TWI381079B - Nano - gold woven fabric and its preparation method - Google Patents
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本發明係一種黃金織布的製備方法，尤其是一種能夠控制顆粒尺寸且製程簡便之奈米黃金織布的製備方法。 The invention relates to a preparation method of a gold woven fabric, in particular to a preparation method of a nano gold woven fabric capable of controlling particle size and having a simple process.
就其性質而論，金(Au)係一種惰性的黃色金屬，且具有柔軟、可撓曲的性質，其結構屬於面心立方體結構，熔點約為1068℃，黃金的許多應用係基於其獨特性質，此獨特性質來自其相對收縮的6s軌道所造成，且金的陰電性在金屬中屬於最高的金屬，其氧化電位高達約1.691伏特，所以不易有電子轉移，也不容易進行氧化還原反應。 As far as its nature is concerned, gold (Au) is an inert yellow metal with soft, flexible properties. Its structure belongs to a face-centered cubic structure with a melting point of about 1068 ° C. Many applications of gold are based on its unique properties. This unique property is caused by its relatively contracted 6s orbital, and the negative electrical property of gold is the highest metal in the metal, and its oxidation potential is as high as about 1.691 volts, so it is not easy to have electron transfer and it is not easy to carry out redox reaction.
然而，經過奈米化之後，一般金的特性則不完全等同於奈米級黃金顆粒的性質，奈米級黃金顆粒的物理和化學性質會隨粒徑的奈米化而改變，隨著粒徑的減少，比表面積會大幅增加、且粒子邊緣及裸露角增加等。因此現今已有很多奈米級黃金粒子的研究，並預期奈米黃金技術將具有廣泛的應用。 However, after nanocrystallization, the general characteristics of gold are not completely equivalent to the nature of nano-sized gold particles. The physical and chemical properties of nano-sized gold particles change with the nanocrystallization of the particle size. The reduction, the specific surface area will increase significantly, and the particle edge and the exposed angle will increase. Therefore, there are many researches on nano-scale gold particles, and it is expected that nano-gold technology will have a wide range of applications.
由於奈米化黃金的表面會形成凹凸不平的原子台階，而有特別的催化活性，如果又配合具有還原性之金屬氧化物載體，即成為活性高的奈米金觸媒。奈米金觸媒所需的反應溫度低，最佳操作溫度為約200K至350K。雖然黃金觸媒並不能完全取代目前最常使用的鉑觸媒，不過在一些特定的情形中，奈米金觸媒具有比鉑觸媒更好的性質。而目前奈米金觸媒能夠應用於燃料電池與氣體偵測器。如以奈米金觸媒製作的火災逃生口罩等。 Since the surface of the nano-gold has a rugged atomic step and has a special catalytic activity, if it is combined with a reducing metal oxide carrier, it becomes a highly active nano-gold catalyst. The nanogold catalyst requires a low reaction temperature and an optimum operating temperature of about 200K to 350K. Although gold catalysts do not completely replace the most commonly used platinum catalysts, in some specific cases, nanogold catalysts have better properties than platinum catalysts. At present, nano-gold catalyst can be applied to fuel cells and gas detectors. Such as fire escape masks made of nano-gold catalyst.
近年來，許多研究對於奈米黃金的催化性質以逐漸了解，且知其具有殺菌的功能，因此應用廣泛，所以目前每年應用黃金的消耗量大約上百公噸。 In recent years, many studies have gradually understood the catalytic properties of nano-gold, and know that it has a bactericidal function, so it is widely used. Therefore, the annual consumption of gold is about 100 metric tons.
由於奈米黃金相較於其他奈米級的金屬具有較高的抗表面氧化能力，所以在空氣中不容易被氧化，對於目前尺寸日益縮小的電子元件而言是非常重要的，另外，奈米黃金亦具有特殊的光學性質，隨著奈米化的不同，奈米黃金會由紅色轉變為紫色。 Because nano-gold has higher resistance to surface oxidation than other nano-grade metals, it is not easily oxidized in air. It is very important for the current shrinking electronic components. In addition, nano-nano Gold also has special optical properties. With the difference in nanocrystallization, nano gold will change from red to purple.
