臺灣博碩士論文加值系統

本研究主要集中在不相容高分子，高密度聚乙烯( High density polyethylene, HDPE )和聚醯胺6( Polyamide 6, PA6 )混摻形成共連續結構後，添加石墨稀(Graphene nanosheets, GNS)產生雙重滲流伐值(double percolation)的複材型態變化，並分析高分子混摻加工參數的改變和GNS含量的變化以及改質劑HDPE-g-MA的添加，對於共連續複材中GNS-GNS導電網路結構的影響關係。
透過四點探針與高阻計量測不同GNS含量複材的導電性質，研究複材在何種濃度下開始形成GNS-GNS的導電網路結構，以掃描式電子顯微鏡(scanning electron microscope, SEM)與transmission electron microscopy, TEM)穿透式電子顯微鏡觀察複材混合後的內部結構變化與GNS分佈情形，並分析結構變化及GNS分佈對於HDPE/PA6/GNS複材的導電性質影響，最後以微視差掃描卡計(Differential scanning calorimetry, DSC)做動態結晶分析，探討複材結構轉變時，結晶行為對結構和導電性質的關係變化。
從SEM及TEM分析HDPE/PA6在比例50/50情形下會產生共連續形態，加入不同含量GNS會使內部結構產生形態變化，透過TEM影像分析圖發現GNS會在HDPE和PA6的兩相介面上形成導電網路，經導電度的測量發現HDPE/PA6-6N/GNS及HDPE/PA6-10k/GNS在GNS含量為3wt%及5wt%時，皆有double percolation的產生，並加入HDPE-g-MA後，HDPE/HDPE-g-MA/PA6-6N/GNS-M在GNS含量為5wt%時導電度更加提升。

This study focused on the morphology change of immiscible polymer, high-density polyethylene(HDPE) and polyamide 6(PA blends with the incorporation of GNSs to produce double double percolation, to find the direct relationship between the GNS content with compatibilizer introduce of blends and the network structure of GNSs.
The conductivities of HDPE/PA6 composites filled with different amounts of GNS were measured by 4-point Probe and Source meter. The morphologies, GNS dispersion and crystallization behavior of HDPE/PA6/GNS composites were investigated by scanning electron microscopy (SEM), transmission electron microscopy (TEM), and differential scanning calorimetry (DSC).
Analysis the ratio 50/50 HDPE/PA6 will produce co-continuous morphology by SEM and TEM, different content GNSs bring about morphology change. The GNSs located in HDPE/PA6 phases form conductive network, we find the double percolation bring in 3wt% and 5wt% of HDPE/PA6-6N/GNS and HDPE/PA6-10k/GNS, Incorporate the HDPE-g-MA will more improve the conductivity of HDPE/HDPE-g-MA/PA6-6N/GNS-M in 5wt%.

誌　　謝 i
摘　　要 ii
Abstract iii
目　　錄 iv
圖目錄 viii
表目錄 x
一、前言 1
二、研究目的 3
三、文獻回顧 4
3.1高密度聚乙烯(High density polyethylene, HDPE) 4
3.2聚醯胺6(Polyamide 6, PA6) 4
3.3 GNS製備 5
3.3.1熱膨脹法製備TEGO 5
3.3.2化學還原法RGO 6
3.4 GNS複材機械特性 6
3.5 GNS複材導電性 7
3.6共連續形態複材導電性 8
3.7奈米粉體對不相容高分子複材的形態影響 9
3.8 混合順序對於GNS分佈影響 10
3.9黏度對奈米粉體的分佈變化 10
3.10混合時間對奈米粉體的分佈變化 12
四、理論 21
4.1 Percolation theory 21
4.2 Double percolation 22
4.3奈米粉體移動機制 22
五、實驗 26
5.1實驗藥品 26
5.2實驗器材與測試儀器 26
5.3實驗步驟 29
5.3.1 熔融混合 29
5.3.2 原子力顯微鏡(AFM) 30
5.3.3 掃描式電子顯微鏡(SEM) 30
5.3.4 穿透式電子顯微鏡(TEM) 31
5.3.5導電度測試 32
5.3.6示差掃描卡計 (DSC) 33
5.3.9機械性質量測 33
5.4實驗流程 34
六、結果與討論 35
6.1石墨稀形態及結構 35
6.1.1 TEM分析GNS的外觀形態 35
6.1.2 AFM掃描分析GNS薄片厚度 35
6.1.3 FTIR分析探討Graphene的結構及性質 35
6.2 SEM分析HDPE/PA6-6N、HDPE/PA6-10k複材結構 36
6.3 HDPE/PA6/GNS複材加工參數 37
6.4 導電度分析HDPE/GNS、PA6-6N/GNS複材 37
6.4.1 導電分析混合時間對HDPE/PA6/GNS-M複材的影響 38
6.4.2 導電分析混合方式對HDPE/PA6-10k/GNS複材的影響 38
6.4.3 導電分析HDPE/PA6-6N/GNS-P、HDPE/PA6-10k/GNS-P複材 39
6.5 TEM分析HDPE/GNS、 PA6-6N/GNS複材中GNS分佈 39
6.5.1 SEM分析HDPE/PA6-6N/GNS-P複材結構變化 40
6.5.2 TEM分析HDPE/PA6-6N/GNS-P複材中GNS分佈 41
6.5.3 SEM分析HDPE/PA6-10K/GNS-P複材結構變化 41
6.5.4 SEM分析混合時間對HDPE/PA6-10K/GNS-M複材影響 42
6.5.5 TEM分析不同混和時間HDPE/PA6-10k/GNS-M複材 43
6.6 HDPE/HDPE-g-MA/PA6/GNS-M加工參數 43
6.7 HDPE/PA6/GNS-M加入HDPE-G-MA後對導電度影響 44
6.7.1 SEM分析HDPE/HDPE-g-MA/PA6複材 44
6.7.2 SEM分析HDPE/HDPE-g-MA/PA6-6N/GNS-M複材 45
6.7.3 SEM分析HDPE/HDPE-g-MA/PA6-10k/GNS-M複材 46
6.7.4 TEM分析HDPE/HDPE-g-MA/PA6-10k/GNS-5wt%-M複材 47
6.8 動態結晶分析 47
6.8.1 動態結晶分析不同混合時間HDPE/PA6-10k/GNS-M 複材 47
6.8.2 動態結晶分析不同混和順序HDPE/PA6-10k/GNS複材 48
6.8.3 動態結晶分析HDPE/PA6/GNS-P複材 48
6.8.4 動態結晶分析HDPE/HDPE-g-MA/PA6/GNS-M複材 50

