Spectroscopic Techniques for Polymer Characterization E-Book
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- Herausgeber: Wiley-VCH GmbH
- Kategorie: Wissenschaft und neue Technologien
- Sprache: Englisch
An insightful exploration of cutting-edge spectroscopic techniques in polymer characterization
In Spectroscopic Techniques for Polymer Characterization: Methods, Instrumentation, Applications, a team of distinguished chemists delivers a comprehensive exploration of the vast potential of spectroscopic characterization techniques in polymer research. The book offers a concise outline of the principles, advantages, instrumentation, experimental techniques, and noteworthy applications of cutting-edge spectroscopy.
Covering a wide range of polymers, from nylon to complex polymeric nanocomposites, the author presents recent developments in polymer science to polymer, analytical, and material chemists, assisting them in keeping track of the progress in modern spectroscopy.
Spectroscopic Techniques for Polymer Characterization contains contributions from pioneers in modern spectroscopic techniques from around the world. The included materials bridge the gap between spectroscopists, polymer scientists, and engineers in academia and industry. The book also offers:
- A thorough introduction to the progress in spectroscopic techniques, including polymer spectroscopy and near-infrared spectroscopy
- Comprehensive explorations of topical polymers studied by spectroscopy, including polymer thin films, fluoropolymers, polymer solutions, conductive polymers
- Practical discussions of infrared imaging, near-infrared imaging, two-dimensional correlation spectroscopy, and far-ultraviolet spectroscopy
- In-depth examinations of spectroscopic studies of weak hydrogen bonding in polymers
Spectroscopic Techniques for Polymer Characterization: Methods, Instrumentation, Applications is a must-read reference for polymer, analytical, and physical chemists, as well as materials scientists and spectroscopists seeking a one-stop resource for polymer characterization using spectroscopic analyses.
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Veröffentlichungsjahr: 2021
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Table of Contents
Cover
Title Page
Copyright
List of Contributors
Preface
General Introduction
Part I: Recent Progress on Spectroscopic Techniques
1 Polymer Spectroscopy – Spectroscopy from the Far‐Ultraviolet to Far‐Infrared/Terahertz and Raman Spectroscopy
1.1 Introduction to Polymer Spectroscopy
1.2 Overview of Molecular Spectroscopy from the Far‐Ultraviolet to Far‐Infrared/Terahertz and Raman Spectroscopy in Polymer Research
1.3 Specific Examples of Molecular Spectroscopy Studies of Polymers
1.4 Perspectives for Polymer Spectroscopy
References
2 FTIR Spectroscopy and Spectroscopic Imaging for the Analysis of Polymers and Multicomponent Polymer Systems
2.1 Investigation of Polymers Using FTIR Spectroscopy and Spectroscopic Imaging
2.2 Investigation of Polymers Subjected to High‐Pressure or Supercritical CO2 Using FTIR Spectroscopy and FTIR Spectroscopic Imaging
2.3 Conclusion
References
3 Interfaces in Polymer Nanocomposites Characterized by Spectroscopic Techniques
3.1 Introduction
3.2 Types of Interactions at the Interface
3.3 Characterization of the Interfaces
3.4 Conclusions
References
4 Far‐Infrared/Terahertz and Low‐Frequency Raman Spectroscopies in Polymers
4.1 Introduction
4.2 Intermolecular Hydrogen Bonds in the Low‐Frequency Region of PHB by QCCs
4.3 Several Types of Intermolecular Hydrogen Bonds in PCL
4.4 Stress‐Induced Crystal Transition of Polybutylene Succinate (PBS)
4.5 The Differences in Intermolecular Hydrogen Bonding Between PET and PBT
4.6 THz Imaging of Polymer Film