目前奈米金屬顆粒的合成方法包括有固相法、氣相法以及液相法； At present, the synthesis method of the nano metal particles includes a solid phase method, a gas phase method, and a liquid phase method;
所述的固相法係指往下切割法(top-down process)以物理的方式縮小金屬顆粒的尺寸，又能在之後藉由混合、造粒、燒結後粉碎的程序合成微粒子，然而，最後的粉碎步驟需要耗費較高的成本，且最終得到的顆粒粒徑也僅能達到約100奈米左右即為其極限，無法再使其有更小的粒徑。而氣相法與液相法係目前相關業者大多採用的往上堆積法(bottom up process)。 The solid phase method refers to a method of physically reducing the size of the metal particles by a top-down process, and then synthesizing the microparticles by a process of mixing, granulating, sintering and pulverizing, however, finally The pulverization step requires a relatively high cost, and the resulting particle size can only reach about 100 nm, which is the limit, and it is no longer possible to make it have a smaller particle size. The gas phase method and the liquid phase method are currently used in the bottom up process.
所述的氣相法包括物理氣相沉積法(PVD)，化學氣相沉積法(CVD)、依反應或熱源不同而區分的化學燃燒製程法、電漿製程法(plasma process、雷射製程法(laser process)與電熱爐加熱過程等。 The gas phase method includes physical vapor deposition (PVD), chemical vapor deposition (CVD), chemical combustion process method according to different reaction or heat source, plasma process (laser process, laser process method) (laser process) and electric furnace heating process.
PVD法係藉由控制原料的材質、冷卻溫度、試驗材料的蒸發溫度等條件而產生顆粒大小約在10~100奈米的顆粒。然而，若欲合成尺寸一致的奈米顆粒，必須在快速高溫之後使其急速冷卻，因此，一次粒子(primary particle) 的成長及燒結步驟的控制相當重要。然而，欲控制此步驟而產生尺寸一致的奈米顆粒並不容易。 The PVD method produces particles having a particle size of about 10 to 100 nm by controlling the material of the raw material, the cooling temperature, and the evaporation temperature of the test material. However, if a nanoparticle of the same size is to be synthesized, it must be rapidly cooled after a rapid high temperature, and therefore, primary particles are used. The growth and control of the sintering step are quite important. However, it is not easy to control this step to produce nanoparticle of uniform size.
CVD法係藉由控制蒸氣及反應氣體的濃度、載體氣體等條件來控制顆粒得大小、結晶形態及構造等，以避免不純物進入顆粒中。然而，若將CVD法使用於合成多成分系的奈米顆粒時，因為需要兩種以上的原料，所以會出現原料蒸氣壓不同的情況，而產生不同的化學反應，容易形成不均等的組成。 The CVD method controls the size, crystal morphology and structure of the particles by controlling the concentration of the vapor and the reaction gas, the carrier gas, etc., to prevent impurities from entering the particles. However, when the CVD method is used to synthesize a multi-component nanoparticle, since two or more kinds of raw materials are required, a vapor pressure of the raw material may be different, and a different chemical reaction may occur, and an uneven composition may be easily formed.
所述的液相法係指在液相中進行化學反應以製造微粒子，包括溶膠-凝膠法(Sol-gel)、逆微胞法(Micelle)、熱皂法(Hot Soap)、噴霧熱分解法等。然而，但溶膠-凝膠法、逆微胞法、熱皂法的原料價格昂貴，且製造過程以及使用設備複雜，因此成本昂貴。 The liquid phase method refers to a chemical reaction in a liquid phase to produce microparticles, including a sol-gel method, a micro-cell method (Micelle), a hot soap method (Hot Soap), and a spray thermal decomposition. Law and so on. However, the raw materials of the sol-gel method, the inverse microcell method, and the hot soap method are expensive, and the manufacturing process and the use equipment are complicated, so that they are expensive.
至於噴霧熱分解法目前多使用在二氧化矽奈米粒子得製造。但其必須先產生次微米級(sub-micron)的微細液滴，再配合使用高周波數的超音波與靜電噴霧法及減壓噴霧法等方法而製造奈米粒子，因此過程亦相當繁複。 As for the spray pyrolysis method, it is currently used in the production of cerium oxide nanoparticles. However, it is necessary to first produce sub-micron fine droplets, and to use a high-frequency ultrasonic wave, an electrostatic spray method, and a vacuum spray method to produce nano particles, and the process is also complicated.
由於奈米黃金的特殊性質繁多，可應用在電子產業(如奈米黃金導線可能成為未來的趨勢)、生技產業(如假牙、心血管支架、生物晶片、或與鈦金屬結合以用於促進人體血液循環、癌症治療等)、化工產業(如塗料)、環境污染控制以及燃料電池等方面，而以下針對其在織物上的研究進行說明。 Due to the special nature of nano gold, it can be applied in the electronics industry (such as nano gold wire may become the future trend), biotechnology industry (such as dentures, cardiovascular stents, biochips, or combined with titanium for promotion). Human blood circulation, cancer treatment, etc., chemical industry (such as paint), environmental pollution control, and fuel cell, etc., and the following is a description of its research on fabrics.
