效能為最好。In order to further determine whether the ferric chloride solution completely reacts into nano metal iron during the chemical reduction process, the present invention further changes the amount of sodium borohydride to prepare a composite film containing nano particles, thereby understanding that sodium borohydride is different. The effect of the amount added on the pervaporation separation performance was carried out with a composite film prepared by having a ferric chloride content of 4% by weight. The twenty-second chart shows the relationship between the amount of different sodium borohydride added to the pervaporation separation performance of the composite film. It can be seen from the figure that the change of the amount of sodium borohydride does have a significant effect on the separation performance, when a smaller amount of boron is added. In the sodium hydride solution, although the ferric chloride ion is not completely reacted into nano-iron particles, the separation performance of the nano-composite film has been significantly improved, and as the amount of sodium borohydride solution increases to 0.18 mL, there will be The highest separation performance, but as the amount of sodium borohydride solution continues to increase, its separation performance is rapidly reduced, even lower than the unmodified polymer film. The reason is that when too much sodium borohydride solution is added, there is too much distilled water in the solution, which leads to easy formation of a dense layer of the film during the film formation process, thereby reducing the separation efficiency; another reason is excessive sodium borohydride solution. It is easy to form metal salts in a polymer solution, and metal salts easily penetrate the surface of the film during film formation, resulting in the formation of voids and reduced separation performance. Therefore, it can be seen from the twenty-second chart that the separation efficiency is best when the sodium borohydride solution is added in an amount of 0.18 mL.

第二十三圖為不同硼氫化鈉添加量對複合薄膜滲透蒸發分離指標(PSI)值關係圖，由圖可知當硼氫化鈉溶液添加量為0.18mL時，其滲透蒸發分離指標值為最大。第二十四、二十五、二十六圖為不同硼氫化鈉添加量製備之奈米金屬複合薄膜之環境掃描式電子顯微鏡(SEM)切面圖，由圖可知當硼氫化鈉添加量為0.18mL時，其奈米金屬複合薄膜有最佳之緻密層厚度。因此可知，當奈米金屬鐵濃度為4 wt%、硼氫化鈉添加量為0.18mL時，會有最好之分離效能。The twenty-third figure shows the relationship between the amount of different sodium borohydride added to the pervaporation separation index (PSI) of the composite film. It can be seen from the figure that when the amount of sodium borohydride solution is 0.18 mL, the pervaporation separation index value is the largest. The twenty-fourth, twenty-fifth, and twenty-sixth drawings are environmental scanning electron microscope (SEM) cut-away views of nano-metal composite films prepared by different amounts of sodium borohydride added. It can be seen from the figure that when the amount of sodium borohydride is 0.18 In the case of mL, the nanocomposite film has the best dense layer thickness. Therefore, it is understood that when the nano metal iron concentration is 4 wt% and the sodium borohydride addition amount is 0.18 mL, the best separation efficiency is obtained.

