臺灣博碩士論文加值系統

本研究使用汽車、電氣及機械設備等方面運用極為廣泛之聚己內醯胺 (Polyamide 6, PA6) 作為基材，填充具有低煙無鹵素優點之環保型無機阻燃劑 — 氫氧化鎂 (Magnesium Hydroxide, MH），搭配適用於聚己內醯胺之無鹵素磷系阻燃劑 —間苯二酚四苯基二磷酸酯 (Resorcinol bis(diphenyl phosphate), RDP)，並添加空心微珠 (cenosphere)，使用雙螺桿擠出機以物理摻混方法熔融製備成 PA6/cenosphere/MH/RDP 高分子阻燃複合材料，依據材料測試規範以射出成型法製備相關測試試片，進行顯微觀察、力學性能試驗、熱性能分析、燃燒性質檢測。TGA 結果顯示，其熱穩定性及熱裂解行為皆有所改變添加，添加 MH 有助於灰燼量之提升; LOI 及 UL-94 結果顯示，PA6 阻燃複合材料相較於純料 PA6 其效果皆有明顯之提升，當搭配添加 46 wt% MH、1 wt% RDP及 3 wt% 空心微珠時，其 LOI 值可達 42% 且 UL-94 達 V-0 等級，比單一阻燃劑之 LOI 值及 UL-94 為高，表示兩種阻燃劑與空心微珠對於阻燃性能有相乘效果。

In this study, we used the Polyamide 6 (PA6) as the matrix which is widely used in electronic industries and automotive production, and added environment-friendly inorganic flame retardants － Magnesium Hydroxide (MH) with halogen-free for the matrix phosphorus flame retardant - Resorcinol bis diphenyl phosphate (RDP), and add cenosphere. PA6/cenosphere/MH/RDP flame retardant polymer composite were melt-mixed by using the twin screw extruder, then injection molding into standard specimen.The properties of composites were characterized by FE-SEM, Tensile testing, Impact testing, TGA, DSC, LOI and UL-94.The TGA results indicate that the thermal stability and the decomposition behavior of PA6 were both changed with the addition of MH,RDP and cenosphere；this resulted shown that add MH contributed to increase the ash content.Compared with the neat PA6, the flame retardant polymer composite PA6 samples have improved LOI and UL-94 rating,for example, the LOI value can be achieved 42% when containing 46 wt% MH, 1 wt% RDP and 3 wt% cenosphere, and the UL-94 rating going from no rating to V-0, higher than add single flame retardants, it denote the two flame retardants and cenosphere have synergistic effects.

中文摘要 i
英文摘要 ii
誌 謝 iii
目 錄 iv
表目錄 vi
圖目錄 vii
符號說明 x
第一章 緒論 1
1-1 前言 1
1-2 研究內容 2
1-2-1 研究動機 2
1-2-2 研究目的 3
1-3 研究流程圖 4
第二章 文獻回顧 5
2-1 高分子材料 5
2-1-1 聚醯胺簡介 5
2-2 空心微珠 7
2-3 阻燃劑 8
2-3-1 阻燃機制 9
2-3-2 氫氧化鎂 10
2-3-3 間苯二酚四苯基二磷酸酯 13
2-4 高分子阻燃複合材料 16
第三章 實驗方法與步驟 18
3-1 實驗材料 18
3-2 實驗儀器 20
3-3 聚己內醯胺/阻燃劑/空心微珠之混煉 22
3-4 聚己內醯胺/阻燃劑/空心微珠複合材料之射出成型製程 26
3-5 實驗分析 28
3-5-1 場發射掃描式電子顯微鏡 28
3-5-2 拉伸試驗 30
3-5-3 衝擊試驗 33
3-5-4 微差掃描熱卡計 36
3-5-5 熱重分析儀試驗 38
3-5-6 極限氧指數試驗 40
3-5-7 水平及垂直燃燒試驗 42
第四章 結果與討論 44
4-1 冷場發射掃描式電子顯微鏡分析 44
4-2 拉伸試驗分析 52
4-2-1抗拉強度 52
4-2-2斷點延伸率 55
4-3 衝擊強度試驗分析 57
4-4 微差掃描熱卡計試驗 59
4-5 熱重分析試驗 61
4-6 PA6 阻燃複合材料之燃燒性質探討 63
第五章 結論 66
參考文獻 67
附錄一 73

1.Balakrishnan, H., Hassan, A., Isitman, N. A., and Kaynak, C., “On the use of magnesium hydroxide towards halogen-free flame-retarded polyamide-6/polypropylene blends,” Polymer Degradation and Stability, 97, 1447-1457, 2012.
2.Beyer, G., “Flame retardant properties of EVA-nanocomposites and improvements by combination of nanofiller with aluminium trihydrate,” Fire and Materials, 25, 193-197, 2001.
3.Cao, X. G., and Zhang, H. Y., “Investigation into conductivity of silver-coated cenosphere composites prepared by a modified electroless process,” Applied Surface Science, 264, 756-760, 2013.