如前所述，由於奈米黃金具有極高的抗表面氧化能力，一般在空氣中不容易被氧化，且奈米黃金的表面對於硫化物具有強的化學反應性，可以吸引菌體內蛋白的硫氫 基，並迅速與其結合，以降低細菌等原生物的酵素活性，或破壞細體的細胞膜，而產生抗菌/殺菌的作用，因此目前已有將奈米黃金結合於織物中，以使得該織物具有殺菌的效果。 As mentioned above, because nano gold has a very high resistance to surface oxidation, it is generally not easily oxidized in the air, and the surface of nano gold has strong chemical reactivity to sulfides, which can attract sulfur in the body. hydrogen Base, and quickly combine with it to reduce the enzyme activity of bacteria such as bacteria, or destroy the cell membrane of the fine body, and produce an antibacterial / bactericidal effect, so the nano gold has been incorporated into the fabric so that the fabric has The effect of sterilization.
目前工業化生產的抗菌纖維，大致分有兩種方式。最常見的是如美國Foss公司、Kosa公司等所使用的方法，在布料染整時以奈米顆粒懸浮液為染料，再把布料放入浸漬，再加壓使懸浮液均勻吸收到纖維內，並壓除過多的液體，最後再控制乾燥過程以使得奈米顆粒得以固定在布料上。另一種是如英國Acords公司、日本東麗公司等所使用的方法，直接在纖維表面上還原出奈米顆粒。除此之外，於2003年Yuranova等人曾使用電漿及紫外光對人造纖維進行表面改質，再將纖維浸漬於硝酸銀水溶液中，使銀離子與纖維表面上的官能基螯合後，加入還原劑使銀離子還原成銀粒子，即可得到具有銀的纖維。 At present, there are two ways to industrially produce antibacterial fibers. The most common methods are used by Foss, Kosa, etc. in the United States. When the cloth is dyed and finished, the nanoparticle suspension is used as a dye, and then the fabric is impregnated, and then the suspension is uniformly absorbed into the fiber. Excess liquid is removed and the drying process is controlled to allow the nanoparticles to be fixed to the fabric. The other is a method used by the British company Acords, Japan Toray, etc. to directly reduce the nanoparticle on the surface of the fiber. In addition, in 2003, Yuranova et al. used plasma and ultraviolet light to modify the surface of rayon, and then immersed the fiber in an aqueous solution of silver nitrate to sequester the silver ion with the functional groups on the surface of the fiber. The reducing agent reduces silver ions to silver particles to obtain fibers having silver.
然而，目前尚未開發出能夠控制奈米黃金顆粒的尺寸，且製程簡便的方法，但黃金奈米顆粒又將會是相關產業未來著重的目標，因此，研究一種製造具有奈米黃金顆粒之織布的方法益形重要。 However, no method has been developed to control the size of nano-gold particles, and the process is simple, but gold nanoparticles will be the focus of the related industry in the future. Therefore, research on a fabric made of nano-gold particles. The method is important.
本發明有鑑於既有並未能開發出能夠控制奈米黃金顆粒之尺寸且製程簡便的方法，因此經過不斷的研究以及無數次的試驗之後，終於發明出此奈米黃金織布的製備方法。 The present invention has been invented and failed to develop a method capable of controlling the size of nano gold particles and having a simple process. Therefore, after continuous research and numerous tests, the preparation method of the nano gold woven fabric was finally invented.
本發明之目的係在於提供一種能夠控制顆粒尺寸且製程簡便之奈米黃金織布的製備方法。 The object of the present invention is to provide a method for preparing a nano gold woven fabric capable of controlling particle size and having a simple process.