接著，本發明實施例即以奈米金屬鐵濃度為4 wt%、硼氫化鈉添加量為0.18mL之組成對其滲透蒸發之進料濃度及進料溫度做實驗驗證。第二十七圖為以4 wt%之氯化鐵離子及以0.18mL之硼氫化鈉溶液進行化學還原反應所製備之奈米顆粒複合薄膜，在90 wt%進料乙醇濃度而改變進料溶液溫度(由15℃增加至45℃)對滲透蒸發性能之影響關係圖。由圖可知隨著溫度之增加，透過量緩慢的上升，但上升幅度並不大，其原因係當進料溫度上升時水合作用只有些微變化，所以對 物質穿透薄膜之穿透能力影響不大，直到進料溫度增加至45℃時透過量才有明顯增加，但其分離係數則是明顯下降。其原因係進料溫度在高溫下，高分子膨潤程度增加，使得高分子鏈間之間隙增大，造成水分子與乙醇分子容易穿透薄膜，導致薄膜透過量上升，但分離係數則下降之情形。Next, in the embodiment of the present invention, the feed concentration and the feed temperature of the pervaporation are verified by the composition of the nano metal iron concentration of 4 wt% and the sodium borohydride addition amount of 0.18 mL. The twenty-seventh picture shows a nanoparticle composite film prepared by chemical reduction reaction of 4 wt% of ferric chloride ion and 0.18 mL of sodium borohydride solution, and changing the feed solution at a feed concentration of 90 wt% of ethanol. Diagram of the effect of temperature (from 15 ° C to 45 ° C) on pervaporation performance. It can be seen from the figure that as the temperature increases, the amount of permeation increases slowly, but the increase is not large. The reason is that when the feed temperature rises, the hydration only slightly changes, so The penetrating ability of the material penetrating film has little effect, and the permeation amount increases only when the feed temperature is increased to 45 ° C, but the separation coefficient is significantly decreased. The reason is that when the feed temperature is high, the degree of swelling of the polymer increases, so that the gap between the polymer chains increases, and the water molecules and the ethanol molecules easily penetrate the film, resulting in an increase in the permeability of the film, but the separation coefficient is decreased. .

第二十八圖為以4 wt%之氯化鐵離子及以0.18mL之硼氫化鈉溶液進行化學還原反應所製備之奈米顆粒複合薄膜，在進料溫度25℃下，改變不同進料乙醇濃度(由10 wt%~90 wt%)對滲透蒸發性能之影響關係圖。由圖可知，隨著進料濃度之增加，其水/乙醇比值明顯降低。原因在於進料濃度之增加，奈米複合薄膜之高分子鏈間之間隙被膨潤開來，使得乙醇分子穿透薄膜，造成其乙醇含量之增多，而降低其滲透蒸發分離性能。The twenty-eighthth image shows a nanoparticle composite film prepared by chemical reduction reaction of 4 wt% ferric chloride ion and 0.18 mL of sodium borohydride solution, and changing different feed ethanol at a feed temperature of 25 ° C Relationship between concentration (from 10 wt% to 90 wt%) on pervaporation performance. As can be seen from the figure, as the feed concentration increases, the water/ethanol ratio decreases significantly. The reason is that the increase of the feed concentration, the gap between the polymer chains of the nanocomposite film is swollen, so that the ethanol molecules penetrate the film, causing an increase in the ethanol content thereof and lowering the pervaporation separation performance.

第二十九圖為以4 wt%之氯化鐵離子及以0.18mL之硼氫化鈉溶液進行化學還原反應所製備之奈米顆粒複合薄膜，在進料溫度25℃、進料乙醇濃度90 wt-%下，改變不同聚嗍碸濃度對滲透蒸發性能之影響關係圖。由圖可知，當高分子濃度增加時，其分離性能會先上升而後下降，在高分子濃度為7g時最好。原因為當高分子濃度較低時，其高分子無法堆積很密集，高分子鏈間之間隙較大，但隨著高分子增加使得高分子鏈之間隙減小，而增加其分離性能，但過多之高分子在奈米金屬鐵之牽引下，容易形成高分子團，使得高分子鏈間 容易出現縫隙，而降低其分離性能，使得透過量隨著高分子濃度之增加，而呈現降低的趨勢。The twenty-ninth figure shows a nanoparticle composite film prepared by chemical reduction of 4 wt% ferric chloride ion and 0.18 mL of sodium borohydride solution at a feed temperature of 25 ° C and a feed ethanol concentration of 90 wt. -%, change the relationship between the concentration of different polyfluorenes on the pervaporation performance. As can be seen from the figure, when the concentration of the polymer increases, the separation performance first rises and then decreases, and is preferably at a polymer concentration of 7 g. The reason is that when the polymer concentration is low, the polymer cannot be densely packed, and the gap between the polymer chains is large, but as the polymer increases, the gap of the polymer chain decreases, and the separation performance is increased, but too much Under the traction of nano metal iron, the polymer is easy to form a polymer group, which makes the polymer chain It is prone to gaps and lowers its separation performance, so that the amount of permeation tends to decrease as the concentration of the polymer increases.

