臺灣博碩士論文加值系統

石化塑膠產品已成為生活中不可或缺的一部分，但石油資源的有限性及廢塑膠對環境之衝擊等問題，皆使塑膠料的回收再利用成為一重要之環保議題；本實驗室先前之研究以常見之聚丙烯(PP)塑膠新料與回收料為樣品，分析不同新料/回收料摻混比例之塑料性質，探討摻混比例與各檢測結果之關係，並建立關係式，惟該研究之新料與回收料來源並不一致，於回收次數上未予以標準化，因此本研究進一步延伸控制回收料之回收次數，並探討不同回收次數與塑料性質之關係。將PP新料依ASTM標準方法射出成型、破碎後，依比例與新料摻混，重複射出成型、破碎、摻混新料之流程至第四次，得不同破碎次數及不同摻混比例之試片，以破碎次數模擬回收次數，對各試片進行塑料性質相關分析及檢測，包括熱性質分析(熔點、黏度、熔融指數)、機械性質分析(衝擊試驗、拉伸試驗)，以及形態學分析(SEM)，並探討破碎次數及摻混比例對PP塑料性質之影響。實驗結果顯示，各試片熔點約為170±2℃(無顯著趨勢)，黏度介於7,870~13,000poise之間(隨轉速提高而減少、隨破碎次數增加而降低、隨舊料摻混比例增加而減少)，熔融指數介於11.28~15.34 g/10min之間(隨破碎次數增加而提高、隨舊料摻混比例增加而增加)，活化能介於23.0~57.6kcal/mol之間(隨破碎次數增加而降低、隨舊料摻混比例提高而降低)，衝擊試驗的衝擊值介於6.05~7.22J/m(無顯著趨勢)，拉伸試驗之楊氏係數介於1878~2608 Mpa之間(隨破碎次數增加而提高、隨舊料摻混比例提高而上升)，SEM照射衝擊試驗之破斷面，結果顯示不同破碎次數之試片皆呈現光滑之破斷表面(無顯著變化)；綜合上述結果，黏度與轉速呈負相關、與破碎次數呈負相關、與舊料摻混比例呈負相關，各試片之熔融指數與破碎次數呈正相關、與舊料摻混比例呈正相關，活化能與破碎次數、舊料摻混比例皆呈負相關，楊氏係數與破碎次數呈正相關、與舊料摻混比例成正相關，熔點及衝擊值受破碎次數與摻混比例之影響並不顯著；迴歸分析方程式可供推估回收次數及摻混比例之參考，各方程式判定係數(R2)皆達0.9以上，整體之研究結果與相關文獻相呼應，可供回收處理相關單位參考。

關鍵詞：熱性質、機械性質、聚丙烯、摻混、消費後塑膠

Petrochemical plastic products have been indispensably part of societies, but the problems caused by limited resources of oils and the impact of waste plastics on environments have drawn attention to recycle and reuse of postconsumer plastics. Previous study has investigated the correlation between virgin/reprocessed polypropylene (PP) chips blending ratio and their physical properties, and establish relationship equations among them. Nonetheless, in that study, the source of the virgin chips was inconsistent with that of the reprocessed material, the number of reprocess times wasn't standardized. Consequently, this study further control the number of reprocess times of the recycled materials, and investigate the relationship between the number of reprocess times and their physical properties. The polypropylene specimens were produced by injection molding according to ASTM standard methods, then crushed and blended with virgin chips with various ratios. The process was repeated until the specimens of the fourth cycle with various blended ratios were obtained. The reprocess cycle in this study is utilized to simulate the number of recycle times in the industry, and based on which to investigate the effects of the number of reprocessed times on the physical properties, including thermal analysis (melt temperature, viscosity, and melt flow index), mechanical properties (impact test and tensile test), and morphology analysis (SEM). The experimental results indicated that the melting peak temperatures of the specimens were in between 170±2℃ (no specific trend observed). The viscosity of the specimens were in between 7,870-13,000 poise, which decreased with increasing rotational speed, reprocessed times, and proportion of reprocessed plastics. The melt flow indexes were in between 11.28-15.34 g/10 min, which increased with increasing reprocess times and proportion of reprocessed plastics. The activation energies (Ea) were in between 23.0-57.6 kcal/mol, which decreased with increasing reprocess times and proportion of reprocessed plastics. The impact strengths were in between 6.05-7.22 J/m (no specific trend observed). The Young’s Modulus (E) were in between 1878-2608 Mpa, which increased with increasing reprocess times and proportion of reprocessed plastics. The result of morphology analysis conducted by SEM revealed decent compatibilities with smooth broken surface among specimens of various reprocessed times, and the distribution characteristics of the specimens did not differ with the blended ratios.
Consolidate the above results, viscosity was negatively correlated with rotational speed, reprocessed times, and the proportion of reprocessed plastics. The melt flow index was positively correlated with the reprocessed times and the proportion of reprocessed plastics. The Ea was negatively correlated with the reprocessed times and the proportion of reprocessed plastics. Young’s Modulus was positively correlated with the reprocessed times and the proportion of reprocessed plastics. Both the melting temperature and impact strength didn't observed any specific trends. The equations obtained from regression analysis can served as reference for estimating the reprocessed times and blending ratios, where the determine coefficient reached higher than 0.9. The overall results of this study are consistent with related literatures, and can serve as reference to relevant organizations.