為達上述目的，本發明係一種奈米黃金織布的製備方法，其係包括：配製一電解液，該電解液包括0.01~0.015 mole/L的亞硫酸金、0.1~0.2 mole/L的檸檬酸鉀、0.4~0.55 mole/L的亞硫酸鈉、0.13~0.25 mole/L的亞硫酸銨之水溶液；將該電解液注入一無電解電鍍反應槽中，再將一織物放置於該無電解電鍍反應槽中，控制該無電解電鍍反應槽之溫度在45~60℃之間恆溫，再將一界面活性劑與一還原劑通入一二氧化碳超臨界流體後置入該無電解電鍍反應槽中，調整該無電解電鍍反應槽中的壓力為大於二氧化碳之超臨界壓力，而溫度係大於二氧化碳之超臨界溫度；經過一特定的反應時間後，即可獲得該奈米黃金織布。 In order to achieve the above object, the present invention is a method for preparing a nano gold woven fabric, which comprises: preparing an electrolyte comprising 0.01 to 0.015 mole/L of gold sulfite and 0.1 to 0.2 mole/L of lemon. Potassium acid, 0.4~0.55 mole/L sodium sulfite, 0.13~0.25 mole/L ammonium sulfite aqueous solution; injecting the electrolyte into an electroless plating reaction tank, and placing a fabric in the electroless plating reaction tank The temperature of the electroless plating reaction tank is controlled to be constant between 45 and 60 ° C, and a surfactant and a reducing agent are introduced into a carbon dioxide supercritical fluid, and then placed in the electroless plating reaction tank, and the adjustment is performed. The pressure in the electroless plating reaction tank is greater than the supercritical pressure of carbon dioxide, and the temperature system is greater than the supercritical temperature of carbon dioxide; after a specific reaction time, the nano gold weaving cloth can be obtained.
其中，該二氧化碳之超臨界壓力係約1040 psi，而該二氧化碳之超臨界溫度為約31℃。 Wherein, the supercritical pressure of the carbon dioxide is about 1040 psi, and the supercritical temperature of the carbon dioxide is about 31 °C.
較佳的是，該界面活性劑係丁二酸二異辛酯磺酸鈉[sodium bis(2-ethylhexyl)sulfosuccinate]；該還原劑為硫脲(thiourea)。 Preferably, the surfactant is sodium bis(2-ethylhexyl)sulfosuccinate; the reducing agent is thiourea.
較佳的是，該無電解電鍍反應槽內的壓力為3,000 psi，溫度為45℃； 其中，於獲得該奈米黃金織布之前，尚包括先將該無電解電鍍反應槽洩壓至常壓，並降溫至常溫後，以安全地取得該奈米黃金織布。 Preferably, the electroless plating reaction tank has a pressure of 3,000 psi and a temperature of 45 ° C; Before obtaining the nano gold woven fabric, the electroless plating reaction tank is first released to a normal pressure, and the temperature is lowered to a normal temperature to securely obtain the nano gold woven fabric.
較佳的是，在洩壓至常壓時，將該無電解電鍍反應槽中的二氧化碳超臨界流體回收以供再利用。 Preferably, the carbon dioxide supercritical fluid in the electroless plating reactor is recovered for reuse when the pressure is released to normal pressure.
本發明又關於一種奈米黃金織布，其係由上述製備方法 所製成者。 The invention further relates to a nano gold woven fabric, which is prepared by the above preparation method Made by.
本發明之原理係在於利用電解質中的水於超臨界流體中配合界面活性劑形成含有奈米金的微乳胞，且藉由二氧化碳超臨界流體之低表面張力以及高質傳的特性使得含有奈米金的微乳胞均勻滲透至織物的纖維中，經由還原劑進行氧化還原反應，使得奈米金能夠均勻沉積在織物中，且藉由本發明之方法能使奈米黃金顆粒的粒徑集中分布，故能得到品質優良的奈米黃金織物。 The principle of the present invention is to form a microemulsion containing nano gold by using a surfactant in a supercritical fluid in combination with water in a supercritical fluid, and to contain naphthalene by the low surface tension of the supercritical fluid of carbon dioxide and the high mass transfer property. The micro-emulsion of the rice gold uniformly penetrates into the fibers of the fabric, and the redox reaction is carried out via the reducing agent, so that the nano gold can be uniformly deposited in the fabric, and the particle size of the nano gold particles can be concentrated by the method of the invention. Therefore, we can get high quality nano gold fabric.
請參看第一圖所示，本發明係一種奈米黃金織布的製備方法，其可利用具有如第一圖所示之管線配置系統來實現，而第一圖所示的管線配置系統僅為例示，並非用於限制本發明之範疇。 Referring to the first figure, the present invention is a method for preparing a nano gold woven fabric, which can be realized by using a pipeline configuration system as shown in the first figure, and the pipeline configuration system shown in the first figure is only The illustrations are not intended to limit the scope of the invention.
