臺灣博碩士論文加值系統

玻璃纖維的特性有不助燃，化學穩定性、抗濕性等優良性能，但因分子為剛性結構且韌性不足，玻纖表面平滑且缺乏反應性，難與基材的良好接著，加工過程中很容易斷裂，耐磨性差，一般都以表面處理改質方式，將未經上漿的玻纖織物含浸矽烷偶合劑後來增進其反應性與可塗佈加工特性，增加其表面粗糙。然而，本研究主要是合成水性PU後塗層於玻纖織物上，因水性PU的耐熱性與耐候性不佳，所以引入的奈米雲母來與PU分子產生化學交聯和分子間的作用力 ，藉由改變不同PTMG軟鏈段的分子量及奈米雲母的添加量，來探討其對FT-IR、TGA、DSC、SEM與粒徑測定儀…，來觀察其官能基、熱性質變化、表面型態、與粒徑大小的差異性；以及塗層織物後，其改變軟鏈段的分子量及奈米雲母的添加量對FT-IR、SEM、UV-vis、吸水率、耐候測試…等多功能玻纖織物相關探討。

In this study was used the method of surface modified treatment to improve the adhesion of glass fabrics and water-borne polyurethane/nano Mica. First, the un-sizing glass fabrics dipped in the silane coupling agent so that covered on the surface of glass fiber to enhance the glass fiber hydrophilic function resulting from improving the processing characteristics for coating on the glass fabrics. Both ends of the silane coupling agent and glass fiber surface were reacted with polyurethane water-borne/Mica Nanocomposites to produce chemical bonding, respectively. The glass fabrics were coated with water-borne polyurethane/Mica resin resulting in interacting with fiber to form the protection film on the surface of glass fibers to improve the defect of loose glass fibers and enhance the thermal stability, chemical stability of process functional glass fabrics.
Water-borne polyurethane with the diisocyanate group was reacted with the various molar ratio (1 wt%、3 wt%、5 wt%) of nano Mica including amino functional group to produce the chemical bond. Water-borne polyurethane/Mica nanocomposited materials were then used by FT-IR、TGA、DSC、SEM、and potential size analyze these chemical structure, thermal properties, surface morphology, molecular weight and particle size….etc. Moreover, the multifunctional glass fabrics were fabricated by dipped on the glass fabrics with coupling agent combined by FT-IR、SEM、UV-vis、Water uptake、Adhesion strength and Weatherability analyze with coating the water-borne polyurethane/Mica nanocomposited materials.

目 錄
摘　要 I
ABSTRACT II
誌 謝 IV
目 錄 V
表目錄 VII
圖目錄 VIII
第一章 緒論 1
1.1研究背景 1
1.2研究動機 4
第二章 文獻回顧 6
2.1 玻璃纖維 6
2.1.1 玻璃纖維的應用與分類 6
2.1.2 玻璃纖維的製造方法[7] 7
2.1.3 玻璃纖維的組成與結構 9
2.2 玻璃纖維的表面處理[9] 9
2.3 玻璃纖維接著機構與破壞形式 12
2.3.1 界面接著[13、14] 12
2.3.2 玻璃纖維表面處理增進界面接著之機構[16、17] 12
2.3.3 界面接著破壞類型[18、19] 16
2.4 水性聚氨酯樹脂 17
2.4.1 水性PU的合成方法 19
2.4.2 水性PU的的合成單體 22
2.5 水性聚氨酯樹脂/奈米複合材料 26
2.5.1 有機/無機複合材料[18,19] 26
2.5.2 奈米雲母 26
2.5.3 助劑 28
2.6 織物後整理樹脂加工[16] 29
第三章 實驗 33
3.1 實驗藥品、材料 33
3.2 實驗流程 35
3.2.1 水性PU之製備 36
3.2.2 水性PU/Mica Nanocomposits之製備 37
3.2.3 水性PU膜之製備 40