4.Chand, N., Sharma, P., and Fahim, M., “Correlation of mechanical and tribological properties of organosilane modified cenosphere filled high density polyethylene,” Materials Science and Engineering A, 527, 5873-5878, 2010.
5.Chen, J., Liu, S., and Zhao, J., “Synthesis, application and flame retardancy mechanism of a novel flame retardant containing silicon and caged bicyclic phosphate for polyamide 6,” Polymer Degradation and Stability , 96, 1508-1515, 2011.
6.Dahiya, J. B., Rathi, S., Bockhorn, H., Hausmann, M., and Kandola, B. K., “The combined effect of organic phoshphinate/ammonium polyphosphate and pentaerythritol on thermal and fire properties of polyamide 6-clay nanocomposites,” Polymer Degradation and Stability , 97, 1458-1465, 2012.
7.Das, A., and Satapathy, B. K., “Structural, thermal, mechanical and dynamic mechanical properties of cenosphere filled polypropylene composites,” Materials &; Design , 32, 1477-1484, 2011.
8.Fang, K., Li, J., Ke, C., Zhu, Q., Tao, K., Zhu, J., and Yan, Q., “Intumescent flame retardation of melamine-modified montmorillonite on polyamide 6: Enhancement of condense phase and flame retardance,” Polymer Engineering &; Science , 51, 377-385, 2011.
9.Feng, J., Hao, J., Du, J., and Yang, R., “Flame retardancy and thermal properties of solid bisphenol A bis(diphenyl phosphate) combined with montmorillonite in polycarbonate,” Polymer Degradation and Stability , 95, 2041-2048, 2010.
10.Haurie, L., Fernandez, A. I., Velasco, J. I., Chimenos, J. M., Lopez Cuesta, J.-M., and Espiell, F., “Thermal stability and flame retardancy of LDPE/EVA blends filled with synthetic hydromagnesite/aluminium hydroxide/montmorillonite and magnesium hydroxide/aluminium hydroxide/montmorillonite mixtures,” Polymer Degradation and Stability , 92, 1082-1087, 2007.
11.Hu, Y. J., Zhang, H. Y., Li, F., Cheng, X. L., and Chen, T. L.,“Investigation into electrical conductivity and electromagnetic interference shielding effectiveness of silicone rubber filled with Ag-coated cenosphere particles,” Polymer Testing , 29, 609-612, 2010.
12.Hu, Z., Chen, L., Lin, G.-P., Luo, Y., and Wang, Y.-Z., “Flame retardation of glass-fibre-reinforced polyamide 6 by a novel metal salt of alkylphosphinic acid,” Polymer Degradation and Stability , 96, 1538-1545, 2011.
13.Kandare, E., Chigwada, G., Wang, D., Wilkie, C. A., and Hossenlopp, J. M., “Probing synergism, antagonism, and additive effects in poly(vinyl ester) (PVE) composites with fire retardants,” Polymer Degradation and Stability , 91, 1209-1218, 2006.
14.Lee, K., Yoon, K., Kim, J., Bae, J., Yang, J., and Hong, S., “Effect of novolac phenol and oligomeric aryl phosphate mixtures on flame retardance enhancement of ABS,” Polymer Degradation and Stability , 81, 173-179, 2003.
15.Lenża, J., Merkel, K., and Rydarowski, H., “Comparison of the effect of montmorillonite, magnesium hydroxide and a mixture of both on the flammability properties and mechanism of char formation of HDPE composites,” Polymer Degradation and Stability , 97, 2581-2593, 2012.
16.Liu, S.-P., Ying, J.-R., Zhou, X.-P., Xie, X.-L., and Mai, Y.-W., “Dispersion, thermal and mechanical properties of polypropylene/magnesium hydroxide nanocomposites compatibilized by SEBS-g-MA,” Composites Science and Technology, 69, 1873-1879, 2009.
17.Luong, D. D., Strbik, O. M., Hammond, V. H., Gupta, N., and Cho, K., “Development of high performance lightweight aluminum alloy/SiC hollow sphere syntactic foams and compressive characterization at quasi-static and high strain rates,” Journal of Alloys and Compounds ,550, 412-422, 2013.
18.Zanetti, M., Camino, G., Canavese, D., Morgan, A. B., Lamelas, F. J., and Wilkie, C. A., “Fire Retardant Halogen - Antimony - Clay Synergism in Polypropylene Layered Silicate Nanocomposites,” American Chemical Society, 14, 189-193, 2002.
19.Meng, X.-F., Shen, X.-Q., and Liu, W., “Synthesis and characterization of Co/cenosphere core–shell structure composites,” Applied Surface Science , 258, 2627-2631, 2012.
20.Perret, B., and Schartel, B., “The effect of different impact modifiers in halogen-free flame retarded polycarbonate blends – II. Fire behaviour,” Polymer Degradation and Stability , 94, 2204-2212, 2009.
21.Samyn, F., and Bourbigot, S., “Thermal decomposition of flame retarded formulations PA6/aluminum phosphinate/melamine polyphosphate/ organomodified clay: Interactions between the constituents,” Polymer Degradation and Stability , 97, 2217-2230, 2012.