該管線配置系統係包括：一二氧化碳儲存槽(10)，其係用以儲存二氧化碳超臨界流體之用；一預備槽(20)，其係裝有界面活性劑以及還原劑，且係以一具有氣閥(22)之管線(21)連通於該二氧化碳儲存槽(10)；一無電解電鍍反應槽(30)，其係裝有電解液(50)，該無電解電鍍反應槽(30)係以一具有幫浦(32)和閥(33)之管線(31)連接至該預備槽(20)，且該無電解電鍍反應槽(30)具有連通至該二氧化碳儲存槽(10)之一迴管線(31)，該迴管線具有閥(32)。 The pipeline configuration system comprises: a carbon dioxide storage tank (10) for storing carbon dioxide supercritical fluid; a preparation tank (20) equipped with a surfactant and a reducing agent, and having The pipeline (21) of the gas valve (22) is in communication with the carbon dioxide storage tank (10); an electroless plating reaction tank (30) is provided with an electrolyte (50), and the electroless plating reaction tank (30) is Connected to the preliminary tank (20) with a line (31) having a pump (32) and a valve (33), and the electroless plating reaction tank (30) has a connection to the carbon dioxide storage tank (10). A line (31) having a valve (32).
而在利用上述管線配置系統進行本發明之方法時，先 配製一電解液(50)，該電解液包括0.01~0.015 mole/L的亞硫酸金、0.1~0.2 mole/L的檸檬酸鉀、0.4~0.55 mole/L的亞硫酸鈉、0.13~0.25 mole/L的亞硫酸銨和水所調配成的水溶液；將該電解液(50)注入該無電解電鍍反應槽(30)中，再將一織物(40)放置於該無電解電鍍反應槽(30)中，控制該無電解電鍍反應槽(30)之溫度在45~60℃之間恆溫；再開啟連接於該預備槽(20)之氣閥(22)以及連接至該無電解電鍍反應槽(30)之管線(31)的閥(33)，藉由該幫浦(32)的作動，讓二氧化碳超臨界流體自該二氧化碳儲存槽(10)流入該預備槽(20)中，以與界面活性劑與還原劑混合，之後再一起通入該無電解電鍍反應槽(30)中，調整該無電解電鍍反應槽(30)中的壓力大於1040 psi、溫度大於31℃；經過一特定的反應時間後，洩壓至常壓且降溫至常溫後即可將該奈米黃金織布自該無電解電鍍反應槽(30)中取出。 And when the method of the present invention is carried out by using the above pipeline configuration system, An electrolyte (50) is prepared, which comprises 0.01 to 0.015 mole/L of gold sulfite, 0.1 to 0.2 mole/L of potassium citrate, 0.4 to 0.55 mole/L of sodium sulfite, and 0.13 to 0.25 mole/L. An aqueous solution prepared by mixing ammonium sulfite and water; injecting the electrolyte (50) into the electroless plating reaction tank (30), and placing a fabric (40) in the electroless plating reaction tank (30), Controlling the temperature of the electroless plating reaction tank (30) to be constant between 45 and 60 ° C; opening the gas valve (22) connected to the preliminary tank (20) and connecting to the electroless plating reaction tank (30) The valve (33) of the pipeline (31), by the operation of the pump (32), allows the carbon dioxide supercritical fluid to flow from the carbon dioxide storage tank (10) into the preparation tank (20) to be combined with the surfactant and the reduction agent. The agent is mixed, and then introduced into the electroless plating reaction tank (30), the pressure in the electroless plating reaction tank (30) is adjusted to be greater than 1040 psi, and the temperature is greater than 31 ° C; after a specific reaction time, the vent The nano gold woven fabric can be taken out from the electroless plating reaction tank (30) after being pressed to atmospheric pressure and cooled to normal temperature.
而在洩壓的同時，可開啟該迴管線(31)的閥(32)，讓二氧化碳超臨界流體經由該迴管線(31)回流至該二氧化碳儲存槽(10)中。 While the pressure is being released, the valve (32) of the return line (31) can be opened, and the carbon dioxide supercritical fluid is returned to the carbon dioxide storage tank (10) via the return line (31).
以下實施例僅用於示範說明本發明。且這些實施例不以任何方式意欲限制本發明之範圍，但用於示範本發明的材料及方法，以使於所屬技術領域中具有通常知識者能夠據以實施本發明。 The following examples are merely illustrative of the invention. The present invention is not intended to limit the scope of the invention in any way, but is intended to exemplify the invention.
本發明所製成的黃金奈米織物於本實施例係以高解析度掃瞄式電子顯微鏡(TEM,Hitachi Model HF-2000 Field Emission Transmission Electron Microscope operating at an accelerating voltage of 200 KV)觀測織物表面的組成型態，以能量散佈光譜儀(EDX,an energy dispersive X-ray analysis)分析奈米黃金粒子的組成。 The gold nanofiber fabric produced by the present invention is a high-resolution scanning electron microscope (TEM, Hitachi Model HF-2000 Field) in this embodiment. Emission Transmission Electron Microscope operating at an accelerating voltage of 200 KV) The composition of the surface of the fabric was observed, and the composition of the nano-gold particles was analyzed by an energy dispersive X-ray analysis (EDX).