4.7 Conclusions
References
5 Near‐Infrared Spectroscopy and Imaging of Polymers
5.1 Introduction to NIR Spectroscopy
5.2 Applications to Polymer Science and Engineering of NIR Spectroscopy
5.3 NIR Imaging for Polymer Sciences
References
6 Far Ultraviolet Spectroscopy for Polymers
6.1 Introduction
6.2 Measurement of ATR–FUV Spectra of Polymer
6.3 ATR–FUV Spectra of Nylons
6.4 ATR–FUV Spectra of Poly(3‐hydroxybutyrate) (PHB) and Its Graphene Nanocomposites
6.5 ATR–FUV Study of Poly(ethylene glycol) (PEG) and Its Complex with Lithium Ion (Li+)
6.6 Summary
References
7 Synchrotron‐Based UV Resonance Raman Spectroscopy for Polymer Characterization
7.1 Basic Principles of Raman and UV Resonance Raman Spectroscopy
7.2 Synchrotron‐Based UV Resonance Raman: Basic Principles and Instrumentation
7.3 SR‐UVRR Characterization of Biopolymers
7.4 UV Resonance Raman Studies on Polymeric Hydrogels
7.5 Conclusions
Acknowledgment
References
8 Sum Frequency Generation Spectroscopy for Understanding the Polymer Dynamics at Buried Interfaces
8.1 Introduction
8.2 Principle
8.3 Examples
8.4 Conclusions
8.4 Acknowledgements
References
9 Application of Two‐Dimensional Correlation Spectroscopy (2D‐COS) in Polymer Studies
9.1 Introduction
9.2 Theory
9.3 Applications of 2D‐COS in Polymer Studies
9.4 Conclusions
References
10 Molecular Dynamics in Polymer Science
10.1 Introduction
10.2 Historical and Theoretical Background
10.3 Applications
10.4 Summary and Perspectives
Acknowledgment
References
11 Spectroscopic Analysis of Structural Transformations Associated with Poly(lactic acid)
11.1 Introduction
11.2 Spectroscopic Tools
11.3 Simulation Studies for Both Ordered and Disordered Structures
11.4 Analysis of Conformational Changes in PLA During Deformation
11.5 Aging Behavior in PLA
11.6 Conclusion
Acknowledgment
References
Part II: Topical Polymers Studied by Spectroscopy
12 Probing Molecular Events in Self‐Healable Polymers
12.1 Introduction
12.2 Microphase Separation
12.3 Entropically Driven Self‐Healing
Acknowledgments
References
13 Recent Application of Vibrational Spectroscopy to Conjugated Conducting Polymers
13.1 Introduction
13.2 Carriers
13.3 Optical Absorption Spectra Upon Chemical Doping
13.4 Raman Spectra of Positive Polarons and Bipolarons Generated Upon Chemical Doping
13.5 Carriers and Electrical Properties Based on ILGTs
13.6 Carrier Mobilities
13.7 Raman Images in the Channel Region
13.8 Carrier Dynamics in Bulk Heterojunction Films
13.9 Conclusions
References
14 Vibrational Spectroscopy for Fluoropolymers and Oligomers
14.1 Perfluoroalkyl‐Containing Compounds
14.2 Spectroscopy for Rf Compounds
References
15 Probing Structures of Conductive Polymers with Vibrational Spectroscopy
15.1 Introduction
15.2 Application of Vibrational Spectroscopy
15.3 Conclusion
References
16 Weak Hydrogen Bonding in Biodegradable Polymers
16.1 Introduction
16.2 Weak Hydrogen Bonding in Poly(3‐hydroxybutyrate)
16.3 Comparison Between Weak and Strong Hydrogen Bonds
16.4 Difference in the Side Chain Length; PHB and PHV
16.5 Polyhydroxyalkanoate Copolymers
16.6 Crystallization Process of PHB
16.7 Other Kinds of CH···O Hydrogen Bonding
16.8 Conclusions
References
Index
End User License Agreement
List of Tables
Chapter 4
Table 4.1 Donor–acceptor interaction energies for the model in Figure 4.5a,b...
Chapter 5
Table 5.1 Frequency, assignment, local symmetry, and dichroism of the charac...
Table 5.2 Avrami parameters calculated from the normalized PC1 scores of fiv...
Table 5.3 Detailed extrusion conditions.
Table 5.4 Results of visual observation of strands.
Table 5.5 Avrami parameters calculated from the crystallization dynamics ana...
Chapter 6
Table 6.1 Values of slope (coordination numbers) and intercept with error ra...
