臺灣博碩士論文加值系統

熱擴散(亦稱為索雷特效應(Ludwig-Soret Effect)或熱泳)意指溫度梯度在多元溶液中造成各成分分子沿溫度梯度方向的不同程度傳輸，致使各成分的濃度分率(莫耳濃度分率或者質量分率)隨時之改變而改變。質量擴散則意指多元溶液中各成分濃度分率梯度所引起的質量傳輸效應。
在過去，本實驗室使用兩道相干的532 nm CW Nd:YVO4雷射光為寫入光源(pump)，另以一道633 nm的CW He-Ne雷射光作為偵測光源(probe)，在摻有微量甲基紅染料的二元混合溶液樣品中進行熱擴散致被迫瑞利散射(Thermal Diffusion Forced Rayleigh Scattering，TDFRS)實驗，藉以調查二元溶液中個別成分的熱擴散與質量擴散效應。當寫入光源在此摻有染料的二元混合溶液中造成熱致光柵(thermally induced grating)時，藉著量測偵測光通過光柵後所產生布拉格繞射光強隨時間變化的情形，我們得以探討二元混合溶液中熱致光柵隨時間變化的情形，進而了解熱擴散與質量擴散機制。
本論文重點在於量測水-乙醇(Water-Ethanol)二元溶液的TDFRS繞射訊號，利用程式模擬探討索雷特係數對繞射訊號的影響，並說明在部分情況下傳統TDFRS可量測出索雷特係數的正負號，以及計畫未來加入外差探測量測技術使實驗更加完整。

The key phenomena involved in this study include thermal and mass diffusions. Here, by thermal diffusion, namely the Ludwig-Soret effect or thermophoresis, we mean mass transport of individual constituents of multi-component solutions induced by the gradient of solution temperature. By mass diffusion we mean mass transport of each constituent induced by the existent gradient of molar fraction of the solutions constituents.
In the past few years, we have employed the technique known as thermal diffusion forced Rayleigh scattering (dubbed TDFRS) to investigate the variation of periodical refractive index induced in binary liquid solutions with a small fraction of methyl red dye dissolved in as the absorber of the pump beams at 532 nm. In TDFRS experiments, we split the output of the 532 nm CW Nd:YVO4 laser into two beams as the pumps, referred to as the writing beams, and a CW He-Ne laser beam at 632.8 nm as the probe, namely, the reading beam. The pump beams intersect in the solutions and create a thermal refraction grating therein to diffract the probe beam. By measuring and analyzing the power of the diffracted 632.8 nm light as a function of time, we investigated how the thermal and mass diffusion properties of the binary solution mixtures evolve with time. To interpret the TDFRS experimental result, we appeal to the thermal and mass diffusions.
In this thesis, we demonstrate that traditional TDFRS can distinguish sign change of the Soret coefficient without optical heterodyne detection schemes for some conditions. We eventually need to modify this technique to enable optical heterodyne detection. Therefore, we further discussed how to install this modification in the thesis.

摘要 I
ABSTRACT II
目錄 III
第一章 緒論 1
1.1 TDFRS發展歷史與文獻 1
1.2 本實驗室的TDFRS研究歷史 3
1.3 研究動機與目的 6
第二章 TDFRS基本理論 7
2.1 光柵的形成以及繞射效率與索雷特係數的關係 8
2.1.1 強度光柵 8
2.1.2 溫度光柵 11
2.1.3 密度光柵 13
2.1.4 質量分率光柵 14
2.1.5 折射率光柵 17
2.1.6 繞射效率與索雷特係數的關係 19
2.2 外差探測技術與外差繞射效率 21
2.2.1 外差探測技術 21
2.2.2 外差繞射效率 24
第三章 實驗架設的改良與量測系統 28
3.1 實驗樣品 28
3.1.1 樣品性質簡介 28
3.1.2 樣品製備流程 30
3.2 實驗架設 31
3.3 高斯光束的聚焦與擴束 34
3.4 繞射訊號探測系統簡介 36
3.4.1 光電倍增管(Photomultiplier tube，PMT) 36
3.4.2 電流前置放大器(Current preamplifier) 41
3.4.3 示波器(Oscilloscope) 41
第四章 實驗結果與討論 43
4.1 三種二元溶液的實驗繞射訊號結果 43
4.1.1 乙醇-水混合溶液不同溶劑體積比的繞射訊號 43
4.1.2 乙醇-二硫化碳混合溶液不同溶劑體積比的繞射訊號 46
4.1.3 甲醇-水混合溶液在不同溶劑體積比時的繞射訊號 48
4.2 水-乙醇二元溶液繞射訊號的理論模擬 50
第五章 結論與展望 54
5.1 結論 54
5.2 未來工作 54
附錄 57
A.光柵的種類與特性 57
A.1光柵的種類 57
A.2光柵的特性 59
B.線性奈米移動平台系統 61
參考文獻 64

1. A. Fick, “On Liquid Diffusion”, Phil. Mag., 10. 30 (1855).
2. C. Ludwig, “Aufbau und Verfall der Säfte and Gewebe. Thierische Wärme,” Wien. Akad. Ber., 20. 539 (1856).
3. C. Soret, “Sur l'etat d'equilibre que prend au point de vue de sa concentration une dissolution saline primitivement homohene dont deux parties sont portees a des temperatures differentes,”Arch. Sci. Phys. Nat, 2. 48 (1879).