Keywords: polypropylene, thermal property, mechanical property, blend, postconsumer recycled plastics

目 錄
摘 要 I
Abstract III
誌 謝 VI
目 錄 VII
表目錄 X
圖目錄 XI
第一章 前 言 1
1-1研究緣起 1
1-2研究目的 2
第二章 文獻回顧 3
2-1國內外相關法規 3
2-2聚丙烯(Polypropylene, PP) 7
2-3高分子材料之熱性質 8
2-3-1熔點 (Tm) 8
2-3-2熔融指數(Melt Index) 10
2-3-3黏度(Viscosity) 10
2-3-4熱裂解動力學-Friedman法 11
2-4高分子材料之機械性質 14
2-4-1材料之衝擊 14
2-4-2材料之拉伸 18
2-5型態學(Morphology) 21
第三章 實驗設備與方法 22
3-1材料 22
3-2儀器設備 23
3-3研究流程與實驗方法 27
3-3-1 原料前處理及試片射出成型 29
3-3-2 試片編號及命名 30
3-3-3 熱性質分析 31
3-3-3-1熔點(Tm) 31
3-3-3-2熔融指數(Melt Index) 31
3-3-3-3黏度試驗(Viscosity Test) 31
3-3-3-4熱重分析(Thermal Gravimetric Analysis, TGA) 32
3-3-3-5熱重分析之動力學活化能 32
3-3-4機械性質分析 33
3-3-4-1衝擊試驗(Impact Test) 33
3-3-4-2拉伸試驗(Tensile Test) 33
3-3-5形態學分析 33
第四章 結果與討論 34
4-1原料前處理 34
4-1-1原料製成試片 34
4-1-2射出成型之加工條件設定 37
4-2各試片之熱性質分析 38
4-2-1各試片之熔點(Tm)分析 38
4-2-2各試片之熔融指數檢測結果 40
4-2-3各試片之黏度檢測結果 42
4-2-4各試片之熱重分析結果 48
4-2-5熱重分析之動力學活化能 52
4-3各試片機械性質分析 54
4-3-1各試片之衝擊試驗結果 54
4-3-2各試片之拉伸試驗結果 55
4-4各試片之形態學觀察 60
4-4-1衝擊試驗之破斷面 60
4-4-2拉伸試驗之破斷面 63
4-5摻混比例及破碎次數推估 66
4-5-1摻混比例推估 66
4-5-2破碎次數推估 76
4-5-3方程式演算 82
第五章 結論與建議 88
5-1結論 88
5-2建議 90
參考文獻 91

