研究生: |
鄭魁丰 Kuei-Feng Cheng |
---|---|
論文名稱: |
高靈敏度PtTFPP/Carbon Black/Polystyrene 氧敏感複合薄膜之光學溶氧感測器應用 Application of High Sensitivity PtTFPP/Carbon Black/Polystyrene Oxygen Sensitive Composite Film to Optical Dissolved Oxygen Sensor |
指導教授: |
邱智瑋
Chih-Wei Chiu |
口試委員: |
游進陽
Chin-Yang Yu 邱顯堂 Hsien-Tang Chiu |
學位類別: |
碩士 Master |
系所名稱: |
工程學院 - 材料科學與工程系 Department of Materials Science and Engineering |
論文出版年: | 2019 |
畢業學年度: | 107 |
語文別: | 中文 |
論文頁數: | 87 |
中文關鍵詞: | 溶氧感測器 、螢光猝滅 、氟苯基鉑卟啉 、碳黑 、聚苯乙烯 |
外文關鍵詞: | Dissolved Oxygen Sensor, Fluorescence Quenching, Platinum Tetrakis Pentrafluoropheny Porphine, Carbon Black, Polystyrene |
相關次數: | 點閱:267 下載:0 |
分享至: |
查詢本校圖書館目錄 查詢臺灣博碩士論文知識加值系統 勘誤回報 |
螢光猝滅(Fluorescence Quenching)是指當螢光染料吸收特定波長的光源時,會從原本穩定的基態,提升至不穩定的激發態,在激發態的情況下,藉由產生螢光的方式來釋放能量,回到穩定的基態,釋放能量的過程與猝滅劑(Quencher)接觸時,會使能量傳遞給猝滅劑,造成螢光強度的減低。
本研究是利用螢光猝滅的原理製作出氧敏感薄膜並將其應用到光學溶氧感測器上。首先將聚苯乙烯(Polystyrene, PS)與氟苯基鉑卟啉(Platinum Tetrakis Pentrafluoropheny Porphine, PtTFPP)摻合,並進一步使用磷酸三丁酯(Tributyl Phosphate, TBP)與碳黑(Carbon Black, CB)改善透氧率與比表面積,藉此提升靈敏度。奈米碳材分散的製程中,CB是使用非離子型界面活性劑Triton-X-100使其均勻分散在其中,最終可以製作出高靈敏度氧敏感薄膜。
研究結果顯示PS與PtTFPP的重量比在150/1時有最高靈敏度(I0/I100)為11.73,Sterm-Volmer曲線的線性率(R2)為0.9955,當添加TBP為PS的3wt%後靈敏度提升到16.51、R2為0.99339,進一步摻合碳黑靈敏度更是到達19.12、R2為0.9916,證實了添加TBP和CB能有效改善薄膜靈敏度。最後我們成功使用簡單且低成本的方式製作出高靈敏度且準確的氧敏感薄膜,在未來可利用此方法發展出各種高靈敏度感測器,並應用於水質檢測的領域上。
Fluorescence quenching means fluorescent dye absorbs a light source of a specific wavelength, it will rise from an originally stable ground state to an unstable excited state, and in the case of an excited state, emit energy by generating fluorescence, and Returning to stable ground state, the process of releasing energy contacts the quencher, and transfers energy to the quencher, resulting in a decrease in fluorescence intensity.
In this study uses the principle of fluorescence quenching to make oxygen sensitive film and apply it to an optical dissolved oxygen sensor. First, polystyrene (polystyrene, PS) is blended with Platinum Tetrakis Pentrafluoropheny Porphine (Platinum Tetrakis Pentrafluoropheny Porphine, PtTFPP), and further used Tributyl Phosphate (Tributyl Phosphate, TBP) and Carbon Black (Carbon Black, CB) improve oxygen permeability and surface area, thereby increasing the sensitivity of fluorescence. In the process of dispersing nano carbon materials, CB is evenly dispersed by using non-ionic surfactant (Triton-X-100). Finally, a highly sensitive oxygen sensitive film can be produced.
The results show that the weight ratio of PS/PtTFPP has the highest sensitivity (I0/I100) of 11.73 at 150/1, the linearity (R2) at Sterm-Volmer curve is 0.9955, and the sensitivity increased to 16.51 after adding TBP to 3 wt%, and R2 is 0.99339. The sensitivity of further blending CB is 19.12 and R2 is 0.9916. It is confirmed that the addition of TBP and CB can effectively improve the sensitivity of the film and have a good linear relationship. Finally, we succeeded in producing high-sensitivity and accurate fluorescent films using a simple and low-cost method. In the future, we can develop various high-sensitivity sensors and apply them to the field of water quality testing.