以下實施例所用的電解質的組成與濃度請參看表一所示：
製備方法Preparation
先使用顯示於表一中的電解質來配製電解液，將配製好的電解液與一聚酯類織物置入一無電解電鍍反應槽中，並使無電解電鍍反應槽中的溫度恆溫在45℃，0.003 mol/L將丁二酸二異辛酯磺酸鈉與0.033 mol/L的硫脲通入二氧化碳臨界流體後導入該無電解電鍍反應槽中，調整無電解電鍍反應槽之空氣壓力閥(air pressure regulaor)與背壓閥(back pressure regulaor)以控制系統壓力為3,000 psi，而溫度係控制在45℃，在此種高於二氧化碳之臨界溫度與臨界壓力的狀況下反應60分鐘；之後，洩壓至常壓，並降溫至常溫後取出奈米黃金織物，該奈米黃金織物已存在有奈 米黃金粒子。 First, the electrolyte is prepared by using the electrolyte shown in Table 1. The prepared electrolyte and a polyester fabric are placed in an electroless plating reaction tank, and the temperature in the electroless plating reaction tank is kept at 45 ° C. 0.003 mol/L, the sodium diisooctyl succinate sulfonate and 0.033 mol/L thiourea were introduced into the critical gas of carbon dioxide, and then introduced into the electroless plating reaction tank to adjust the air pressure valve of the electroless plating reaction tank ( Air pressure regulaor) with a back pressure regulaor to control the system pressure to 3,000 psi, while the temperature system is controlled at 45 ° C, reacting for 60 minutes at a critical temperature above the critical temperature of carbon dioxide and critical pressure; After releasing the pressure to normal pressure and cooling to normal temperature, the nano gold fabric is taken out, and the nano gold fabric already exists. Rice gold particles.
分析結果Analysis result
請參看第二A圖以及附件一所示，奈米黃金織物內的黃金純度大於99.9%。由顯微照片觀之，請參看第二B圖，可看出奈米黃金織物表面呈平坦狀，分析後奈米黃金顆粒之平均粒徑為6.03 nm。 Please refer to Figure A and Figure 1 for the gold purity in nano-gold fabrics greater than 99.9%. From the photomicrograph, please refer to the second B picture, it can be seen that the surface of the nano gold fabric is flat, and the average particle size of the nano gold particles after analysis is 6.03 nm.
製備方法Preparation
本實施例大致與實施例1相同，其不同之處在於該無電解電鍍反應槽中的溫度係恆溫在55℃，而反應時所控制的壓力係控制在2,000 psi，而溫度係控制55℃，在此種高於二氧化碳之臨界溫度與臨界壓力的狀況下反應60分鐘；之後，洩壓至常壓，並降溫至常溫後取出奈米黃金織物，該奈米黃金織物已存在有奈米黃金粒子。 This embodiment is substantially the same as Embodiment 1, except that the temperature in the electroless plating reaction tank is kept at 55 ° C, and the pressure controlled during the reaction is controlled at 2,000 psi, and the temperature is controlled at 55 ° C. The reaction is carried out for 60 minutes under the condition that the critical temperature is higher than the critical temperature of the carbon dioxide; after that, the pressure is reduced to the normal pressure, and after the temperature is lowered to the normal temperature, the nano gold fabric is taken out, and the nano gold fabric already has the nano gold particles. .
分析結果Analysis result
請參看第三A圖以及附件二所示，奈米黃金織物內的黃金純度大於99.9%。由顯微照片觀之，請參看第三B圖，可看出奈米黃金織物表面呈平坦狀，分析後奈米黃金顆粒之平均粒徑為6.43nm。 Please refer to Figure A and Figure 2 for the gold purity in nano-gold fabrics greater than 99.9%. From the photomicrograph, please refer to the third B picture, it can be seen that the surface of the nano gold fabric is flat, and the average particle size of the nano gold particles after analysis is 6.43 nm.
製備方法Preparation
本實施例大致與實施例1相同，其不同之處在於該無電解電鍍反應槽中的溫度係恆溫在55℃，而壓力係控制在 1,250 psi，而溫度係控制在55℃，在此種高於二氧化碳之臨界溫度與臨界壓力的狀況下反應60分鐘；之後，洩壓至常壓，並降溫至常溫後取出奈米黃金織物，該奈米黃金織物已存在有奈米黃金粒子。 This embodiment is substantially the same as Embodiment 1, except that the temperature in the electroless plating reaction tank is constant at 55 ° C, and the pressure system is controlled at 1,250 psi, and the temperature is controlled at 55 ° C, in this condition above the critical temperature of carbon dioxide and the critical pressure for 60 minutes; after that, the pressure is released to normal pressure, and after cooling to room temperature, the nano gold fabric is taken out, Nano gold fabrics already exist with nano gold particles.