Chapter 7
Table 7.1 Schematic representation of the main molecular vibrational motions...
Table 7.2 Characteristic vibrational frequencies of some molecular groups fo...
Table 7.3 Assignment of the prominent Raman bands of DNA observed in the UVR...
Chapter 13
Table 13.1 Highest mobilities of positive polarons and bipolarons.
List of Illustrations
Chapter 1
Figure 1.1 The region of electromagnetic wave from 200 nm to 1 mm.
Figure 1.2 Four possible hydrogen‐bonding arrangements of the carboxylic aci...
Figure 1.3 FT‐IR spectra of PAA measured from 40 to 140 °C (10 °C intervals ...
Figure 1.4 FT‐IR spectra of PAA in the C = O stretching region measured at (...
Figure 1.5 An FT‐Raman spectrum of PAA measured at 64 °C.
Figure 1.6 Enlarged Raman spectrum of PAA between 1850 and 1550 cm
−1
s...
Figure 1.7 FT‐NIR spectra of PAA measured from 40 to 140 °C (in 10 °C interv...
Figure 1.8 (a) FIR spectra of nylon‐6 in the α‐form measured from 29 to 194 ...
Figure 1.9 Temperature dependence of the FIR intensity of nylon‐6 at (a) 294...
Figure 1.10 (a) Raman spectra of nylon‐6 in the α‐form collected at 22, 90, ...
Figure 1.11 (a) Polarized Raman and (b) FIR spectra of nylon‐6 in the α‐form...
Figure 1.12 Comparisons of the experimental (top) and calculated (bottom) (a...
Figure 1.13 Atomic motion of the FIR active modes of nylon‐6 in the α‐form c...
Figure 1.14 Calculated (a) Raman and (b) FIR spectra of nylon‐6 in the α‐for...
Figure 1.15 (a) A NIR DR spectrum of LLDPE sample and (b) that of PE.
Figure 1.16 NIR spectra of the 16 kinds of LLDPE and PE investigated (a) bef...
Figure 1.17 Second derivative of the NIR spectra shown in Figure 1.16a.
Figure 1.18 Score plot of PCA factors 1 and 2 for the 16 kinds of LLDPE and ...
Figure 1.19 A PC weight‐loadings plot of factor 1 for the score plot shown i...
Figure 1.20 Loadings plot of regression coefficients for the PLS calibration...
Figure 1.21 Time‐dependent IR spectra of asymmetric PLLA/PDLA 4/1 blend, whi...
Figure 1.22 Time‐dependent variations of IR band intensity of SC at 908 cm
−1
...
Figure 1.23 POM images of the asymmetric blend sample of PLLA/PDLA (4 : 1) c...
Figure 1.24 (a) Optical image of the blend sample after isothermal crystalli...
Figure 1.25 (a) Curve‐fitting results in the 800 to 600 cm
−1
region at...
Figure 1.26 Schematic illustrations of isothermal crystallization process of...
Figure 1.27 SEM images of nanoporous silver microstructures showing (a) the ...
Figure 1.28 (a) SERS spectrum of PATP from the center of a hexapodal silver ...
Figure 1.29 A silver microparticle in a PHB/PDLLA polymer blend. (a) An opti...
Figure 1.30 (a) Scheme showing a silver particle embedded in double‐layered ...
Figure 1.31 Chemical structure of SBR.
Figure 1.32 Raman spectra of (a) pure SBR, (b) pure MWCNTs, and (c) 1 parts ...
Figure 1.33 (a) Raman and (b) TERS spectra of 1 phr SBR/MWCNT nanocomposites...
Figure 1.34 Enlarged TERS spectra of 1 phr SBR/MWCNTs from Figure 1.33: (a) ...
Figure 1.35 Peak intensity plots of (a) the vinyl band (2990 cm
−1
) vs....
Figure 1.36 Schematic diagram of the surface structure of SBR/MWCNT nanocomp...
Chapter 2
Figure 2.1 Spinodal curves of the PHB/PLA blends with different
M
w
calculate...
Figure 2.2 (a) Visual image, PLA‐specific FTIR image, and PHB‐specific FTIR ...