[1] P. Majumdar, R. Nomula, and J. Zhao, Activatable triplet photosensitizers: magic bullets for targeted photodynamic therapy, J. Mater. Chem. C 2014, 2, 5982-5997.
[2] X. D. Wang, and O. S. Wolfbeis, Optical methods for sensing and imaging oxygen: materials, Spectroscopies and Applications, Chemical Society Reviews 2014, 43, 3666-3761.
[3] 陳偉榮,溶氧監測探頭核心技術取得大突破280億大市場即將爆發,中國水產養殖年刊,2017。
[4] R. Steiner, Why do veins appear blue? A new look at an old question, Applied Optics 1996, 35, 1151-1160.
[5] J. K. Fredrickson, J. M. Zachara, D. L. Balkwill, D. Kennedy, S. W. Li, H. M. Kostandarithes, M. J. Daly, M. F. Romine, and F. J. Brockman, Geomicrobiology of high-level nuclear waste-contaminated vadose sediments at the hanford site, washington state, Appl. Environ. Microbiol 2004, 70, 4230-4241.
[6] H. Zhu, Y. Tian, S. Bhushan, F. Su, and D. R. Meldrum, High Throughput Micropatterning of Optical Oxygen Sensor for Single Cell Analysis, IEEE Sens J 2012, 12, 1668-1672.
[7] S. M. Grist, L. Chrostowski, and K. C. Cheung, Optical oxygen sensors for applications in microfluidic cell culture, Sensors (Basel) 2010, 10, 9286-9316.
[8] D. R. Lide, CRC Handbook of Chemistry and Physics, 2008, 87.
[9] W. S. Hou, Y. Y. Cheng, and I. Z. Cheng, Research of Self-operated Low-cost Dissolved Oxygen Sensor (II), Journal of Taiwan Agricultural Engineering 2008, 54, 14-26.
[10] K. Koren, K. E. Brodersen, S. L. Jakobsen, and M. Kuhl, Optical sensor nanoparticles in artificial sediments-A new tool to visualize O2 dynamics around the rhizome and roots of seagrasses, Environ. Sci. Technol. 2015, 49 2286-2292.
[11] H. Tschiersch, G. Liebsch, and L. Borisjuk, A. Stangelmayer, H. Rolletschek, An imaging method for oxygen distribution, respiration and photosynthesis at a microscopic level of resolution, New Phytol 2012, 196, 926-936.
[12] 劉橋陽,分光光度法測定水中溶解氧,環境工程,2008,26,92-94.
[13] 華中師範大學,分析化學,高等教育出版社,2001.
[14] 朱承軒,溶膠-凝膠基體參雜奈米粒子在高靈敏度光纖氧氣與二氧化碳感測器之研究,國立成功大學博士論文,機械工程研究所,2009.
[15] 葉耀宗;黃建豪;張學明,螢光材料之發展現況及展望,工業材料雜誌,2016,352.
[16] 陳暘,以八乙基铂卟啉为氧敏剂的溶解氧敏感膜研究,江南大學碩士論文,2015.
[17] W. Xu, R. Schmidt, M. Whaley, J. N. Demas, B. A. Degaff, E. K. Karikari, and B. L. Farmer, Oxygen Sensors Based on Luminescence Quenching: Interactions of Pyrene with the Polymer Supports, Anal. Chem 1995, 67, 3172-3180.
[18] R. J. Trebra, and T. H. Koch, Photochemistry of Coumarin Laser Dyes: The role of singlet oxygen in the Photo-Oxidation of Coumarin 311, J. Photochem 1986, 35, 33-46.
[19] P. Kiernan, C. Mcdonagh, B. D. Maccraith, and K. Mongey, Ruthenium-doped sol-gel derived silica films: Oxygen Sensitivity of optical decay times, Journal of Sol-Gel Science and Technology 1994, 2, 513-517.
[20] C. S. Chu, T. S. Yeh, and Y. L. Lo, Highly sensitive optical fiber oxygen sensor using Pt(II) complex embedded in sol–gel matrices, Sens. Actuators B Chem. 2006, 119, 701-707.
[21] 邱微微,基於螢光猝滅原理的溶解氧敏感膜的研究,江南大學碩士論文,2013.
[22] C. S. Chu, Optical fiber oxygen sensor based on Pd(II) complex embedded in sol–gel matrix, J. Lumin. 2013, 135, 5-9.
[23] C. S. Chu, and C. Y. Chuang, Ratiometric optical fiber dissolved oxygen sensor based on metalloporphyrin and CdSe quantum dots embedded in sol–gel matrix, J. Lumin. 2015, 167, 114-119.
