臺灣博碩士論文加值系統

生物食入塑膠微粒(micro-plastics)，腸胃道不僅遭受到擦傷、阻塞等物理性侵害，還會暴露於塑膠上的化學添加劑。這些化學添加劑涵蓋了所有從水體內吸附、累積到塑膠顆粒上的持久性、生物累積性和毒性化學物質。理解塑膠微粒表面在自然環境中老化的改變，擴展我們對於污染物與海洋塑膠垃圾之間交互作用的知識。微量金屬與疏水性有機化合物的吸(脫)附程度和速度受到海岸環境中，如聚丙烯(PP)和聚氯乙烯(PVC)等吸附劑表面型態的影響，而這些表面型態和化學特性能夠解釋塑料、微生物和汙染物三者之間的交互作用。本研究的主要目的係了解在人工海水中或空氣中的聚丙烯和聚氯乙烯塑膠粒暴露於熱、紫外光和陽光老化一段時日後，化學官能基、形態等表面特性的改變。
為瞭解塑膠廢棄物在自然環境中的老化宿命，本研究利用新鮮的聚丙烯和聚氯乙烯塑膠粒暴露在太陽光、UVB紫外光、熱和人工海水，並以環境掃描式電子顯微鏡(ESEM)，加裝能量分散式光譜儀(EDS)觀測表面形態；另用傅里葉轉換紅外光譜(FTIR)鑑定環境老化後，聚丙烯和聚氯乙烯表面上的化學官能基。
熱和UVB紫外線老化產生特有的聚氯乙烯表面形態。此外，新增的化學官能基證實老化過程歷經脫氯化氫(dehydrochlorination) 和氧化(oxidation)反應機制並且改變了聚氯乙烯的化學特性。然而，無論聚氯乙烯在海水中或沒有在海水中，經過太陽光的暴露老化所產生的不均勻表面，似乎是源自於其表面的降解，且沒有新的化學官能基產生。這表示聚氯乙烯的化學特性在海洋環境中會穩定存在好長的一段時日。
本研究中，太陽光和UVB紫外線老化分別致使聚丙烯表面產生35%和12%的老化裂痕。再者，羰基和羥基在表面生成後逐漸延伸到內部。然而，在光照條件下，PP塑膠粒處於乾燥環境比漂浮在海水有更嚴重的降解程度。當海水中沒有抑菌劑時，生物膜的生成會延緩PP塑膠粒的光降解。研究結果更顯示PP塑膠粒無論在陸地或海洋環境生物食入塑膠微粒(micro-plastics)，腸胃道不僅遭受到擦傷、阻塞等物理性侵害，還會暴露於塑膠上的化學添加劑。這些化學添加劑涵蓋了所有從水體內吸附、累積到塑膠顆粒上的持久性、生物累積性和毒性化學物質。理解塑膠微粒表面在自然環境中老化的改變，擴展我們對於污染物與海洋塑膠垃圾之間交互作用的知識。微量金屬與疏水性有機化合物的吸(脫)附程度和速度受到海岸環境中，如聚丙烯(PP)和聚氯乙烯(PVC)等吸附劑表面型態的影響，而這些表面型態和化學特性能夠解釋塑料、微生物和汙染物三者之間的交互作用。本研究的主要目的係了解在人工海水中或空氣中的聚丙烯和聚氯乙烯塑膠粒暴露於熱、紫外光和陽光老化一段時日後，化學官能基、形態等表面特性的改變。
為瞭解塑膠廢棄物在自然環境中的老化宿命，本研究利用新鮮的聚丙烯和聚氯乙烯塑膠粒暴露在太陽光、UVB紫外光、熱和人工海水，並以環境掃描式電子顯微鏡(ESEM)，加裝能量分散式光譜儀(EDS)觀測表面形態；另用傅里葉轉換紅外光譜(FTIR)鑑定環境老化後，聚丙烯和聚氯乙烯表面上的化學官能基。
熱和UVB紫外線老化產生特有的聚氯乙烯表面形態。此外，新增的化學官能基證實老化過程歷經脫氯化氫(dehydrochlorination) 和氧化(oxidation)反應機制並且改變了聚氯乙烯的化學特性。然而，無論聚氯乙烯在海水中或沒有在海水中，經過太陽光的暴露老化所產生的不均勻表面，似乎是源自於其表面的降解，且沒有新的化學官能基產生。這表示聚氯乙烯的化學特性在海洋環境中會穩定存在好長的一段時日。
本研究中，太陽光和UVB紫外線老化分別致使聚丙烯表面產生35%和12%的老化裂痕。再者，羰基和羥基在表面生成後逐漸延伸到內部。然而，在光照條件下，PP塑膠粒處於乾燥環境比漂浮在海水有更嚴重的降解程度。當海水中沒有抑菌劑時，生物膜的生成會延緩PP塑膠粒的光降解。研究結果更顯示PP塑膠粒無論在陸地或海洋環境，主要的老化機制為光氧化，非熱氧化。
，主要的老化機制為光氧化，非熱氧化。