Figure 2.3 A schematic illustration of disrelation mapping based on 2D corre...
Figure 2.4 ATR–FTIR images of PMMA/PEG‐2000000 blends (a, b) and PMMA/PEG‐20...
Figure 2.5 Disrelation maps of (a) PMMA/PEG‐2000000 and (b) PMMA/PEG‐2000 bl...
Figure 2.6 FTIR spectra of (a) an amorphous s‐PS film and (b) a δ‐crystallin...
Figure 2.7 FTIR images based on the distribution of the integrated absorbanc...
Figure 2.8 (a) FTIR spectra and (b) difference spectra of PLLA during the co...
Figure 2.9 Synchronous (a) and asynchronous (b) correlation spectra of PLLA ...
Figure 2.10 ATR–FTIR spectroscopic images of the PS/PVME blend before (a, c)...
Figure 2.11 ATR–FTIR spectroscopic images of the PMMA/PEO interface. The ima...
Figure 2.12 (a) ATR–FTIR spectroscopic images of the PCL/PLA blend at 30 °C ...
Figure 2.13 (a) FTIR spectrum and (b) its second derivative in the
ν
(C ...
Figure 2.14 ATR–FTIR spectra of noninteracting CO
2
sorbed by polybutadiene (...
Figure 2.15 The schematic for the formation of CO
2
–polymer complexes.
Figure 2.16 Schematic of the in situ ATR–FTIR spectroscopy to study the CO
2
...
Chapter 3
Figure 3.1 Near‐infrared spectra of silica‐filled PDMS networks. Each curve ...
Figure 3.2 Raman spectra (780.6 nm excitation) of (a) pristine SWCNTs, (b) f...
Figure 3.3 Oxidation of graphene sheet to form graphene oxide.
Figure 3.4 Mooney–Rivlin plots for: (a) unfilled poly(dimethylsiloxane) (PDM...
Figure 3.5
T
g
data from bulk polymer and polymer nanocomposites determined t...
Figure 3.6
Photoluminescence
(
PL
) spectra of (a) CHE (in situ nanocomposite)...
Figure 3.7 Synthesis procedure of luminescent PDMS/carbon dot nanocomposite ...
Figure 3.8 Fits to the free induction decay with two or three components for...
Figure 3.9 Different relaxation components for rubber filled with grafted si...
Figure 3.10 Synchronous (a) and asynchronous (b) correlation spectra derived...
Figure 3.11 (A) FTIR spectra of hardener (red) and cured epoxy resin (blue);...
Figure 3.12 Deconvoluted Raman spectrum of a graphite of grade 4124 from Asb...
Figure 3.13 Comparison between the dispersive behavior of graphite and multi...
Figure 3.14 Dependence of the 2D Raman band position upon strain during the ...
Chapter 4
Figure 4.1 Chemical structure and weak hydrogen bondings between CH
3
and C=O...
Figure 4.2 Polarized THz spectra of PHB measured using stretched PHB film. T...
Figure 4.3 Temperature‐dependent THz absorption spectra of PHB.
Figure 4.4 (a) Temperature‐dependent THz spectra of PCL in the temperature r...
Figure 4.5 Model structures of PCL used for the NBO calculations. The struct...
Figure 4.6 The calculated (bottom) and experimental (top) THz spectra of PCL...
Figure 4.7 (a) THz and (b) low‐frequency Raman spectra of PBS during heating...
Figure 4.8 THz polarization spectra of PBS at room temperature with several ...
Figure 4.9 The temperature‐dependent THz spectra and their second derivative...
Figure 4.10 The temperature‐dependent low‐frequency Raman spectra of (a) PET...
Figure 4.11 A visible image 2 cm
2
PCL film and its corresponding THz imaging...
Figure 4.12 The THz images of (a) as‐pressed PCL film and (b) after melt rem...
Figure 4.13 The THz images of (a) the sample is placed at 90° to the THz wav...
Chapter 5
Figure 5.1 Experimental and calculated NIR spectra of low‐concentration (5 ×...
Figure 5.2 (a) The IR spectrum of a PDMS film of 125 μm in thickness and (b)...
