표면 패터닝과 기능기 도입을 통한 고분자 소재의 젖음성 제어 및 유기오염물질 제거 성능 고도화 = Surface Patterning and Functionalization of Polymeric Materials for Wettability Control and Enhanced Organic Pollutant Removal

다국어 초록 (Multilingual Abstract)

Frequent spills of crude oil, organic solvents, and volatile organic compounds (VOCs) caused by industrialization and marine transportation pose serious threats to aquatic ecosystems and human health. Because spilled organic pollutants exhibit diverse behaviors such as dispersion, sedimentation, and volatilization, conventional sorbents, including polypropylene (PP) pads and boom skimmers, show limited efficiency and generate substantial secondary waste. Herein, we present an integrated surface engineering strategy for polymeric films and membranes to enhance adsorption, separation efficiency, and antifouling performance. A micro-patterned polyolefin elastomer (POE) film fabricated via mesh-assisted thermal pressing exhibited increase in effective contact area and more than twice the adsorption rate for toluene and crude oil compared to a flat film. GC–MS analysis confirmed that the recovered oil composition closely matched that of the original crude oil, indicating reusability. To enable rapid response to large-scale spills, a sprayable POE adsorbent using low-toxicity bio-based solvents was developed, achieving ~1.4 times higher oil removal efficiency than commercial PP sorbents. In addition, metal–ligand-mediated surface modification of PVDF membranes produced superhydrophilic and underwater superoleophobic surfaces, enabling 98–99% separation efficiency and high flux for various oil emulsions with excellent long-term stability. These results demonstrate a versatile polymer surface engineering platform for sustainable treatment of organic pollutant spills and oily wastewater.

목차 (Table of Contents)

• 1. Introduction 1
• 1.1. Background 1
• 1.2. Organic Pollutants 3
• 1.3. Mechanisms for Organic Pollutant Removal 4
• 1.3.1. Adsorption 4
• 1.3.2. Absorption 5
• 1.3.3. Separation 5
• 1.4. Factors Affecting Removal Efficiency 7
• 1.4.1. Surface Morphology and Roughness 7
• 1.4.2. Hydrophilicity/Hydrophobicity 8
• 1.4.3. Swelling Behavior and Polymer-solvent Interactions 10
• 1.4.4. Oil/solvent Viscosity Dependence 11
• 2. SurfaceEngineered and Sustainable Polyolefin Sorbents for Efficient Oil and Chemical Spill Remediation 12
• 2.1. SquareWettability Patterned, Recyclable Polyolefin Elastomer Sorbents for Efficient Chemical and Oil Spill Collection 12
• 2.1.1. Introduction 12
• 2.1.2. Experimental Section 15
• 2.1.2.1. Materials 15
• 2.1.2.2. Fabrication of Patterned Films 16
• 2.1.2.3. Fabrication of Fluorescent and Magnetic POE Films 17
• 2.1.2.4. Characterizations 18
• 2.1.2.5. Sorption Capacity of Sorbent Materials 19
• 2.1.2.6. Gravimetric Analysis of Relative Absorption and Dissolution 20
• 2.1.2.7. Film Swelling Ratio Measurement 21
• 2.1.3. Results and Discussion 22
• 2.1.3.1. Fabrication and Characterization of Patterned POE Films 22
• 2.1.3.2. Optimization of Surface Pattern Geometry and Spacing 27
• 2.1.3.3. Effect of Surface Patterning on Organic Chemical Absorption 35
• 2.1.3.4. Swelling Kinetics of Pattern-Engineered POE Films 40
• 2.1.3.5. Functional Versatility of Pattern-Engineered POE Films 44
• 2.1.3.6. Recyclability of Pattern-Engineered POE Films 49
• 2.1.4. Conclusion 54
• 2.2. Sustainable Sprayable Polyolefin Sorbents Enabled by Bio-Solvents for Large Scale Oil and Chemical Spill Recovery 55
• 2.2.1. Introduction 55
• 2.2.2. Experimental Section 57
• 2.2.2.1. Materials 57
• 2.2.2.2. Preparation of Sprayable Adsorbent Solution 58
• 2.2.2.3. Preparation of Magnetic Nanoparticle (MNP) 60
• 2.2.2.4. Preparation of MNP-integrated P/L/C-POE14 Sorbent 61
• 2.2.2.5. Characterizations 62
• 2.2.2.6. Solubility Distance and Relative Energy Difference 63
• 2.2.2.7. Absorption Ratio of VLSFO 64
• 2.2.2.8. Volume Fraction of POE Film 65
• 2.2.2.9. Initial Absorption Rate 66
• 2.2.2.10. Absorption Capacity of Organic Solvent 67
• 2.2.3. Results and Discussion 68
• 2.2.3.1. Chemical Analysis of Bio-based Solvents 68
• 2.2.3.2. Characteristics of POE Film Forming 74
• 2.2.3.3. Optimization of POE Concentration for Spray Application 80
• 2.2.3.4. Evaluation of Sprayable Sorbent Efficiency Under Simulated Spill Conditions 86
• 2.2.4. Conclusion 93
• 3. Metal-Functionalized Surface-Engineered PVDF Membranes for Enhanced Separation and Antifouling Performance 94
• 3.1. Introduction 94
• 3.2. Experimental Section 97
• 3.2.1. Materials 97
• 3.2.2. Preparation of Pristine PVDF Membrane (P-m) 98
• 3.2.3. Fabrication of APTES-Functionalized PVDF Membrane (APTES-m) 99
• 3.2.4. Synthesis of CatecholMetal (Fe/Cu) Coordinated PVDF Membranes (Fe/Cum) 100
• 3.2.5. Characterizations 101
• 3.2.6. Porosity of the Membranes 102
• 3.2.7. Pure Water and Emulsion Flux of the Membrane 103
• 3.2.8. Oil rejection of membrane 104
• 3.2.9. Recyclability of membrane 105
• 3.2.10. Membrane resistance 106
• 3.3. Results and Discussion 107
• 3.3.1. Structural and Chemical Characterization of Membranes 107
• 3.3.2. Surface Wettability and Antifouling Performance 112
• 3.3.3. Oil/Water Separation and Pollutant Removal Performance 116
• 3.3.4. Chemical Stability Evaluation 121
• 3.3.5. Reusability and Long-Term Stability 127
• 3.4. Conclusion 134
• 4. Summary 135
• References 136
• Abstract 153