【1】Miskolczi, N. (2013). Co-pyrolysis of petroleum based waste HDPE, poly-
lactic-acid biopolymer and organic waste. Journal of Industrial and Engineering Chemistry, 19(5), 1549-1559.
【2】行政院環境保護署，統計資料庫。
http://statis91.epa.gov.tw/epa/stmain.jsp?sys=100
【3】嚴萱，(2015)，聚丙烯塑膠回收料與新料混摻比例之驗證研究，國立高雄第一科技大學，碩士論文。
【4】行政院環境保護署，環保法規資料庫。
http://www.epa.gov.tw/lp.asp?ctNode=30596&CtUnit=793&basedsd=7&mp=epa
【5】行政院環境保護署，應回收廢棄物回收清除處理稽核認證作業手冊(廢塑膠容器類)。
【6】財團法人塑膠工業技術發展中心，消費後塑膠再生料驗證資訊網。
http://pcrp.pidc.org.tw/index.php
【7】林建中，高分子材料學：高分子材料機械性質，文京圖書有限公司。
【8】Wesly Wm.,(1991)，熱分析，陳達道譯，國立編譯館，台北。
【9】Chui, J.,(1965), Du Pont Thermogram,2 No3,9.
【10】郭季畇，(2008)，高密度聚乙烯塑膠循環再利用之物理特性評估研究，國立高雄第一科技大學，碩士論文。
【11】林建中，高分子材料性質與應用，高立圖書有限公司。
【12】Doyle, C. D. (1961). Kinetic analysis of thermogravimetric data. Journal of Applied Polymer, 5(15), 285-292.
【13】Friedman, H. L.(1965). Kinetics of thermal degradation of char-forming plastics from thermogravimetry. Application to a Phenolic Plastic, Anal. Chem, 37, 768.
【14】李育德、顏文義、莊祖煌，(1988)，聚合物特性，高立圖書有限公司。
【15】William F.Smith,(2005)，材料科學概論，劉品均，施佑蓉譯，美商麥格羅．希爾國際股份有限公司。
【16】劉國雄等，(2006)，工程材料科學全華科技圖書股份有限公司。
【17】衝擊破壞測試實驗http://memo.cgu.edu.tw/gwo-mei/%E5%8C%96%E6%9D%90HTM/%E5%AF%A6%E9%A9%97%E5%85%AB%20%20%E8%A1%9D%E6%93%8A%E7%A0%B4%E5%A3%9E%E6%B8%AC%E8%A9%A6%E5%AF%A6%E9%A9%97.html
【18】許興旺，鑄品檢測能力本位訓練教材衝擊試驗 編號：PMF-CQC0305。
【19】邱顯堂，(1998)，高分子物性，國立編譯館。
【20】Aurrekoetxea, J., Sarrionandia, M. A., Urrutibeascoa, I., & Maspoch, M. L.(2003). Effects of injection moulding induced morphology on the fracture behavior of virgin and recycled polypropylene. Polymer, 44, 6959-6964.
【21】Dasari, A, Rohrmann, J., &, R. D. K.(2003). Microstructural aspects of surface deformation processes and fracture of tensile strained high isotactic polypropylene. Materials Science and Engineering, 358, 372-383.
【22】羅聖全，研發奈米科技的基本工具之一 電子顯微鏡介紹-SEM，小奈米大世界http://www.materialsnet.com.tw/AD/ADImages/AAADDD/MCLM100/download/equipment/EM/FE-SEM/FE-SEM005.pdf
 
【23】射出成型步驟參考網站
http://sparc.nfu.edu.tw/~changsl/untitled_3.htm
【24】國立台灣工業技術學院化工系編輯小組，”化學技術實習”，民國83年。
【25】劉士榮，高分子材料手冊。
【26】Poulakis, J. G., & Papaspyrides, C. D. (1997). Recycling of polypropylene by the dissolution/reprecipitation technique: I. A model study. Resources, Conservation and Recycling, 20(1), 31
【27】Mehat, N. M., & Kamaruddin, S. (2011). Optimization of mechanical properties of recycled plastic products via optimal processing parameters using the Taguchi method. Journal of Materials Processing Technology, 211(12), 1989–1994.
【28】Cornelissen, T., Yperman, J., Reggers, G., Schreurs, S., & Carleer, R. (2008). Flash co-pyrolysis of biomass with polylactic acid. part 1: Influence on bio-oil yield and heating value. Fuel, 87(7), 1031-1041.
【29】Badia, J., & Strömberg, E. (2012). Material valorisation of amorphous polylactide. Influence of thermo-mechanical degradation on the morphology, segmental dynamics, thermal and mechanical performance. Polymer Degradation and Stability, 97, 670–678.
【30】承耀精密塑膠射出模具網，塑膠射出流程
http://www.mold-ok.com/product-info.asp?id=120