分析結果Analysis result
請參看第四A圖以及附件三所示，奈米黃金織物內的黃金純度大於99.9%。由顯微照片觀之，請參看第四B圖，可看出奈米黃金織物表面呈平坦狀，分析後奈米黃金顆粒之平均粒徑為9.53nm。 Please refer to Figure 4A and Annex III for the gold purity in nano-gold fabrics greater than 99.9%. From the photomicrograph, please refer to the fourth B picture, it can be seen that the surface of the nano gold fabric is flat, and the average particle size of the nano gold particles after analysis is 9.53 nm.
製備方法Preparation
本實施例大致與實施例1相同，其不同之處在於先將該無電解電鍍反應槽中的溫度係恆溫在60℃，再將壓力控制在1,500 psi，而溫度係控制在60℃，在此種高於二氧化碳之臨界溫度與臨界壓力的狀況下反應60分鐘；之後，洩壓至常壓，並降溫至常溫後取出奈米黃金織物，該奈米黃金織物已存在有奈米黃金粒子。 This embodiment is substantially the same as Embodiment 1, except that the temperature in the electroless plating reaction tank is first thermostated at 60 ° C, the pressure is controlled at 1,500 psi, and the temperature is controlled at 60 ° C. The reaction is carried out for 60 minutes under the condition that the critical temperature of carbon dioxide is higher than the critical temperature; after that, the pressure is reduced to normal pressure, and after cooling to normal temperature, the nano gold fabric is taken out, and nano gold particles are already present in the nano gold fabric.
分析結果Analysis result
如第五A圖以及附件四所示，奈米黃金織物內的黃金純度大於99.9%。由顯微照片觀之，請參看第五B圖，可看出奈米黃金織物表面呈平坦狀，分析後奈米黃金顆粒之平均粒徑為10.77nm。 As shown in Figure 5A and Annex IV, the gold purity in the nano-gold fabric is greater than 99.9%. From the photomicrograph, please refer to the fifth B picture, it can be seen that the surface of the nano gold fabric is flat, and the average particle size of the nano gold particles after analysis is 10.77 nm.
製備方法Preparation
此比較例大致與實施例1相同，其不同之處在於該無電解電鍍反應槽中的溫度係恆溫在55℃，而壓力係控制在常壓下14.22 psi，而溫度係控制在55℃，反應時間60分鐘，以獲得一黃金織物。 This comparative example is substantially the same as that of Example 1, except that the temperature in the electroless plating reaction tank is kept at 55 ° C, and the pressure system is controlled at 14.22 psi under normal pressure, and the temperature is controlled at 55 ° C. Time 60 minutes to get a gold fabric.
分析結果Analysis result
如第六A圖以及附件五所示，黃金織物上的黃金純度大於99.9%，然而，由顯微照片觀之，請參看第六B圖，絕大部分的黃金顆粒之粒徑皆大於1微米(1000奈米)，顯示非以本發明所提供之條件無法製備出如本發明一樣的奈米黃金織物。 As shown in Figure 6A and Annex V, the gold purity on the gold fabric is greater than 99.9%. However, as seen from the photomicrograph, please refer to Figure B. The majority of the gold particles are larger than 1 micron. (1000 nm), showing that nano gold fabrics as in the present invention could not be prepared without the conditions provided by the present invention.
由以上實施例的結果顯示本發明所提供之電解質種類、電解質濃度範圍以及溫度和壓力等條件確實可將超臨界流體應用於製備奈米黃金織物，其中又以實施例1為本發明之較佳實施例，並由分析結果可知藉由調整超臨界流體壓力與溫度，可控制奈米黃金織物中的奈米黃金顆粒之粒徑分布，而壓力越高，則奈米黃金顆粒之粒徑分布越為集中，且表面粗糙度越低，故藉由本發明可獲得品質穩定的奈米黃金織布。 The results of the above examples show that the electrolyte type, the electrolyte concentration range, and the temperature and pressure conditions provided by the present invention can indeed apply the supercritical fluid to the preparation of the nano gold fabric, and the first embodiment is the preferred embodiment of the present invention. In the embodiment, it can be seen from the analysis result that the particle size distribution of the nano gold particles in the nano gold fabric can be controlled by adjusting the pressure and temperature of the supercritical fluid, and the higher the pressure, the more the particle size distribution of the nano gold particles is. In order to concentrate, and the surface roughness is lower, a nano-gold woven fabric of stable quality can be obtained by the present invention.