第三十、三十一、三十二圖為以4 wt%之氯化鐵離子及以0.18mL之硼氫化鈉溶液進行化學還原反應所製備之奈米顆粒複合薄膜在不同聚嗍碸高分子濃度時之環境掃描式電子顯微鏡(SEM)切面圖，由圖中可以明顯看出，當聚嗍碸高分子濃度增加時，其緻密層會增厚，但是過多之高分子卻容易造成高分子團，反而無法有效增加其緻密層厚度，且會造成緻密層結構之鬆散，以至於無法有效提升其分離性能。The thirty-th, thirty-first, and thirty-second figures are nano-particle composite films prepared by chemical reduction reaction of 4 wt% ferric chloride ion and 0.18 mL of sodium borohydride solution in different polyfluorene polymers. The environmental scanning electron microscope (SEM) cut-away view at the concentration shows that when the concentration of the polyfluorene polymer increases, the dense layer will thicken, but the excessive polymer tends to cause the polymer mass. On the contrary, it is unable to effectively increase the thickness of the dense layer, and the structure of the dense layer is loose, so that the separation performance cannot be effectively improved.

本發明以化學還原法製備含奈米金屬顆粒複合薄膜之製備方法經由以上實驗可得如下結論：The preparation method of preparing nanometer metal particle composite film by chemical reduction method of the invention can obtain the following conclusions through the above experiment:

一、以化學還原法製備奈米金屬鐵複合薄膜，其滲透蒸發分離能確實有明顯之提升，在奈米金屬鐵濃度4 wt%時有最好之分離效能，之後隨著奈米鐵濃度之增加，其分離效能也逐漸降低，而透過量也逐漸升高。1. Preparation of nano-metal iron composite film by chemical reduction method, the pervaporation separation energy can be obviously improved, and the best separation efficiency is obtained when the nano-metal iron concentration is 4 wt%, and then with the nano-iron concentration When it is increased, its separation efficiency is also gradually reduced, and the amount of permeation is gradually increasing.

二、奈米金屬鐵在高分子溶液中，因其奈米粒子與分子鏈糾纏效應，會提高高分子溶液之黏滯性，增加非對稱性薄膜之緻密層厚度，而提高其分離性能；但過多之奈米金屬鐵卻形成團聚現象，造成奈米鐵金屬顆粒過大，過多未完全反應之氯化鐵，在成膜過程中會迅速穿透薄膜緻密層，增加薄膜之缺陷，降低非對稱性薄膜緻密層之緻密度，反而使得分離性能降低，透過量升高。2. Nano-metal iron in polymer solution, due to the entanglement effect of nano-particles and molecular chains, will increase the viscosity of the polymer solution, increase the thickness of the dense layer of the asymmetric film, and improve its separation performance; Excessive nano-metal iron forms agglomeration, which causes the nano-iron metal particles to be too large. Too much incompletely reacted ferric chloride will quickly penetrate the dense layer of the film during film formation, increasing the defects of the film and reducing the asymmetry. The density of the dense layer of the film, on the contrary, reduces the separation performance and increases the amount of transmission.

三、硼氫化鈉溶液之添加量在0.18mL時有最高之分離性能，過多之硼氫化鈉溶液則容易造成薄膜緻密層破洞，且金屬鹽類容易穿透薄膜表面，導致形成孔洞而降低其分離性能。3. The addition amount of sodium borohydride solution has the highest separation performance at 0.18 mL. Excessive sodium borohydride solution easily causes the dense layer of the film to be broken, and the metal salt easily penetrates the surface of the film, resulting in the formation of pores and lowering thereof. Separation performance.

