Spectroscopic Techniques for Polymer Characterization

Yukihiro Ozaki obtained his Ph.D. in chemistry in 1978 from Osaka University. Since 1993 he was a professor in the Department of Chemistry, School of Science and Technology until the end of March, 2018. Currently, Ozaki is a professor emeritus of Kwansei Gakuin University. Ozaki's research programs have been concerned with basic studies and applications of far-ultraviolet (FUV), near-infrared (NIR), and far-infrared (FIR)/Terahertz, and Raman spectroscopy. His spectroscopy research covers from basic studies of spectroscopy such as a theory of plasmon-enhanced Raman scattering, the development of new types of instruments like a surface plasmon resonance-NIR spectrometer to applications involving those to polymers, nano materials, and biological samples. Ozaki received several awards including Bomem-Michelson Award (2014), Chemical Society of Japan Award (2017), The Medal with Purple Ribbon from Japanese Emperor (2018), and Pittsburgh Spectroscopy Award (2019).Harumi Sato obtained her Ph.D. from Gunma University in 1996. She was a postdoctoral fellow in the Department of Chemistry, School of Science and Technology, Kwansei Gakuin University during 1999-2012. In 2012, she joined Kobe University as an associate professor of Graduate School of Human Development and Environment of Kobe University. She is currently a full professor of Kobe University since 2018. Her research interest lies in understanding the polymer structure, physical properties, and intermolecular interactions by infrared (IR) spectroscopy, Raman spectroscopy, and terahertz spectroscopy (THz). Her current work focuses on weak hydrogen bonds of biodegradable polymers. She received several awards for her contributions in polymer science and polymer spectroscopy: Award for Encouragement of Research in Polymer Science from the Society of Polymer Science of Japan (2003), Masao Horiba Award (2005).

• List of Contributors xiiiPreface xviiGeneral Introduction xixPart I Recent Progress on Spectroscopic Techniques 11 Polymer Spectroscopy – Spectroscopy from the Far-Ultraviolet to Far-Infrared/Terahertz and Raman Spectroscopy 3Yukihiro Ozaki and Harumi Sato1.1 Introduction to Polymer Spectroscopy 31.1.1 Outline of Polymer Spectroscopy 31.1.2 Brief History of Polymer Spectroscopy 51.2 Overview of Molecular Spectroscopy from the Far-Ultraviolet to Far-Infrared/Terahertz and Raman Spectroscopy in Polymer Research 61.2.1 IR and Raman Spectroscopy Analyses 61.2.2 FIR/Terahertz and Low-Frequency Raman Spectroscopy 81.2.3 Near-Infrared (NIR) Spectroscopy 81.2.4 SERS and TERS Spectroscopy 91.2.5 FUV Spectroscopy 91.3 Specific Examples of Molecular Spectroscopy Studies of Polymers 101.3.1 Infrared, Raman, and NIR Spectroscopic Evidence for the Coexistence of Hydrogen Bond Types in Poly(Acrylic Acid) 101.3.2 Low-Frequency Vibrational Modes of Nylon-6 Studied by Using IR and Raman Spectroscopies and Density Functional Theory Calculations 161.3.3 NIR Spectra of Linear Low-Density Polyethylene and Their Chemometrics Analysis 211.3.4 Study of the Crystallization Behavior of Asymmetric PLLA/PDLA Blend by IR and Raman Spectroscopy and Raman Imaging 231.3.5 3D SERS Imaging Using Chemically Synthesized Highly Symmetric Nanoporous Silver Microparticles 281.3.6 Tip-Enhanced Raman Scattering Spectroscopy Study of Local Interactions at the Interface of Styrene–Butadiene Rubber/Multiwalled Carbon Nanotube