Figure 5.3 (a) Positions of local chain axis and transition moment with resp...
Figure 5.4 Strain dependence of the dichroic difference spectra for a silica...
Figure 5.5 (a) and (b) dichroic functions versus strain function for unfille...
Figure 5.6 (a) and (b) Time‐dependent changes of the NIR spectra in the regi...
Figure 5.7 (a) Normalized PC1 score plot (*) obtained from the NIR differenc...
Figure 5.8 Top and bottom panels depict Avrami plots of the crystallization ...
Figure 5.9 Molecular structure of poly(3‐hydroxybutyrate‐
co
‐3‐hydroxyhexanoa...
Figure 5.10 Chemical structure of poly(3‐hydroxybutyrate‐
co
‐3‐hydroxyhexanoa...
Figure 5.11 A NIR spectrum in the 11 000 to 4000 cm
−1
region of Experi...
Figure 5.12 Enlargements of online NIR spectra in the (a) 4800 to 4600 cm
−1
...
Figure 5.13 Difference spectra calculated using Exp‐4 as the reference in th...
Figure 5.14 Time‐dependent variations in the second‐derivative spectra measu...
Figure 5.15 Time‐dependent variations of the NIR spectra of the extruded str...
Figure 5.16 Temporal intensity changes of the peak at 5129 cm
−1
in the...
Figure 5.17 Schematic diagram of NIR imaging measurement and acquisition of ...
Figure 5.18 Outline view of the imaging instrument, including the developed ...
Figure 5.19 Score images of PHB/PLLA blends derived from PLSR. PHB/PLLA (a) ...
Figure 5.20 (a) Photos of stretched sample of PLA and (b) NIR images for cry...
Figure 5.21 FT‐NIR images based on the integrated
ν
(NH) + amide II abso...
Figure 5.22 Images of samples subjected to UV‐irradiation for crystalline/am...
Figure 5.23 NIR images of the water content of (a) dried, (b) undried, and w...
Figure 5.24 NIR spectra of PLA with different molding conditions. (a) KM‐tra...
Figure 5.25 NIR images of the (a) flexural strength, (b) flexural strain, (c...
Chapter 6
Figure 6.1 Chemical structures of (a) nylon‐6, (b) nylon‐11, (c) nylon‐12, (...
Figure 6.2 (a) ATR–FUV spectra of nylon‐6, ‐11, ‐12, ‐6/6, and ‐6/12, and li...
Figure 6.3 Correlation between average alkyl chain and intensity ratio of
I
1
...
Figure 6.4 (a) Tr–FUV spectra of nylon‐6, ‐11, ‐12, ‐6/6, and ‐6/12 in cast ...
Figure 6.5 Peak position of band near 195 nm of Tr spectra vs. that of band ...
Figure 6.6 Calculated spectra of model compounds of nylon‐6, ‐11, and ‐12 in...
Figure 6.7 Computational trimer models of hydrogen bonded systems for (a) ny...
Figure 6.8 Distributions of π–π* transitions with relatively strong (
f
≥ 0.1...
Figure 6.9 Typical MOs relevant to π–π* transition in trimer model of nylon‐...
Figure 6.10 Graphene‐concentration‐dependent ATR–FUV–DUV spectra of PHB and ...
Figure 6.11 Simulated (TD–CAM‐B3LYP/aug‐cc‐pVDZ) FUV–DUV spectra of (a) α‐cr...
Figure 6.12 ATR–FUV spectra in 145–200 nm wavelength region for
diethylene g
...
Figure 6.13 Dependence of absorbance on concentration of Li
+
for mixture...
Figure 6.14 (a) Band shift (
δλ
) of three bands at 155, 163, 177 nm...
Figure 6.15 Complex structure models of (a) Int 1, (b) Int 2, and (c) Int 3....
Figure 6.16 Simulation spectra of neat PEG and complexes (Int 1, Int 2, and ...
Figure 6.17 Plots of intensity ratio (log([
A
]/[
A
0
])) vs. concentration ratio...
Chapter 7
Figure 7.1 Graphical representation of the molecular vibration in terms of t...