由以上說明可知，本發明以化學還原法製備含奈米金屬顆粒複合薄膜之製備方法，主要技術內容係先以化學還原法配置鑄膜溶液，其過程係將氯化鐵(Iron(III)Chloride，FeCl₃ )溶入N-甲基2-四吡咯酮(N-methyl-2pyrrolidnone，NMP)溶劑混合攪拌均勻，另將硼氫化鈉(Sodiumborohydride，NaBH₄ )溶解於蒸餾水中，配製成硼氫化鈉水溶液，然後將硼氫化鈉水溶液加入上述氯化鐵NMP溶液中進行化學還原反應，反應完全後形成含奈米鐵之N-甲基2-四吡咯酮(NMP)溶液，接著取聚嗍碸(polysulfone，PSF)高分子顆粒溶於上述奈米鐵溶液中，於室溫下經過混合攪拌完全溶解後，靜置待鑄膜溶液中氣泡完全去除，即完成鑄膜溶液之配置；接著即利用上述鑄膜溶液以濕式相轉換法製備出含奈米金屬顆粒複合薄膜；其中，奈米金屬鐵濃度為4 wt%及硼氫化鈉溶液之添加量為0.18mL時所製備之含奈米金屬顆粒複合薄膜，其滲透蒸發分離指標(PSI)為最佳。It can be seen from the above description that the preparation method of the nanometer-containing metal particle composite film is prepared by the chemical reduction method, and the main technical content is that the casting film solution is firstly arranged by a chemical reduction method, and the process is iron chloride (Iron (III) Chloride , FeCl ₃ ) dissolved in N-methyl-2-pyrrolidone (NMP) solvent mixed and stirred uniformly, and dissolved sodium borohydride (Sodiumborohydride, NaBH ₄ ) in distilled water to prepare hydroboration a sodium aqueous solution, and then adding an aqueous solution of sodium borohydride to the above-mentioned iron chloride NMP solution for chemical reduction reaction, and after completion of the reaction, a solution of N-methyl 2-tetrapyrrolidone (NMP) containing nano iron is formed, followed by polycondensation. (polysulfone, PSF) polymer particles are dissolved in the above-mentioned nano-iron solution, completely dissolved at room temperature after mixing and stirring, and the bubbles in the solution to be cast are completely removed, that is, the configuration of the casting solution is completed; The cast film solution is prepared by a wet phase conversion method, wherein the nano metal-containing composite film is prepared by using a nano metal iron concentration of 4 wt% and a sodium borohydride solution of 0.18 mL; One Composite films, pervaporation separation index (PSI) is the best.

綜上所述，本發明確為一種前所未見之製備方法，經多方實驗及測試，證實效果良好，深具產業上利用價值，方提出發明專利申請。懇請審查後早日准予專利、實感德便。In summary, the present invention is indeed a preparation method that has never been seen before. After many experiments and tests, it is proved that the effect is good, and the industrial use value is deeply used, and the invention patent application is filed. I would like to ask for a patent as soon as possible after the review.

第一圖係習知薄膜相關作用示意圖。The first figure is a schematic diagram of the related functions of the conventional film.

第二圖係習知薄膜進行滲透蒸發作用示意圖。The second figure is a schematic diagram of the conventional method for pervaporation of a film.

第三圖係本發明成膜定型時間對光穿透率之影響關係圖。The third graph is a graph showing the influence of the film formation time on the light transmittance of the present invention.

第四圖係本發明不同硼氫化鈉添加量成膜定型時間對光穿透率之影響關係圖。The fourth graph is a graph showing the effect of different sodium borohydride addition amount on the light transmittance of the present invention.

第五圖係本發明不同氯化鐵含量成膜定型時間對光穿透率之影響關係圖。The fifth graph is a graph showing the influence of different ferric chloride content forming time on the light transmittance of the present invention.

第六圖係未添加氯化鐵時硼氫化鈉溶液對高分子溶液黏度之影響關係圖。The sixth graph is the relationship between the effect of sodium borohydride solution on the viscosity of the polymer solution when no ferric chloride is added.

