電漿處理與接枝感溫性聚合高分子水膠及其功能性研究

本研究主要分為三部分，在第一部分中使用電漿沉積薄膜與改質材料表面功能，以異丙醇電漿與六甲基二矽胺烷電漿於聚苯乙烯上沉積薄膜並探討其細胞貼覆性，另外以大氣電漿作高分子類材料的親水化改質，第二部分是以UV光接枝聚合可逆熱致變色材料，將其應用於節能材料上，探討其阻光節能特性，最後一部分即以表面處理為基礎結合電漿表面活化、自我組織單層薄膜 (self-assemble monolayers, SAMs) 與UV光接枝聚合技術製備感溫性奈米金粒子。首先利用冷電漿聚合方法，於聚苯乙烯 (polystyrene, PS) 表面上沉積醇類或有機矽烷類高分子膜，測試其細胞貼附性。以異丙醇電漿處理表面後，使PS增加親水性，且由纖維母細胞、Caco2 cells與黑色素細胞做培養，其貼附性不亞於市販細胞培養皿。另外電漿具有表面改質的功能，而傳統的電漿技術由於需在真空下進行，大氣電漿系統不需真空設備，相較於傳統系統就製程方面於成本上有絕對的優勢，以大氣電漿做高分子材料的親水化表面改質，由於熱塑性聚胺酯 (Thermoplastic Urethane，TPU) 及其纖維、聚酯 (Polyester，PE) 纖維與聚苯乙烯 (Polystyrene，PS)等高分子材料其具安定性但表面屬疏水性且表面能低，不易做後續塗佈，限制了其應用，因此使用大氣電漿做表面改質，以崩潰電壓較低的氦氣或加上氧氣為工作氣體改變不同的電漿活化時間、氣體比例與功率觀察TPU及其纖維,聚酯纖維與聚苯乙烯親水性的變化，探討其最佳製程之時間參數。大氣電漿表面改質前後TPU與聚酯纖維親水性是利用水接觸角檢測，TPU可由未處裡94°在大氣電漿處理後降為50°，聚酯纖維也由未處裡的128°降為64°，而表面元素分析及鍵結種類和百分比率則是利用化學分析電子光譜儀 (Electron Spectroscopy for chemical Analysis System ，ESCA) 分析，電漿表面改質後的 TPU其氧元素含量由 13.66％增加到 31.54%，並以掃描式電子顯微鏡 (scanning electron microscope，SEM) 觀察 TPU 及其纖維與聚酯纖維表面形態變化。第二部份，由於全球能源消耗大部分來自化石燃料，燃燒化石燃料會產生大量二氧化碳，被認定為造成地球暖化的主要元凶。而較熱的光線一旦進入生活空間即會增加室內空氣溫度，故若有一可變色材料，能適時阻隔大量的太陽熱能，藉由高溫之阻擋陽光透過，則應可達到舒適與節能之目的。因此以UV光接枝聚合可逆熱致變色感溫性高分子，製成三明治夾板，以模擬屋測量其室內溫度變化，此高分子在高於變色溫度時即變成不透明性，達到減少室內溫度，節約空調能源之效果。而在熱致變色感溫性高分子厚度在2 mm時，其在空氣中測得知溫度換算節能率可達0.55。奈米金粒子(Nano-Au)具有表面電漿共振 (Surface plasmon resonance，SPR) 的特性，因此特有的光學性質，常被用於生物檢測方面，但奈米金粒子成本較高，在本研究的最後一部份中以電漿處理、SAMs與接枝聚合方式製備感溫性奈米金粒子，其有升高溫度使其奈米材料沉降的特性，可回收奈米金粒子。首先以電漿處理產生自由基之方法，將含羧基硫醇之11-Mercaptoundecanoic acid (mua)修飾後的奈米金粒子Nano-Au(mua)，使用冷電漿輝光於 Nano-Au(mua) 表面產生自由基，即可以UV光接枝將聚異丙基丙烯醯胺 (poly(N-isopropylacrylamide)，PNIPAAm) 感溫性高分子結合於奈米金粒子上Nano-Au(mua)-g-PNIPAAm。穩定、快速且方便的將奈米金粒子表面進行修飾。結果得知以氧電漿處理後再接枝上感溫性 PNIPAAm呈紫紅色，且 Nano-Au(mua)-g-PNIPAAm 有溫度感應性，加熱 40℃ 15 分鐘後可使奈米金粒子沉降，以 UV-Vis 光譜儀檢測其上清液在波長 520 nm 時完全無吸收峰，下層金粒子沉降在 520nm則有明顯的吸收峰，表示仍具有奈米金粒子 SPR 的特性，並以表面為金電極的石英晶體微天平（Quartz Crystal Microbalance，QCM）確認固定上感溫性高分子的頻率變化，在接枝感溫性高分子後其頻率較原始的 QCM 下降 13687±81 Hz。