3.2.4 矽烷偶合劑混合液配置 40
3.2.5 玻纖織物表面處理之方法 40
3.2.6 功能性玻纖織物製備 41
3.3 實驗儀器 42
3.3.1 傅立葉轉換紅外線光譜(FTIR-ATR) 42
3.3.2 熱重量分析儀測定(TGA) 43
3.3.3 示差掃描熱量分析儀測定(DSC) 44
3.3.4 紫外光/可見光光譜分析(UV-vis) 45
3.3.5 掃描式電子顯微鏡(SEM) 46
3.3.6 靜態接觸角量測儀 47
3.3.7 粒徑分析儀 48
3.3.8 織物之耐候性測定 49
3.3.9 黃變指數測定 50
3.3.10 平行塗佈機 51
第四章 結果與討論 52
4.1 水性PU之FT-IR分析[31][32][33] 52
4.2 水性PU/Mica Nanocomposits之FT-IR 56
4.3 熱重量分析(TGA) [34,35,36] 59
4.4 示差掃描熱量分析儀測定(DSC)[37,38,39,40,41] 61
4.5 紫外光/可見光光譜分析 63
4.6 粒徑分析儀 64
4.7 靜態濕潤角測試 67
4.8 掃描式電子顯微鏡檢測(SEM) 69
4.8.1 水性PU /Mica奈米複合材料之薄膜表面型態[46,47,48] 69
4.8.2 未處理玻璃纖維織物之表面型態 73
4.8.3 經偶合劑處理後之玻璃纖維表面型態 73
4.8.4 水性PU /Mica塗佈於經偶合劑處理過玻纖織物之表面型態 76
4.9 吸水率(Water uptake)之分析[27] 78
4.10 耐候性試驗 80
第五章 結論 83
參考文獻 85

1.錢世准，玻璃纖維紡織品的開發動向，玻璃纖维，2001年，第5期
2.周準，張萬平，玻璃纖維紡織品的開發動向，玻璃纖维，2006年，第1期
3.李熙，汪輝，玻纖織物阻燃塗層配方的研究，玻璃纖维，2009年，第5期
4.H. Abdul Razak, C.S. Chua, H. Toyoda, Weatherability of coated fabrics as roofing material in tropical environment, Building and Environment, 2004, 39 , p87 – 92
5.M. V. Pandya, D. D. Seshande and D. G. Hundiwale, J of Appl. Polym. Sci. 1986, 32, 4945.
6.M. V. Pandya, D. D. Seshande and D. G. Hundiwale, J of Appl. Polym. Sci. 1988, 35, 7, 1803.
7.http：//www.npc.com.tw/emd-new/di3/bc2-02-01.htm
8.R.L. Gorowara, W.E. Kosik, S.H. McKnight, R.L. McCullough, Molecular characterization of glass fiber surface coatings for thermosetting polymer matrix/glass fiber composites, Composites: Part A 32 (2001) 323–329
9.Yanjun Xie , Silane coupling agents used for natural fiber/polymer composites： A review, Composites： Part A , 2010, 41 , p806–819
10.許小芳，申世杰，矽烷偶聯劑處理玻璃纖維對複合材料，航太材料工藝，2010，第三期
11.DiBenedetto A T，Connelly S M，Lee W C， The properties of organosiloxane／polyester interfaces at an e-glass fiber surface, J．Adhesion, 1995, 52, p41—64
12.D.M. Laura, H. Keskkula, J.W. Barlow, D.R. Paul, Effect of glass fiber surface chemistry on the mechanical properties of glass fiber reinforced, rubber toughened nylon 6, Polymer , 2002, 43, p4673–4687
13.程時遠，”膠黏劑”,北京,化學工業出版社, (2001).
14.徐祖順，”織物用膠黏劑及黏接技術”,北京,化學工業出版社,(2004)
15.W. A. Zisman. Surface chemistry of plastic reinforced by strong fibers. Product Research and Development, 1963, 8, 2, p98-111
16.Montaudo G. Scamporrino E, Vitalini. J.Polym. Sci., Polym Chem. 1983, 21, 3361—3371.
17.Ramazan Benrashid, Gordon L Nelson. J. Fire Sci. ,1993, 11, 371—393．
18.黃麗，”聚合物複合材料”,北京,中國輕工業出版社,(2001)
19.沃丁柱，”複合材料大全”,北京, 化學工業出版社,(1990)
20.陶聖如，”阻燃材料與技術” 北京, 化學工業出版社，(1992)
21.歐育湘．新世紀前10年全球阻燃劑發展預測，化工進展，1999, 18, 6, 29—32.