4. D. Enskog, “Zur Elektronentheorie der Dispersion und Absorption der Metalle”, Ann. Physik, 38. 742 (1912).
5. S. Chapman,“The Kinetic Theory of Simple and Composite Monatomic Gases: Viscosity, Thermal Conduction, and Diffusion,”Proc. R. Soc. Lond. A., 93. 1 (1916).
6. E. D. Eastman, ”Thermodynamics for Non-isothermal Systems, “J. Am. Chem. Soc., 48. 1482 (1926).
7. J. Chipman, ”The Kinetic Theory of Simple and Composite Monatomic Gases: Viscosity, Thermal Conduction, and Diffusion,“J. Am. Chem. Soc., 48. 2577 (1926).
8. H. Kogelnik, “Coupled Wave Theory for Thick Hologram Gratings,”Bell System Technical Journal, 48. 2909 (1969).
9. H. J. Eichler, G. Salje, and H. Stahl, ”Thermal diffusion measurements using spatially periodic temperature distributions induced by laser light, “J. Appl. Phys., 44. 5383 (1973).
10. D. W. Pohl, S. E. Schwarz, and V. Irniger, ”Forced Rayleigh Scattering, “Phys. Rev. Lett., 33. 32 (1973).
11. K. Thyagarajan, and P. Lallemand, ”Determination of the thermal diffusion ratio in a binary mixture by forced Rayleigh scattering, “Opt. Commun., 26. 54 (1978).
12. S. Park, J. Sung, H. Kim, and T. Chang, ”Complementary Grating Effect in Forced Rayieigh Scattering,“ J. Phys. Chem., 95. 7121 (1991).
13. W. Köhler, ”Thermodiffusion in polymer solutions as observed by forced Rayleigh scattering,“J. Phys. Chem., 98. 660 (1993).
14. S. Park, H. Yu, and T. Chang, ”A New Analysis Scheme for Complex Forced Rayleigh Scattering Profiles,“ Macromolecules, 26. 3086 (1993).
15. W. Köhler, and B. Müller, ”Soret and mass diffusion coefficients of toluene n-hexane mixtures,“J. Chem. Phys., 103. 4367 (1995).
16. W. Köhler, and P. Rossmanith, ”Aspects of Thermal Diffusion Forced Rayleigh Scattering: Heterodyne Detection, Active Phase Tracking, and Experimental Constraints,“ J. Phys. Chem., 99.5838 (1995).
17. C. Debuschewitz, and W. Köhler, ”Molecular Origin of Thermal Diffusion in Benzene-Cyclohexane Mixtures,“Phys. Rev. Lett., 87. 055901 (2001).
18. P. Bordat, D. Reith, and F. Müller-Plathe, ”The influence of interaction details on the thermal diffusion in binary Lennard-Jones liquids,“J. Chem. Phys., 115. 8978 (2001).
19. Kousaku Maeda, Naoki Shinyashiki, Shin Yagihara, Simone Wiegand, and Rio Kita, “How does thermodiffusion of aqueous solutions depend on concentration and hydrophobicity?”Eur Phys J E Soft Matter. 37(10):94 (2014).
20. S. Wiegand, H. Ning, and H. Kriegs,”Thermal diffusion forced Rayleigh scattering setup optimized for aqueous mixtures,“J. Chem. Phys. B, 111.14169 (2007).
21. Y. Kishikawa, H. Shinohara, K. Maeda, Y. Nakamura, S. Wiegand, and R. Kita, ”Temperature dependence of thermal diffusion for aqueous solutions of monosaccharides, oligosaccharides, and polysaccharides,“Phys. Chem. Chem. Phys., 14. 10147 (2012).