Figure 7.2 Representation of the quantized vibrational energy: vibrational e...
Figure 7.3 Infrared absorption spectra of formamide and
N,N
‐dimethylformamid...
Figure 7.4 Virtual energy diagram representing the elastic and the two inela...
Figure 7.5 Raman spectra of formamide and
N,N‐
dimethylformamide obtain...
Figure 7.6 Virtual energy diagram representing the Raman and resonance Raman...
Figure 7.7 Resonance Raman spectra of formamide and
N,N
‐dimethylformamide co...
Figure 7.8 Technical layout of the synchrotron‐based UVRR setup at BL10.2‐IU...
Figure 7.9 Radiation wavelength as a function of the gap aperture for Figure...
Figure 7.10 Image on the CCD of the elastic peak for 250 nm of excitation wa...
Figure 7.11 Example of experimental setup developed on IUVS@Elettra for in s...
Figure 7.12 Steps of the formation of sDNA/[BMIM]Cl 1% w/v ionogel as descri...
Figure 7.13 SR‐UVRR spectra of sDNA/[BMIM]Cl 1% w/v ionogel obtained using 2...
Figure 7.14 (a) 266 nm‐excited UVRR spectra of sDNA/[BMIM]Cl 1% w/v ionogel ...
Figure 7.15 (a) 250 nm‐excited UVRR spectra of sDNA/[BMIM]Cl 1% w/v ionogel ...
Figure 7.16 Scheme of synthesis of cyclodextrin nanosponges cross‐linked pol...
Figure 7.17 (a) Experimental Raman spectra of the β‐CDPMA14 polymeric hydrog...
Figure 7.18 (a) Hydration dependence of isotropic UV Raman profiles for β‐CD...
Figure 7.19 (a) Experimental isotropic Raman spectra of NS hydrogels hydrate...
Figure 7.20 Isotropic UV Raman profiles of the β‐CDPMA1
n
hydrogel (
n
= 4, 6,...
Figure 7.21 (a) Temperature evolution of isotropic Raman profiles for β‐CDPM...
Figure 7.22 Temperature evolution of the dephasing time
τ
deph
associate...
Figure 7.23 Temperature evolution of the wavenumber position of the modes
ν
...
Figure 7.24 pH evolution of UV Raman spectra collected on β‐CDEDTA18 gel swo...
Figure 7.25 (a) Hydration dependence of parameter C for β‐CDEDTA18 gel swoll...
Chapter 8
Figure 8.1 A schematic representation of the optical geometry used in SFG sp...
Figure 8.2 (a) Neutron reflectivity for a dPS film in air, water, methanol, ...
Figure 8.3 (a) SFG spectra for PS at the air, D
2
O,
d
4
‐methanol, and
d
14
‐hexa...
Figure 8.4 SFG spectra for water on PS and quartz in the O–H vibrational reg...
Figure 8.5 SFG spectra for PS and quartz at the methanol interface in the (a...
Figure 8.6 Time dependence of the intensity of the SFG signal at 3060 cm
−1
...
Figure 8.7 SFG spectra for PS (a) spin‐coated and (b) solvent‐cast films on
Figure 8.8 SFG spectra for PS (a) spin‐coated and (b) solvent‐cast films on ...
Figure 8.9 (a) SFG spectra with the ssp polarization combination for PI film...
Figure 8.10 (a) SFG intensity ratio of the C−H antisymmetric to symmetric st...
Figure 8.11 (a) Temperature dependence of SFG peak intensity at 2965 cm
−1
...
Figure 8.12 SFG spectra collected from (a) spin‐coated and (b) solvent‐cast ...
Scheme 8.1 Plausible local conformations of SBR chains at the quartz interfa...
Figure 8.13 SFG ssp spectra for (a) spin‐coated and (b) solvent‐cast SBR fil...
Figure 8.14 The temperature dependence of SFG intensity at 2900 cm
−1
(...
Figure 8.15 (a) Time dependence of the SFG intensity at 2900 cm
−1
for ...
Chapter 9
Figure 9.1 The scheme of the generalized 2D‐COS.
Figure 9.2 Temperature‐dependent IRRAS spectra of spin‐coated films of PHBHx...