22.Zoran S. P., The effect of soft-segment length and concentration on phase separationin segmented polyurethanes, Journal ofpolymer science, 1989,27(4), 545-548
23.李曉萱”水性聚氨酯的硬段結晶與黏接性能”, 北京,化學工業出版社，(1993)
24.Dawn M. Crawford, Robert G. Bass, Thomas W. Haas, Strain effects on thermal transitions and mechanical properties of thermoplastic polyurethane elastomers, Thermochimica Acta, 1998 , 323 , p53-63
25.涂偉萍，”水性塗料,北京,化學工業出版社,(2006)
26.閆福安，”水性樹脂與水性塗料”,北京, 化學工業出版社,(2009)
27.詹明惠，水性PU-矽化合物混成樹脂型塗佈劑之合成及其物性之探討，碩士論文，中國文化大學應用化學所，台北，2004。
28.Zhiyong Ren, Dezhu Ma, Xiaozhen Yang, H-bond and conformations of donors and acceptors in model polyether based polyurethanes Polymer, 2003 , 44 , p6419–6425
29.Michael Alexandre, Philippe Dubois, Polymer-layered silicate nanocomposites: preparation, properties and uses of a new class of materials, Materials Science and Engineering, 2000, 28, p3-10
30.劉力洵、李俊偉、張志謙，玻璃纖維/聚丙烯複合材料界面研究，材料科學與工藝，2000，8，2，p105-107
31.Aswini K. Mishra, Rama Shanker Mishra, Ramanuj Narayan, K.V.S.N. Raju*,Effect of nano ZnO on the phase mixing of polyurethane hybrid dispersions, Progress in Organic Coatings , 2010, 67 , p405–413
32.Jean-Luc Gardette, Infrared analysis of the photochemical behaviour of segmented polyurethanes:aliphatic poly(ether-urethane)s, Polymer, 1998 , Vol. 39 No. 24 , p5973–5980,
33.J.H. Li , R.Y. Hong, M.Y. Li , H.Z. Li, Y. Zheng, J. Ding, Effects of ZnO nanoparticles on the mechanical and antibacterial properties of polyurethane coatings, Progress in Organic Coatings , 2009, 64 , p504–509
34.T. L. Wang, T. H. Hsieh, Polymer Degradation and Stability, 1996, vol.55, p.95-102.
35.K. Mequanint, R. Sanderson and H. Pasch, PolymerDegradation and Stability, 2002,vol.77, p.121-128.
36.Fernanda M. B. Coutnho, Marcia C. Delpech, Polymer Degradation and Stability, 2003, vol.81, p.19-27.
37.郭安庭，硬質鏈段不規則性對PU 奈米形態之影響(II)，碩士論文，國立中央大學化學工程與材料工程研究所，桃園，2006。
38.蔡東穎，非極性式poly-ip based PU 之軟質段末端改質對形態的影響，碩士論文，國立中央大學化學工程與材料工程研究所，桃園，2006。
39.Jae Hyung Park, Ki Dong Park, You Han Bae, PDMS-based polyurethanes with MPEG grafts: synthesis, characterization and platelet adhesion study, Biomaterials 1999 , 20 , p943-953
40.D.K. Chattopadhyay, B. Sreedhar, K.V.S.N. Raju, The phase mixing studies on moisture cured polyurethane-ureas during cure, Polymer, 2006 ,47 p3814–3825
41.Umaprasana Ojha, Pallavi Kulkarni, Rudolf Faust, Syntheses and characterization of novel biostable polyisobutylene based thermoplastic polyurethanes, Polymer , 2009, 50, p3448–3457
42.J. W. C. Van Bogart , D. A. Bluemke , and S. L. Cooper , , Annealing-induced morphological changes in segmented elastomers, Polymer , 1981 v22 , p1428 ,
43.謝添壽，「嵌段式PU的結構與性質(II)」，博士論文，國立中央大學化學工程與材料工程研究所，桃園，1997
44.Wang Jing-hui, Study on the stability of inverse emulsions containing polymerisable emulsifier, Thermosetting Resin, 2008, vol.23, No.5, p8-11
45.SHEN Yi-ding, WANG Chun-lei, FEI Gui-qiang, WANG Hai-hua, The influence of cationic degree on fluorinated acrylate copolymer emulsion andthe surface properties of its membrane, TECHNOLOGY, 2009, Vol. 30, No. 14, p18-21
46.Bin Wei, Strengthening of basalt fibers with nano-SiO2–epoxy composite coating, Materials and Design, 2011 , 32, 4180–4186
47.Uday Konwar, Mesua ferrea L. seed oil based highly thermostable and biodegradable polyester/clay nanocomposites, Polymer Degradation and Stability , 2009, 94, p2221–2230
48.ShengWen Zhang, Facile synthesis of waterborne UV-curable polyurethane/silica nanocomposites and morphology, physical properties of its nanostructured films, Progress in Organic Coatings , 2011, 70 , p1–8
49.董詠春,“滌綸的深色加工”,江蘇印染, 1990, 第3期, p7-11
50.鐘正宏，聚胺脂發泡體之耐黃變性質與光穩定性質研究，碩士論文，國立勤益技術學院材料與化學工程研究所，台中，2006。
51.林玲修，玻璃纖維表面處理對接著性改良之研究，博士論文，國立台灣科技大學纖維及高分子所，台北，2002。
52.John Comyn, Handbook of Adhesives and Sealants, Volume 2, 2006, Pages 1-50