Marine life which ingests plastic debris may not only undergo physical harm, such as blockage and internal abrasion but is also exposed to chemicals in plastics. To understand the surface alteration and chemical properties of plastic waste degraded in the environment could expand our knowledge of the interaction of marine debris between contaminants and microorganisms. The degree and rate of (de)sorption of hydrophobic organic contaminants (HOCs) and trace metal are affected by the surface characteristics of sorbents, such as eroded polypropylene (PP) and polyvinyl chloride (PVC), in the marine environment. The primary objective of this research is to understand the surface properties such as altered surface functional groups and surface topography of degraded PP and PVC pellets exposed to heat, ultraviolet B (UVB) radiation and solar radiation either in artificial seawater or in air for different period of time.
To understand the fate of plastic waste in the natural environment, fresh polypropylene and PVC pellets were exposed to sunlight, UVB ultraviolet light, heat and artificial seawater in this study. The morphology of eroded PP and PVC was examined using Environmental Scanning Electron Microscope (ESEM), equipped with Spectrometers Energy Dispersion X-ray (EDS). Fourier-transform infrared spectroscopy (FTIR) was used to identify functional groups on the PP and PVC surface after environmental erosion.
Thermal and UVB degradation resulted in characteristic PVC morphologies. In addition, the formation of functional groups was evidence of dehydrochlorination and oxidation during the degradation process which altered the chemical properties of PVC. In contrast, for solar exposure with or without seawater, unevenness of the surface was noted that seems to originate from degradation on the surface of the PVC; in addition, no new functional groups were found. This suggests that the chemical properties of PVC are durable over extended periods in the marine environment.
In this study, solar and UVB degradation resulted in 35% and 12% cracks on the surface of eroded PP pellets, respectively. Furthermore, carbonyl and hydroxyl groups formed on the surface gradually extended to the interior. Nevertheless, under photo-irradiation, PP pellets floating in seawater revealed less degradation than those in a dry environment. The presence of biofilm may delay the photo-degradation of PP pellets in the seawater. Results also demonstrated that the photo oxidation dominated over thermal oxidation during the aging process in the terrestrial and marine environments.

論文審定書 i
誌謝 ii
中文摘要 iv
Abstract vi
Table of Contents viii
List of Figures xii
List of Tables xx
List of abbreviations xxi
Chapter 1 Introduction 1
1.1 Overview of plastic debris in global environments 1
1.2 Effects of plastic waste on organisms 5
1.2.1 Plastic ingestion 5
1.2.2 Plastic entanglement 7
1.2.3 Chemical effects on organisms 8
1.2.4 Ecological effects of biodiversity 11
1.3 Composition and Degradation of Polymers 11
1.3.1 Polymer Composition 11
1.3.2 Polymer Degradation 19
1.3.3 Polyvinyl chloride Degradation 21
1.3.4 Polypropylene Degradation 23
1.4 Aim of the Study 25
1.5 Significance 26
1.6 Relationship to published work 26
Chapter 2 Materials and methods 29
2.1 Materials and sample preparation 29
2.1.1 Materials 29
2.1.1.1 Polyvinyl chloride 29
2.1.1.2 Polypropylene 31
2.1.1.3 Chemicals 32
2.1.1.4 Artificial seawater 32
2.1.2 Weathering experiment 32
2.1.2.1 Degradation of PVC and PP exposed to solar radiation 33
2.1.2.2 Degradation of PVC and PP exposed to ultraviolet B radiation 37
2.1.2.3 Degradation of PVC and PP exposed to high temperatures 37
2.2 Surface and interior characterization 38
2.2.1 Scanning electron microscopes (SEMs) 38
2.2.2 Brunauer–Emmett–Teller (BET) 38
2.2.3 Texture analysis of PVC and PP samples 39
2.3 Fourier transform infrared spectroscopy (FTIR) 40
Chapter 3 Results and Discussion 41
3.1 Polyvinyl chloride 41
3.1.1 Scanning electron microscopy 41
3.1.2 Surface area and porosimetry 53
3.1.3 Fourier transform infrared spectroscopy 55
3.1.4 Environmental implications 61
3.2 Polypropylene 61
3.2.1 Scanning electron microscopy 61
3.2.2 Fourier transform infrared spectroscopy 70
3.2.3 Environmental implications 77
Chapter 4 Conclusions and suggestions 79
4.1 Conclusions 79
4.1.1 Polyvinyl chloride 79
4.1.2 Polypropylene 80
4.2 Suggestions for future works 81
References 83
Appendix 1 100
Appendix 2 106
Appendix 3 116
Appendix 4 132
Curriculum vitae 134