[24] I. Okura, Photostable Optical Oxygen Sensing Material: Platinum Tetrakis(pentafluorophenyl)porphyrin Immobilized in Polystyrene, Anal. Commun. 1997, 34, 185-188.
[25] L. Liang, G. Li, Z. Mei, J. Shi, Y. Mao, T. Pan, C. Liao, J. Zhang, and Y. Tian, Preparation and application of ratiometric polystyrene-based microspheres as oxygen sensors, Anal Chim Acta 2018, 1030, 194-201.
[26] K. Zhang, H. Zhang, W. Li, Y. Tian, S. Li, J. Zhao, and Y. Li, PtOEP/PS composite particles based on fluorescent sensor for dissolved oxygen detection, Materials Letters 2016, 172, 112-115.
[27] S. Lee, and J. W. Park, Luminescent oxygen sensors with highly improved sensitivity based on a porous sensing film with increased oxygen accessibility and photoluminescence, Sens. Actuators B Chem. 2017, 249, 364-377.
[28] Y. Mao, Z. Mei, J. Wen, G. Li, Y. Tian, B. Zhou, and Y. Tian, Honeycomb structured porous films from a platinum porphyrin-grafted poly(styrene-co-4-vinylpyridine) copolymer as an optical oxygen sensor, Sens. Actuators B Chem 2018, 257, 944-953.
[29] C. A. Kelly, C. Toncelli, J. P. Kerry, and D. B. Papkovsky, Discrete O2 sensors produced by a spotting method on polyolefin fabric substrates, Sens. Actuators B Chem 2014, 203, 935-940.
[30] Y. Mao, Y. Gao, S. Wu, S. Wu, J. Shi, B. Zhou, and Y. Tian, Highly enhanced sensitivity of optical oxygen sensors using microstructured PtTFPP/PDMS-pillar arrays sensing layer, Sensors and Actuators B: Chemical 2017, 251, 495-502.
[31] S. A. U. Hasan, Y. Jung, S. Kim, C. L. Jung, S. Oh, J. Kim, and H. Lim, A Sensitivity Enhanced MWCNT/PDMS Tactile Sensor Using Micropillars and Low Energy Ar(+) Ion Beam Treatment, Sensors (Basel) 2016, 16.
[32] C. S. Chu, Y. L. Lo, and T. W. Sung, Enhanced oxygen sensing properties of Pt(II) complex and dye entrapped core-shell silica nanoparticles embedded in sol-gel matrix, Talanta 2010, 82, 1044-51.
[33] C. S. Chu, and Y. L. Lo, Optical fiber dissolved oxygen sensor based on Pt(II) complex and core-shell silica nanoparticles incorporated with sol–gel matrix, Sens. Actuators B Chem. 2010, 151, 83-89.
[34] C. S. Chu, T. W. Sung, and Y. L. Lo, Enhanced optical oxygen sensing property based on Pt(II) complex and metal-coated silica nanoparticles embedded in sol–gel matrix, Sens. Actuators B Chem. 2013, 185, 287-292.
[35] 黃海松,塑化劑,工業技術研究院,1981.
[36] A. Mills, Controlling the sensitivity of optical oxygen sensors, Sens. Actuators B Chem. 1998, 15, 60-68.
[37] 謝立生,碳黑物性與應用入門,高分子期刊,1998,51-58.
[38] 陳俊勳,生物可分解高分子正溫度係數效應之研究,國立臺北科技大學碩士論文,有機高分子研究所,2006.
[39] 謝立生,高分子工業,1998,77期,51-56.
[40] 陳佳莉,全球碳黑產業現況,台灣工業銀行,2007.
[41] A. I. Medlia, and F. A. Heckman, Morphology of aggregates—II. Size and shape factors of carbon black aggregates from electron microscopy, Carbon 1969, 7, 577-582.
[42] J. B. Donnet, Fifty years of research and progress on carbon black, Carbon 1994, 32, 1305-1310.
[43] J. A. A. E. Romero, Additives: special carbon blacks for plastics, Plastics engineering 1995, 5, 153-161.
[44] J. B. Donnet, Carbon black: science and technology, CRC Press, 1993.
[45] Derjaguin, Theory of the stability of strongly charged lyophobic sols and the adhesion of strongly charged particles in solutions of electrolytes, Acta Physicochim 1941, 14, 633-662.
[46] E. J. W. Verwey, Theory of the stability of lyophobic colloids, J. Phys. Chem 1947, 51, 631-636.
[47] 趙承琛,界面科學基礎,復文書局,2007.
[48] J. Lehmann, The observation of the crystallization of high polymer substances from the solution by nuclear magnetic resonance, Colloid & Polymer Science 1966, 212, 167-168.