Nanocomposites 341.4 Perspectives for Polymer Spectroscopy 39References 412 FTIR Spectroscopy and Spectroscopic Imaging for the Analysis of Polymers and Multicomponent Polymer Systems 45Huiqiang Lu, Andrew V. Ewing, and Sergei G. Kazarian2.1 Investigation of Polymers Using FTIR Spectroscopy and Spectroscopic Imaging 452.1.1 Investigation of Miscibility in Polymer Blends 462.1.2 Investigation of Intermolecular Interactions 472.1.2.1 Investigation of Partially Miscible PMMA–PEG Blends Using Two-Dimensional Disrelation Mapping 482.1.3 Investigation of Crystallization in Polymers 512.1.3.1 Investigation of Solvent-Induced Crystallization in Polymers 512.1.3.2 Investigation of the Crystallization Process of PHB, PLLA, and Their Blends 532.2 Investigation of Polymers Subjected to High-Pressure or Supercritical CO2 Using FTIR Spectroscopy and FTIR Spectroscopic Imaging 552.2.1 Morphology of Polymeric Materials under High-Pressure or Supercritical CO2 562.2.2 Investigation of Interaction in Polymers under High-Pressure or Supercritical CO2 592.2.2.1 Investigation of the Effect of High-Pressure CO2 on the H-Bonding in PEG–PVP Blends 602.2.2.2 Investigation of the Mechanism of Interaction between CO2 and Polymers through the Thermodynamic Parameters Produced from In Situ ATR–FTIR Spectroscopy 612.2.3 Investigation of Crystallization in Polymers under High-Pressure or Supercritical CO2 612.2.4 The Investigation of Structural Changes and Crystallization Kinetics of Polymers Exposed to High-Pressure CO2 through In Situ High-Pressure FTIR and FT-Raman Spectroscopy 642.2.5 Investigation of Swelling and CO2 Sorption into the Polymers under High-Pressure or Supercritical CO2 652.3 Conclusion 67References 683 Interfaces in Polymer Nanocomposites Characterized by Spectroscopic Techniques 75Liliane Bokobza3.1 Introduction 753.2 Types of Interactions at the Interface 763.3 Characterization of the Interfaces 803.3.1 Fluorescence Spectroscopy 823.3.2 Solid-State NMR Spectroscopy 853.3.3 Vibrational Spectroscopy 883.3.3.1 Infrared Spectroscopy 893.3.3.2 Raman Spectroscopy 913.4 Conclusions 95References 964 Far-Infrared/Terahertz and Low-Frequency Raman Spectroscopies in Polymers 107Harumi Sato4.1 Introduction 1074.2 Intermolecular Hydrogen Bonds in the Low-Frequency Region of PHB by QCCs 1084.3 Several Types of Intermolecular Hydrogen Bonds in PCL 1094.4 Stress-Induced Crystal Transition of Polybutylene Succinate (PBS) 1134.5 The Differences in Intermolecular Hydrogen Bonding Between PET and PBT 1154.6 THz Imaging of Polymer Film 1174.7 Conclusions 120References 1205 Near-Infrared Spectroscopy and Imaging of Polymers 125Daitaro Ishikawa, Yuta Hikima, and Yukihiro Ozaki5.1 Introduction to NIR Spectroscopy 1255.1.1 Principles of NIR Spectroscopy 1255.1.2 Characteristics and Advantages of NIR Spectroscopy 1265.1.3 Analysis of NIR Spectra 1265.2 Applications to Polymer Science and Engineering of NIR Spectroscopy 1285.2.1 Polarized NIR Spectroscopy Studies of Molecular Orientation of Polymers 1285.2.2 Isothermal Crystallization Kinetics of Poly(3-hydroxybutyrate) 1345.2.3 Crystallization of Poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) During Melt Extrusion Promoted by Residual Crystals 1405.2.3.1 Outline of Online NIR Analysis and Online NIR Monitoring of the Residual Crystal Amount at the Extruder Outlet Nozzle 1405.2.3.2 Amount of Residual Crystals at the Extruder Outlet 1415.2.3.3 Crystallization of Extruded