22.Song, L., Hu, Y., Lin, Z., Xuan, S., Wang, S., Chen, Z., and Fan, W., “Preparation and properties of halogen-free flame-retarded polyamide 6/organoclay nanocomposite,” Polymer Degradation and Stability , 86, 535-540, 2004.
23.Wang, W., Li, Q., Wang, B., Xu, X.-T., and Zhai, J.-P., “Synthesis of fly ash cenosphere/polyaniline and mullite/polyaniline core–shell composites,” Materials Chemistry and Physics , 135, 1077-1083, 2012.
24.Xu, X. N., Lu, L. G., Tin, Q. Ming., Wang, D. W., “Kinetic study on pyrolysis of rolysis of bisphenol a diphosphate flame-retarded PC/ABS,” Fire safety science, Vol.18, No.2,2009
25.Zhao, B., Hu, Z., Chen, L., Liu, Y., Liu, Y., and Wang, Y.-Z., “A phosphorus-containing inorganic compound as an effective flame retardant for glass-fiber-reinforced polyamide 6,” Journal of Applied Polymer Science , 119, 2379-2385, 2011.
26.Znetti , M., Camino, G., Canavese, D., Morgan, A. B., Lamelas, F. J., and Wilkie, C. A., 2002, “Fire retardant holagen-antimony-clay synergism in ployproplene layered silicate nanocomposites, ” Chemistry of Materials, 14, 189-193, 2002.
27.Zong, R., Hu, Y., Wang, S., and Song, L., “Thermogravimetric evaluation of PC/ABS/montmorillonite nanocomposite,” Polymer Degradation and Stability , 83, 423-428, 2004.
28.丁雪佳、盧冬梅、余鼎聲、張立群、徐日煒、白健，“空心微珠填充尼龍6的研究” ，塑料，第 32 卷，第 2 期，2003。
29.李秀娟，“聚乙烯／氫氧化鎂／蒙脫土奈米複合材料之阻燃特性、機械性質與熱穩定性研究”，國立雲林科技大學環境與安全衛生工程學系，碩士論文，2011。
30.余承儐，“聚乳酸/氫氧化鋁/奈米黏土複合材料之阻燃性質”， 國立台北科技大學化學工程研究所，碩士論文，2010。
31.吳信宏，“以微波輔助萃取搭配液相層析質譜儀檢測固態樣品中六溴環十二烷之方法開發”，國立中央大學化學研究所，碩士論文，2007。
32.宋曉嵐、黃學輝，“無機材料科學基礎”，化學工業出版社，第 1 ~ 16 頁，2006。
33.周森，“複合材料－奈米．生物科技”，全威圖書有限公司，第 85 ~ 88 頁，2009。
34.林碧蘭、路新瀛、陳勤，“空心微珠/環氧樹脂高強浮力材料的性能及斷裂分析” ，複合材料學報，第 28 卷，第 3 期，2011。
35.柳元涵，“新穎氮磷共乘難燃添加劑之合成、鑑定與性質探討”，國立成功大學化學工程學系，碩士論文，2002。
36.陳旭，“無鹵阻燃劑對PC/ABS聚合體物性之影響”，逢甲大學紡織工程研究所，碩士論文，2007。
37.徐國財、張立德，“奈米複合材料”，五南圖書出版公司，2004，第 350 ~ 355 頁。
38.倪禮忠、陳麒，“聚合物基複合材料”，華東理工大學出版社，第 1 ~ 7 頁，1995。
39.張婷婷、鄭實，“磷酸酯類阻燃劑在PC/ABS合金中的應用” ，廣東化工，第 36 卷，第 7 期，2009。
40.焦劍、姚軍燕，“功能高分子材料”，化學工業出版社，第 1 ~ 5 頁，2007。
41.賈修偉，“奈米阻燃材料”，化學工業出版社，第 25 ~ 27 頁，2004。
42.齊寶森等主編，“新型材料及其應用”，哈爾濱工業大學出版社，第 55 ~ 60 頁，2007。
43.潘文群，“高分子材料分析與測試”，化學工業出版社，第 121 ~ 134 頁，2004。
44.劉正英、楊鳴波，“工程塑料改性技術”，化學工業出版社，第 29 ~ 116 頁，2007。
45.歐育湘、李建軍，“材料阻燃性能測試方法”，化學工業出版社，第 17 ~ 31 頁，2007。
46.魏禾霖，“聚碳酸酯/ABS/蒙脫土奈米複合材料同時添加兩種阻燃劑之特性研究”，國立雲林科技大學環境與安全衛生工程學系，碩士論文，2012。
47.新達精細化學，“紡織品應用材料”，2010，http://www.nu-tech.com.tw/web/blog/2011/05/17/%E7%A3%B7%E7%B3%BB%E9%98%BB%E7%87%83%E5%8A%91%E7%9A%84%E6%87%89%E7%94%A8/
48.Global Chemical Network，間苯二酚四苯基二磷酸酯之化學結構式，http://www.chemnet.com/Products/supplier.cgi?f=pclist;lang=en;site=chemnet;region=;skey=57583-54-7%20tetraphenylmphenylenebis%28phosphate%29;use_cas=1;rand_id=