第七圖係本發明添加氯化鐵時硼氫化鈉溶液對高分子溶液黏度之影響關係圖。The seventh figure is a graph showing the influence of the sodium borohydride solution on the viscosity of the polymer solution when the ferric chloride is added according to the present invention.

第八、九、十圖係未添加任何物質之高分子薄膜環境掃描式電子顯微鏡放大不同倍率切面圖。The eighth, ninth and tenth drawings are polymer film scanning electron microscopes without any substance added to magnify different magnification cut charts.

第十一、十二、十三圖係添加硼氫化鈉之高分子薄膜環境掃描式電子顯微鏡放大不同倍率切面圖。The eleventh, twelfth, and thirteenth images are obtained by adding a sodium borohydride polymer film to an environmental scanning electron microscope to magnify different magnification cut charts.

第十四、十五、十六圖係本發明含奈米金屬顆粒之高分子複合薄膜環境掃描式電子顯微鏡放大不同倍率切面圖。The fourteenth, fifteenth and sixteenth drawings are diagrams showing the magnification of different magnifications of the polymer scanning electron microscope containing the nano metal particles of the present invention.

第十七圖係本發明添加不同氯化鐵濃度之奈米金屬顆粒複合薄膜於90wt%乙醇25℃對滲透蒸發之影響關係圖。Figure 17 is a graph showing the effect of the nano metal particle composite film of different ferric chloride concentrations on the pervaporation of 90 wt% ethanol at 25 ° C according to the present invention.

第十八圖係本發明添加不同氯化鐵濃度之奈米金屬顆粒複合薄膜於90wt%乙醇25℃之滲透蒸發分離指標值關係圖。The eighteenth figure is a graph showing the relationship between the index values of the pervaporation separation of the nano metal particle composite film of the present invention added with different ferric chloride concentrations at 90 ° C ethanol at 25 ° C.

第十九、二十、二十一圖係本發明添加不同奈米金屬鐵濃度之 奈米金屬顆粒複合薄膜環境掃描式電子顯微鏡放大不同倍率切面圖。The nineteenth, twenty-first, twenty-first embodiment of the present invention adds different nano metal iron concentrations The nano-metal particle composite film environmental scanning electron microscope magnifies different magnification cut charts.

第二十二圖係本發明不同硼氫化鈉添加量之奈米金屬顆粒複合薄膜於90wt%乙醇25℃對滲透蒸發之影響關係圖。The twenty-second graph is a graph showing the effect of different nano borohydride addition amount of nanometer metal particle composite film on pervaporation of 90 wt% ethanol at 25 ° C according to the present invention.

第二十三圖係本發明不同硼氫化鈉添加量之奈米金屬顆粒複合薄膜滲透蒸發分離指標值關係圖。The twenty-third figure is a relationship diagram of the pervaporation separation index values of the nano metal hydride composite film with different amounts of sodium borohydride added according to the present invention.

第二十四、二十五、二十六圖係本發明不同硼氫化鈉添加量之奈米金屬複合薄膜環境掃描式電子顯微鏡放大不同倍率切面圖。The twenty-fourth, twenty-fifth, and twenty-sixth drawings show the different scanning magnification electron microscopes of the nano-metal composite film with different sodium borohydride addition amount in the present invention.

第二十七圖係本發明以4 wt%氯化鐵離子及0.18mL硼氫化鈉溶液製備之奈米金屬顆粒複合薄膜在90 wt%進料乙醇濃度下改變進料溶液溫度對滲透蒸發性能之影響關係圖。The twenty-seventh embodiment of the present invention is a nano metal particle composite film prepared by using 4 wt% ferric chloride ion and 0.18 mL of sodium borohydride solution to change the temperature of the feed solution to pervaporation performance at a concentration of 90 wt% of feed ethanol. Impact diagram.