Strands 1455.2.3.4 Analysis of Extruded Strand Crystallization Using the Avrami Equation 1465.3 NIR Imaging for Polymer Sciences 1485.3.1 Introduction 1485.3.2 Theory of NIR Imaging 1485.3.2.1 Acquisition of Hypercube 1485.3.2.2 Data Transfer and Mapping 1495.3.2.3 Feature of NIR Imaging Devices 1505.3.3 Applications of NIR Imaging 1515.3.3.1 Monitoring of Crystal Evolution Combined with Chemometrics 1515.3.3.2 Quality Evaluation Potential for Wide Area 1535.3.3.3 Diffusion Process Monitoring 1535.3.3.4 Degradable Process Monitoring of Biodegradable Polymer 1545.3.3.5 Rapid Evaluation of the Water Content in PLA Pellets 1565.3.3.6 Nondestructive Detection of Degraded Polylactic Acid Moldings 157References 1606 Far Ultraviolet Spectroscopy for Polymers 165Yusuke Morisawa and Nami Ueno6.1 Introduction 1656.2 Measurement of ATR–FUV Spectra of Polymer 1666.3 ATR–FUV Spectra of Nylons 1676.4 ATR–FUV Spectra of Poly(3-hydroxybutyrate) (PHB) and Its Graphene Nanocomposites 1726.5 ATR–FUV Study of Poly(ethylene glycol) (PEG) and Its Complex with Lithium Ion (Li+) 1766.6 Summary 181References 1817 Synchrotron-Based UV Resonance Raman Spectroscopy for Polymer Characterization 183Barbara Rossi, Mariagrazia Tortora, Sara Catalini, Alessandro Gessini, and Claudio Masciovecchio7.1 Basic Principles of Raman and UV Resonance Raman Spectroscopy 1837.1.1 Molecular Vibrations and Raman Effect 1837.1.2 Resonance Raman (RR) Scattering 1917.1.3 Fundamental Applications of UV Resonance Raman Spectroscopy 1937.2 Synchrotron-Based UV Resonance Raman: Basic Principles and Instrumentation 1937.2.1 Synchrotron-Based UVRR Setup on IUVS@Elettra 1947.3 SR-UVRR Characterization of Biopolymers 1977.4 UV Resonance Raman Studies on Polymeric Hydrogels 2037.4.1 Water Confinement in Polysaccharide Hydrogels 2047.4.2 Phase Transition in Thermo-Sensitive Polysaccharide Hydrogels 2087.4.3 Water and Polymer Dynamics in pH-Responsive Polysaccharide Hydrogels 2127.5 Conclusions 215Acknowledgment 217References 2178 Sum Frequency Generation Spectroscopy for Understanding the Polymer Dynamics at Buried Interfaces 227Daisuke Kawaguchi and Keiji Tanaka8.1 Introduction 2278.2 Principle 2288.3 Examples 2308.3.1 Nonsolvent Interface 2308.3.1.1 Polystyrene 2308.3.2 Solid Interface 2388.3.2.1 Polystyrene 2388.3.2.2 Polyisoprene 2408.3.2.3 Poly(styrene-co-butadiene) Rubber [89] 2448.4 Conclusions 250Acknowledgements 251References 2519 Application of Two-Dimensional Correlation Spectroscopy (2D-COS) in Polymer Studies 259Yeonju Park, Isao Noda, and Young Mee Jung9.1 Introduction 2599.2 Theory 2609.2.1 Background 2609.2.2 Properties of 2D-COS 2609.3 Applications of 2D-COS in Polymer Studies 2619.3.1 Applications of Conventional 2D-COS 2619.3.1.1 Biodegradable Polymers 2619.3.1.2 Thermo-Responsive Polymers 2629.3.2 2D Hetero-Spectral Correlation Analysis 2679.3.3 Two-Dimensional (2D) Gradient-Mapping Method 2699.3.4 Chemometric Techniques Combined with 2D-COS 2709.3.5 Smooth Factor Analysis 2729.3.6 Projection 2D-COS 2759.3.7 2D-COS for Hyperspectral Imaging 2789.4 Conclusions 284References 28410 Molecular Dynamics in Polymer Science 297Mateusz Z. Brela, Marek Boczar, and Marek J. Wójcik10.1 Introduction 29710.2 Historical and Theoretical Background 29910.3 Applications 30210.3.1 Vibrational Spectra of Hydrogen-Bonded Polymers 30310.3.2 Studies of Interactions between Polymers and Water 30410.3.3 Mechanical Properties of Polymers 30610.3.4 Interphase