[1]M. I. Kohan, Nylon Plastics Handbook, (1995).
[2]T. Kuilla, S. Bhadra, D. Yao, N. H. Kim, S. Bose, J. H. Lee, Prog. Polym. Sci., 35, 1350 (2010).
[3]J. R. Potts, D. R. Dreyer, C. W. Bielawski, R. S. Ruoff, Polym., 52, 5 (2012).
[4]W. S. Hummers, R. E. Offeman, J. Am. Chem. Soc., 80, 1339 (1958).
[5]L. Staudenmaier, Ber. Dtsch. Chen. Ges, 31, 1481 (1898).
[6]24.A. Buchsteiner, A. Lerf, Jr. A. Pieper, J. Phys. Chem. B, 110, 22328 (2006).
[7]V. G. Ruess, F. Vogt, Monatsh. Chem., 78, 222 (1948).
[8]S. Park, R. S. Ruoff, Nat. Nanotechnol., 5, 217 (2009).
[9]D. R. Dreyer, S. Murali, Y. Zhu, R. S. Ruoff, C. W. Bielawski, J. Mater, Chem., 21. 3443 (2011).
[10]S. Park, J. An, R. D. Piner, I. Jung, D. Yang, A. Velamakanni, S. T. Nguyen, R. S. Ruoff, Chem. Mater., 20, 6592 (2008).
[11]X. Zhao, Q. Zhang, D. Chen, Macromolecules, 43, 2357 (2010).
[12]Fangming Du, Robert C. Scogna, Wei Zhou, Stijn Brand, John E. Fischer, and Karen I. Winey, Macromolecules, 37, 9048 (2004).
[13]S. Stankovich, D. A. Dikin, G. H. B. Dommett, K. M. Kohlhaas, E. J. Zimney, E. A. Stach, R. D. Piner, S. T. Nguyen and R. S. Ruoff, Nature, 442, 282 (2006).
[14]46.H. B. Zhang, W. G. Zheng, Q. Yan, Y. Yang, J. W. Wang, Z. H. Lu, G. Y. Ji, Z. Z. Yu, Polym., 51, 1191 (2010).
[15]J. Liang, Y. Wang, Y. Huang, Y. Ma, Z. Liu, J. Cai, C. Zhang, H. Gao, Y. Chen, Carbon, 47, 922 (2009).
[16]48.S. Ansari, E. P. Giannelis, J. Polym. Sci. Part B Polym. Phys., 47, 888 (2009).
[17]49.H. B. Zhang, W. G. Zheng, Q. Yan, Z. G. Jiang, Z. Z. Yu, Carbon, 50, 5117 (2012).
[18]M. Sumita, K. Sakata, S. Asai, K. Miyasaka, H. Nakagawa, Polym. Bull., 25, 265(1991).
[19]P. Pötschke, A. R. Bhattacharryya, A. Janke, Carbon, 42, 965 (2004).
[20]13.A. Göldel, G. Kasaliwal, P. Pötschke, Macromol Rapid Commun., 30, 423(2009).
[21]51.O. Meincke, D. kaempfer, H. Weickmann, C. Friedrich, M. Vathauer, H. Warth, Polym, 45, 739(2004).
[22]F. Xiang.,Yunyun Shi, X. Li, T. Huang, C. Chen, Ya. Peng, Y. Wang, Eur. Polym. J., 48, 350(2012).
[23]D. Yan, H. B. Zhang, Y. Jia, J. Hu, X. Y. Qi, Z. Zhang, Z. Z. Yu, ACS Appl. Mater. Interface, 4, 4740(2012).
[24]J. Feng, C. M. Chan, J. X. Li, Polym Eng Sci, 42, 1058(2003).
[25]F. Fenouillot, P.Cassagnau, J.-C. Majeste, Polym, 50, 1333 (2009).
[26]54.L. Elias, F. Fenouillot, J. C. Majeste, G. Martin, P. Cassagnau, Appl.Phys., 46, 1976(2008).