第二十八圖係本發明以4 wt%氯化鐵離子及0.18mL硼氫化鈉溶液製備之奈米金屬顆粒複合薄膜在進料溫度25℃下改變進料乙醇濃度對滲透蒸發性能之影響關係圖。The twenty-eighth figure shows the effect of changing the ethanol concentration of the feed on the pervaporation performance at a feed temperature of 25 ° C at a nano metal particle composite film prepared by using 4 wt% ferric chloride ion and 0.18 mL of sodium borohydride solution. Figure.

第二十九圖係本發明以4 wt%氯化鐵離子及0.18mL硼氫化鈉溶液製備之奈米金屬顆粒複合薄膜在進料溫度25℃及進料乙醇濃度90 wt%下改變不同聚嗍碸濃度對滲透蒸發性能之影響關係圖。The twenty-ninth aspect of the present invention is a nano metal particle composite film prepared by using 4 wt% ferric chloride ion and 0.18 mL of sodium borohydride solution to change different polyfluorene at a feed temperature of 25 ° C and a feed ethanol concentration of 90 wt %. Diagram of the effect of cerium concentration on pervaporation performance.

第三十、三十一、三十二圖為本發明以4 wt%氯化鐵離子及0.18mL硼氫化鈉溶液及不同高分子濃度製備之奈米金屬顆粒複合薄膜環境掃描式電子顯微鏡放大不同倍率切面圖。The thirty-th, thirty-first, and thirty-second diagrams are different in the environment scanning electron microscope magnification of the nano metal particle composite film prepared by using 4 wt% ferric chloride ion and 0.18 mL of sodium borohydride solution and different polymer concentrations. Magnification cutaway.

Claims (1)

一種以化學還原法製備含奈米金屬顆粒複合薄膜之製備方法，主要先以化學還原法配置鑄膜溶液，其過程係將氯化鐵(Iron(III)Chloride，FeCl₃ )溶入N-甲基2-四吡咯酮(N-methyl-2-pyrrolidnone，NMP)溶劑混合攪拌均勻，另將硼氫化鈉(Sodium borohydride，NaBH₄ )溶解於蒸餾水中，配製成硼氫化鈉水溶液，然後將硼氫化鈉水溶液添加量0.18mL加入上述氯化鐵NMP溶液中進行化學還原反應，反應完全後形成含奈米金屬鐵濃度為4 wt%之N-甲基2-四吡咯酮(NMP)溶液，接著取聚嗍碸(polysulfone，PSF)高分子顆粒溶於上述含奈米金屬鐵濃度為4 wt%之N-甲基2-四吡咯酮(NMP)溶液中，於室溫下經過混合攪拌完全溶解後，靜置待鑄膜溶液中氣泡完全去除，即完成鑄膜溶液之配置；接著即利用上述鑄膜溶液以濕式相轉換法製備出含奈米金屬顆粒複合薄膜。A preparation method for preparing a nanometer-containing metal particle composite film by a chemical reduction method, which firstly configures a casting solution by a chemical reduction method, wherein a process of dissolving iron (Iron (III) Chloride, FeCl ₃ ) into N-A N-methyl-2-pyrrolidnone (NMP) solvent is mixed and stirred uniformly, and sodium borohydride (NaBH ₄ ) is dissolved in distilled water to prepare an aqueous solution of sodium borohydride, and then boron is added. 0.18 mL of an aqueous solution of sodium hydride was added to the above-mentioned iron chloride NMP solution for chemical reduction reaction, and after completion of the reaction, a N-methyl 2-tetrapyrrolidone (NMP) solution containing a metal iron concentration of 4 wt% was formed, followed by The polysulfone (PSF) polymer particles are dissolved in the above N-methyl 2-tetrapyrrolidone (NMP) solution containing 4% by weight of metal iron, and completely dissolved by stirring at room temperature. After that, the bubbles in the solution to be cast are completely removed, that is, the configuration of the casting solution is completed; then, the composite film containing the nano metal particles is prepared by the wet phase conversion method using the above casting solution.