22. 陳震偉， The Z-scan studies on simple molecular liquids with ultrashort laser pulses, 國立中正大學物理研究所，2008。
23. 張哲愷，有機染料溶液中質量傳輸與熱透鏡效應之研究，國立中正大學物理研究所，2011。
24. 林宥瑜，有機溶液中熱擴散和對流效應之研究，國立中正大學物理研究所，2011。
25. 李晉宜，有機染料在秒時域的質量傳輸性質研究，國立中正大學物理研究所，2009。
26. 陳奕豪，有機溶液之索雷特效應研究，國立中正大學物理研究所，2009。
27. 李新熛，有機染料的質量擴散性質之研究，國立中正大學物理研究所，2003。
28. 陳鈺鈞，溶液中熱擴散致被迫瑞利散射的時間特性研究，國立中正大學物理研究所，2011。
29. 黃承鈞，溶液中熱擴散致被迫瑞利散射效應之理論分析，國立中正大學物理研究所，2012。
30. 林承漢，二元混合溶液中熱擴散致被迫瑞利散射的機制研究，國立中正大學物理研究所，2012。
31. 陳柏帆，熱擴散致被迫瑞利散射的外差訊號，國立中正大學物理研究所，2013。
32. 巫俊樺，藉由熱擴散致瑞利散射實驗探討質量擴散理論，國立中正大學物理研究所，2015。
33. 林琪峰，二元溶液中熱擴散致被迫瑞利散射的研究，國立中正大學物理研究所，2015。
34. G. Hummer and A. Tokmakoff, Preface: Special Topical on Biological Water, J. Chem. Phys., 141, 22D101, 2014.
35. D. Landau, E.M. Lifshitz, Course of Theoretical Physics. Volume 6. Fluid mechanics, (Pergamon Press) (1987).
36. 廖健宇，二元溶劑溶液的熱透鏡效應研究，國立中正大學物理研究所，2003。
37. Yi-Ci Li, Yu-Ting Kuo, Po-Yuan Huang, Sidney S. Yang, Cheng-I Lee and Tai-Huei Wei, Thermal lensing effect of CS2 studied with femtosecond laser pulses, Phys. Chem. Chem. Phys., 17, 24738 (2015).
38. H. J. Eichler, P. Günter, and D. W. Pohl, Laser-Induced Dynamic Gratings, Springer-Verlag Berlin (1986).
39. W. Köhler, and S. Wiegand, Thermal nonequilibrium phenomena in fluid mixtures, (Springer Verlag, 2002).
40. A. Perronace, C. Leppla, F. Leroy, B. Rousseau, and S. Wiegand,”Soret and mass diffusion measurements and molecular dynamics simulations of n-pentane–n-decane mixtures,“J. Chem. Phys. 116, 3718 (2002).
41. W. Köhler, and R. Schӓfer, ”Polymer Analysis by Thermal-Diffusion Forced Rayleigh Scattering,“Adv. Polym. Sci.151, 1(2000).
42. Rio Kita, Simone Wiegand, and Jutta Luettmer-Strathmann, ”Sign change of the Soret coefficient of poly(ethylene oxide) in water/ethanol mixtures observed by thermal diffusion forced Rayleigh scattering,“J. Chem. Phys. 121, 3874 (2004).
43. R.C. Weast, M.J. Astle, W.H. Beyer, CRC handbook of chemistry and physics, 89 ed, CRC press Boca Raton, FL (2009).
44. 陳藝夫，甲基紅溶液在奈秒時域的非線性光學性質研究，國立中正大學物理研究所，2008。
45. 范紹翊，光偏極方向對摻雜偶氮染料易經的熱透鏡效應研究，國立中正大學物理研究所，2007。
46. 宋毓英，激光原理與技術，科學出版社，2010。
47. 周城，高斯光束經望遠鏡和薄透鏡組合系統的聚焦特性，光學精密工程，2007。
48. 繆家鼎、徐文娟、牟同升，光電技術，五南圖書，2003。
49. B. Rousseau, C. N.-Draghi and J. B. Avalos, The Role of Molecular Interactions in the Change of Sign of the Soret Coefficient, Europhys. Lett., 67, 976(2004).
50. D. Landau, E.M. Lifshitz, Course of Theoretical Physics. Volume 6. Fluid mechanics, (Pergamon Press), (1987).
51. Martin K, Spinks D, Measurement of the speed of sound in ethanol/water mixtures. Ultrasound in Medicine & Biology . Volume 27, Issue 2, (2001).
52. Che-Kai Chang, Chang-Chi Leu, Tai-Huei Wei, Sidney Yang, Tzer-Hsiang Huang, Yinglin Song, Study of Transient Thermal Lensing Effect in C60-Toluene Solution, Chem. Phys. Lett. 484, pp. 225-230, (2010).
53. O. Mishima and H. E. Stanley, The Relationship Between Liquid, Supercooled and Glassy Water, Nature, 396, 329, (1998).
54. J. R. Errington and P. Debenedetti, Relationship Between Structural Order and the Anomalies of Liquid Water, Nature, 409, 318, (2001).
55. P. C. Mehta and V. V. Rampal, Lasers and Holography, World Scientific (1993).
56. H.J. Eichler, P. Günter, D.W. Pohl, Laser-induced dynamic gratings, Springer-Verlag Berlin, (1986).