Figure 9.3 Asynchronous 2D correlation spectra of PHBHx (a), 70/30 PHBHx/PEG...
Figure 9.4 FTIR spectra of the NiPAAm gelation process measured at 22 (a) an...
Figure 9.5 Synchronous (a, c, e, g) and asynchronous (b, d, f, h) 2D correla...
Figure 9.6 Temperature‐dependent FTIR spectra of linear PNiPAAm gel during t...
Figure 9.7 Synchronous (a, c) and asynchronous (b, d) hetero‐region 2D corre...
Figure 9.8 Synchronous (a) and asynchronous (b) 2D hetero‐spectral XPS/IR co...
Figure 9.9 2D gradient map of
dA(ν
,
T)
/
dT
as a function of
ν
and
T
Figure 9.10 Synchronous 2D correlation spectra of spin‐coated films of PHBHx...
Figure 9.11 Synchronous PCA 2D correlation spectra of spin‐coated films of P...
Figure 9.12 Temperature‐dependent IR spectra of PHB thin film measured at 4 ...
Figure 9.13 Synchronous (a), synchronous projection (b), and synchronous nul...
Figure 9.14 Chemical images of the C = O stretching region at each temperatu...
Figure 9.15 Temperature‐dependent FTIR spectra extracted at parts A (a, c) a...
Figure 9.16 Synchronous (a, c, e, g) and asynchronous (b, d, f, h) 2D correl...
Chapter 10
Figure 10.1 (a) Shows the structure of PHB and evolution of O–H distance alo...
Figure 10.2 Simulation results for PNIPAM in water at 280 K obtained with th...
Figure 10.3 Hydrogen bonds differentiate polymer crystal forms. Solving the ...
Figure 10.4 Models of composite structures after MD simulations in which PAA...
Chapter 11
Figure 11.1 Schematic drawing of a bioresorbable polymeric scaffold.
Figure 11.2 Two proposed forms of the PLA α‐crystals are shown schematically...
Figure 11.3 Spherulite observed under polarized optical microscopy. The appr...
Figure 11.4 Polarized infrared spectra of PLA 1.2% D, electrospun into fiber...
Figure 11.5 Cryogenic infrared spectra of PLA 1.2% D spherulite, prepared by...
Figure 11.6 Polarized Raman spectra of 3D spherulite of PLA 1.2% D α‐crystal...
Figure 11.7 Simulated and experimental Raman data of poly(ethylene oxide) so...
Figure 11.8 Schematic drawing of backbone structure of a PLA repeat.
Figure 11.9 Polarized Raman spectra of PLA. The drawing direction of the sam...
Figure 11.10 Polarized infrared spectra of drawn poly(lactic acid) film take...
Figure 11.11 Calculated spectra of four helices (2
1
, 3
1
, 4
1
, and 5
1
) predict...
Figure 11.12 Measured and simulated (
A
modes only) Raman spectra for a 3
1
he...
Figure 11.13 Experimental Raman spectra of biaxially stretched films.
Figure 11.14 Plotting of the spectral intensity ratio
R
vs.
f
tg′t
for ...
Figure 11.15 The percentage of tg′t conformation and the crystallinities of ...
Figure 11.16 The increase in the degree of crystallinity of Raman bands in t...
Figure 11.17 Unit cells of the α and α′ structures from literature.
Figure 11.18 Simulated Raman spectra with the variable helix model [11, 12]....
Figure 11.19 Molecular models of a 10
3
PLA helix chain containing 30% 3
1
def...
Chapter 12
Figure 12.1 Self‐healing mechanisms. (a) Physical self‐healing processes inc...
Figure 12.2 (a) chemical structure of synthesized thermoplastic polyurethane...
Figure 12.3 Asynchronous 2D‐FT‐IR correlation spectra of PURP (A1) and PURM ...
Figure 12.4 (A) Optical images of damaged TPU fibers:
M
W
≈ 72 kDa (A1–A3), a...
Figure 12.5 2D‐FT‐IR spectra of TPUs upon damage (A) and repair (B); Synchro...