關鍵字

感溫性高分子；接枝聚合；電漿；表面改質；奈米金

並列摘要

The investigation divided into three sessions. At first thin film deposition and surface modification used plasma treatment. Hexamethyldisilazane (HMDSZ) and isopropanol (IPA) plasma deposited thin film on polystyrene (PS) and discussed the cell attachment. In addition surface modification polymeric used atmospheric pressure plasma to increase the hydrophilicity is also attempted. The second session polymerization reversible thermosensitive polymer used UV graft polymerization and application on energy-saving material, analyzed the light resistance. The last session preparation thermosensitive gold nano particles based surface modification theory combination of plasma surface activation, self-assembled monolayesrs (SAMs) and UV graft polymerization technology First of all, used cold plasma deposition poly lactic acid-like and organic silicon-like thin film on PS and analyzed the cell attachment. After IPA plasma treated the hydrophilicity increase on PS, cell culture of fibroblast, Caco2 and melanocyte, the cell attachment not inferior to commercial tissue culture polystyrene (TCPS). Additionally, surface modification is one of the functions of plasma treatment. The traditional plasma technology works under vacuum system, atmospheric pressure plasma without vacuum equipment, compared to traditional plasma have absolute advantage in the system at the cost of the equipment. As thermoplastic urethane (TPU), PS and polyester fabric with stability, but its surface is hydrophobic and low surface energy, difficult to do coating and limiting its application. So take use of helium gas with low breakdown voltage and work with oxygen atmospheric pressure plasma surface modification change the treatment time, gas ratio and power for different plasma, observed the hydrophilic change of TPU and polyester fabric and to explore the best parameters. After atmospheric pressure plasma treatment, the water contact angle of TPU changes from 94° to 50° and PE fabric changes from 128° to 64°. The ESCA results demonstrated oxygen percentage of TPU raised from 13.66％ to 31.54% and scanning electron microscopy (SEM) were used for characterize the surface morphology. The second session of the study, the electricity consumption is too much in air conditioner so that the power source is wasted in livelihood (such as building and transportation). For the purpose to save energy and to reduce the electricity consumption in air conditioner, must began to reduce the heat energy from outside in to increase the efficiency of air conditioner. Therefore, if a thermochromism material to cut off a large of heat when the sunshine, should fit the aim in comfortable and save energy. the investigate of thermochromism reversible smart polymer poly N-isopropylacrylamide (PNIPAAm), to develop the smart sandwich like plywood could be heat reflection and get in the light. To resist the superheat rays from outside in when the high temperature, enable the bright from outdoor to enter in low temperature. The result showed the thickness of thermochromism for 2mm the energy saving ratio is 0.55. Gold nano particles are widely used in surface plasmon (SPR) resonance studies. SPR technology has become a leading technology in the field of real-time observation of biomolecular interactions. But there are expensive and easily to aggregate when keep for long time of gold nano particles. So the technology of prepare thermosensitive gold nano particles by plasma modification and UV graft polymerization has been developed in this study. The thermosensitive gold nano particle could settle to the bottom in the liquid when raise the temperature and the thermosensitive gold nano particle could be recycle. Gold nano particles (Nano-Au) were reduced by trisodium citrate combined with hydrogen tetrachloroaurate (Ⅲ) tetrahydrate (chloroauric acid) and modified with 11-mercaptoundecanoic acid (MUA) by the self-assembled monolayesrs (SAMs). The surface graft polymerization of N-isopropylacrylamide (NIPAAm) was carried out by two steps, using O2 plasma pretreatment of the surface on MUA SAM modified Nano-Au to form the peroxide groups on Nano-Au (MUA), and then subsequently using UV light to induce grafting thermosensitive polymer. The thermosensitive gold nano particles were wine-red and could settle to the bottom in the liquid which heating to 40℃ and maintain 15 min. The thermosensitive gold nano particles were characterized with UV-vis. The surface plasmon resonance is clearly visible as a peak in the in 520 nm of thermosensitive gold nano particles settle to the bottom in the liquid and the upper solution not showed any peak. The investigated the frequency shift of the gold film electrode of a quartz crystal microbalances (QCM) made by steps of applying self-assembling monolayer (SAM), plasma treatment and UV-induced graft polymerization on the surface. The frequency decrease 13687±81 Hz.

並列關鍵字

Thermosensitive Polymer ； Graft Polymerization ； Plasma ； Surface Modification ； Gold Nano Particle

參考文獻

[1] Yu-Cheng Lin, Yu-chia Tsao, Woo-Hu Tsai, Tsui-Shan Hung, Ko-Shao Chen, Shu-Chuan Liao, “The enhancement method of optical fiber biosensor based on surface plasmon resonance with cold plasma modification,” Sensors and Actuators B: Chemical 133(2008)370-373

[2] E.M. Liston, L. Martinu, M.R. Wertheimer, “Plasma surface modification of polymers for improved adhesion: a critical review,” Journal of Adhesion Science and Technology 7(1993)1091-1127

[3] A. Valanezhad, K. Tsuru, M. Maruta, G. Kawachi, S. Matsuya, K. Ishikawa, “Novel Ceramic Coating on Titanium with High Mechanical Properties,” Bioceramics Development and Applications 1(2010)1-3

[4] Ko-Shao Chen, Jui-Che Tsai, Chih-Wei Chou, Mu-Rong Yang, Jen-Ming Yang, "Effect of additives on the photo-induced grafting polymerization of n-isopropylacrylamide gel onto PET and PP nonwoven fabric surface," Materials Science & Engineering C20 (2002) 203-208

[5] John Affinito, Peter Martin, Mark Gross, Chris Coronado, Eric Greenwell, “Vacuum deposited polymer/metal multilayer films for optical application,” Thin Solid Films 270(1995)43-48

國際替代計量

電漿處理與接枝感溫性聚合高分子水膠及其功能性研究

未授權

主題瀏覽