(10)‧‧‧二氧化碳儲存槽 (10) ‧‧‧CO2 storage tank
(20)‧‧‧預備槽 (20) ‧‧‧Reservoir
(21)‧‧‧管線 (21)‧‧‧ pipeline
(22)‧‧‧氣閥 (22)‧‧‧ gas valve
(30)‧‧‧無電解電鍍反應槽 (30)‧‧‧Electroless plating reactor
(31)‧‧‧迴管線 (31)‧‧‧Return pipeline
(32)‧‧‧幫浦 (32)‧‧‧
(33)‧‧‧閥 (33) ‧‧‧Valves
(40)‧‧‧織物 (40) ‧ ‧ fabrics
(50)‧‧‧電解液 (50) ‧‧‧ electrolyte
第一圖係本發明之管線流程示意圖。 The first figure is a schematic diagram of the pipeline process of the present invention.
第二A圖係為本發明實施例1之黃金純度EDX分析圖。 The second A is a gold purity EDX analysis chart of Example 1 of the present invention.
第二B圖係為本發明實施例1之粒徑分析TEM圖。 The second B diagram is a TEM image of the particle size analysis of Example 1 of the present invention.
第三A圖係為本發明實施例2之黃金純度EDX分析圖。 The third A is a gold purity EDX analysis chart of Example 2 of the present invention.
第三B圖係為本發明實施例2之粒徑分析TEM圖。 The third B diagram is the TEM image of the particle size analysis of Example 2 of the present invention.
第四A圖係為本發明實施例3之黃金純度EDX分析圖。 The fourth A diagram is a gold purity EDX analysis chart of Example 3 of the present invention.
第四B圖係為本發明實施例3之粒徑分析TEM圖。 The fourth B diagram is the TEM image of the particle size analysis of Example 3 of the present invention.
第五A圖係為本發明實施例4之黃金純度EDX分析圖。 Figure 5A is a gold purity EDX analysis chart of Example 4 of the present invention.
第五B圖係為本發明實施例4之粒徑分析TEM圖。 Fig. 5B is a TEM image of the particle size analysis of Example 4 of the present invention.
第六A圖係為本發明比較例1之黃金純度EDX分析圖。 The sixth A graph is the gold purity EDX analysis chart of Comparative Example 1 of the present invention.
第六B圖係為本發明比較例1之粒徑分析TEM圖。 Fig. 6B is a TEM image of the particle size analysis of Comparative Example 1 of the present invention.
附件一係對應第二A圖之電腦輸出原圖。 Attachment 1 corresponds to the computer output original picture corresponding to the second A picture.
附件二係對應第三A圖之電腦輸出原圖。 Attachment 2 is the original output of the computer corresponding to the third A picture.
附件三係對應第四A圖之電腦輸出原圖。 The third part of the annex corresponds to the computer output original picture of the fourth A picture.
附件四係對應第五A圖之電腦輸出原圖。 Attachment 4 corresponds to the original computer output of Figure 5A.
附件五係對應第六A圖之電腦輸出原圖。 The fifth part of the annex corresponds to the original computer output of Figure 6A.
(10)‧‧‧二氧化碳儲存槽 (10) ‧‧‧CO2 storage tank
(20)‧‧‧預備槽 (20) ‧‧‧Reservoir
(21)‧‧‧管線 (21)‧‧‧ pipeline
(22)‧‧‧氣閥 (22)‧‧‧ gas valve
(30)‧‧‧無電解電鍍反應槽 (30)‧‧‧Electroless plating reactor
(31)‧‧‧迴管線 (31)‧‧‧Return pipeline
(32)‧‧‧幫浦 (32)‧‧‧
(33)‧‧‧閥 (33) ‧‧‧Valves
(40)‧‧‧織物 (40) ‧ ‧ fabrics
(50)‧‧‧電解液 (50) ‧‧‧ electrolyte
Claims (10)
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| TW200517538A (en) * | 2003-11-10 | 2005-06-01 | Teijin Ltd | Carbon fiber nonwoven fabric, and production method and use thereof |
| CN1933906A (en) * | 2004-03-16 | 2007-03-21 | 哥伦比亚化学公司 | Deposition of dispersed metal particles onto substrates using supercritical fluids |
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| CN1933906A (en) * | 2004-03-16 | 2007-03-21 | 哥伦比亚化学公司 | Deposition of dispersed metal particles onto substrates using supercritical fluids |
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