Interactions 30710.4 Summary and Perspectives 309Acknowledgment 311References 31111 Spectroscopic Analysis of Structural Transformations Associated with Poly(lactic acid) 317Shaw L. Hsu and Xiaozhen Yang11.1 Introduction 31711.2 Spectroscopic Tools 31911.2.1 Vibrational Features of PLA Crystals 32111.2.2 Analysis of Disordered PLA Chains 32311.2.3 Description of Anisotropic PLA – Polarized Spectra 32711.3 Simulation Studies for both Ordered and Disordered Structures 32911.4 Analysis of Conformational Changes in PLA during Deformation 33411.5 Aging Behavior in PLA 33811.6 Conclusion 340Acknowledgment 340References 340Part II Topical Polymers Studied by Spectroscopy 34512 Probing Molecular Events in Self-Healable Polymers 347Qianhui Liu, Lei Li, and Marek W. Urban12.1 Introduction 34712.2 Microphase Separation 34912.3 Entropically Driven Self-Healing 35312.3.1 Free Radical and Cationic Recombination 35512.3.2 Van der Waals Interactions 36012.3.3 Chemical Sensing of Damage–Repair Cycle 361Acknowledgments 365References 36513 Recent Application of Vibrational Spectroscopy to Conjugated Conducting Polymers 367Yukio Furukawa13.1 Introduction 36713.2 Carriers 36913.3 Optical Absorption Spectra upon Chemical Doping 37113.3.1 P3HT 37113.3.2 Poly(2,5-bis(3-hexadecylthiophene-2-yl)thieno[3,2-b]thiophene)(PBTTT-C16) 37213.4 Raman Spectra of Positive Polarons and Bipolarons Generated Upon Chemical Doping 37413.4.1 P3HT 37413.4.2 PBTTT-C16 37513.5 Carriers and Electrical Properties Based on ILGTs 37713.5.1 ILGTs 37713.5.2 Raman Spectra of ILGTs Fabricated with P3HT 37813.5.3 Raman Spectra of ILGTs Fabricated with PBTTT-C16 38013.6 Carrier Mobilities 38313.7 Raman Images in the Channel Region 38313.8 Carrier Dynamics in Bulk Heterojunction Films 38613.8.1 Photoexcitation Dynamics on Femto- and Picosecond Time Scales 38613.8.2 Microsecond Recombination Dynamics of Long-Lived Carriers 38713.9 Conclusions 388References 38814 Vibrational Spectroscopy for Fluoropolymers and Oligomers 393Takeshi Hasegawa14.1 Perfluoroalkyl-Containing Compounds 39314.1.1 Molecular Conformation on Phase Diagram 39314.1.2 Molecular Vibration of an Rf Group 39614.1.3 The SDA theory 40014.2 Spectroscopy for Rf Compounds 40214.2.1 ROA analysis of Rf Compounds 40214.2.2 Surface Modes of Phonon and Polariton 40514.2.3 Summary and Perspective 408References 40915 Probing Structures of Conductive Polymers with Vibrational Spectroscopy 413Jianming Zhang and Yuan Yuan15.1 Introduction 41315.2 Application of Vibrational Spectroscopy 41315.2.1 Chain Packing/Aggregate Mode Identification 41315.2.2 Conformation-Sensitive Bands Identification 41415.2.3 Doping-Sensitive Bands Identification 41515.2.4 Thermally Induced Phase Transitions 41715.2.5 Structural Dynamics 41815.2.6 Chemical Composition/Morphology Analysis in Conductive-Polymer-Based Blends 42015.2.7 Surface/Interface Molecular Orientation 42315.2.8 Structure and Dynamics of Charge Carriers 42515.2.9 Electric-Field-Induced Structural Changes 42915.3 Conclusion 431References 43116 Weak Hydrogen Bonding in Biodegradable Polymers 435Harumi Sato16.1 Introduction 43516.2 Weak Hydrogen Bonding in Poly(3-hydroxybutyrate) 43616.3 Comparison between Weak and Strong Hydrogen Bonds 43816.4 Difference in the Side Chain Length; PHB and PHV 43916.5 Polyhydroxyalkanoate Copolymers 44216.6 Crystallization Process of PHB 44316.7 Other Kinds of CH⋅⋅⋅O Hydrogen Bonding 44316.8 Conclusions 447References 449Index 453