Figure 12.6 (a) monomers and catalyst utilized in the synthesis of OXE‐CHI‐P...
Figure 12.7 AFM images of undamaged (A1), damaged (A2), UV‐exposed (A2
1
, A2
2
Figure 12.8 (a) Cohesive energy density (CED) as a function of molar ratio f...
Figure 12.9 (A) Copolymerization of methyl methacrylate (MMA),
n
‐butyl acryl...
Figure 12.10 (A) Molecular modeling simulations of p(MMA/nBA/SNO) films: mec...
Chapter 13
Figure 13.1 Chemical structures of conjugated polymers: (a)
trans
‐polyacetyl...
Figure 13.2 Chemical structures of (a) a positive polaron and (b) a positive...
Figure 13.3 Schematic electronic structures. (a) Neutral polymer; (b) positi...
Figure 13.4 Changes in the VIS/NIR absorption spectrum of a P3HT film doped ...
Figure 13.5 Changes in the VIS–NIR absorption spectrum of a P3HT film doped ...
Figure 13.6 Optical absorption spectral changes of a PBTTT‐C16 film upon FeC...
Figure 13.7 Raman spectra of (a) neutral P3HT, (b) chemically formed positiv...
Figure 13.8 Raman spectra of neutral PBTTT‐C16 upon FeCl
3
doping. Excitation...
Figure 13.10 Chemical structures of some ionic liquids.
Figure 13.9 Device structure of the ILGT fabricated with P3HT and [BMIM][TFS...
Figure 13.11 Relation between −
I
D
and −
V
G
at
V
D
= −100 mV for a P3HT ILGT....
Figure 13.12 Raman spectra of the ITO/[BMIM][TFSI]/P3HT structure as a funct...
Figure 13.13 Conductivity and mobility as a function of doping level.
Figure 13.14 Relation between −
I
D
and −
V
G
at
V
D
= −0.01 V for an unannealed ...
Figure 13.15 Raman spectral changes of an unannealed PBTTT‐C16 ILGT upon app...
Figure 13.16
σ
and
μ
versus
x
plots for an unannealed PBTTT‐C16 IL...
Figure 13.17
I
D
–
V
D
characteristics at
V
G
= −1.0 V.
Figure 13.18 Raman images of the channel region of a transistor at
V
G
= −1.0...
Figure 13.19 Cross sections of the Raman images in the channel region at
V
G
...
Figure 13.20 Femtosecond time‐resolved NIR inverse Raman spectra from a P3HT...
Figure 13.21 Time evolution of the photoinduced infrared absorption spectrum...
Chapter 14
Figure 14.1 Schematics of R
f
chain (left) and normal alkyl chain (right)....
Figure 14.2 Phase diagram of PTFE.
Figure 14.3 Raman spectra of PTFE at different temperatures.
Figure 14.4 Raman shift at the boundary of Phases II and III.
Figure 14.5 (a) The C–F stretching vibration region of IR spectra of a compo...
Figure 14.6 (a) The C–F stretching vibration region of Raman spectra of the ...
Figure 14.7 The helical conformation of an R
f
group with
D
15
.
Figure 14.8 Schematic view of the SDA theory.
Figure 14.9 Infrared pMAIRS spectrum of a single‐monolayer LB film of MA‐R
f
9...
Figure 14.10 Conformational energy against the torsion angle for a hydrocarb...
Figure 14.11 (a) The ROA measurement setup built on a Raman imaging microsco...
Figure 14.12 (a) ROA spectra of seven crystals of MA‐R
f
9. (b) Visual image o...
Figure 14.13 IR ATR spectra of C
n
F
2
n
+2
(
n
= 6−9) with time during an eva...
Figure 14.14 (a) Electric relative permittivity of a crystal of NaCl involvi...
Figure 14.15 (a) The unpolarized IR ATR spectra of thick and very thin C
6
F
14
Figure 14.16 Wavenumber plots with time for the same R
f
alkanes as used for ...
Chapter 15
Figure 15.1 Room‐temperature FTIR spectra of the
δ
(C
b
–H) vibration mode...
Figure 15.2 (a, b) Raman spectra of as‐cast (a, red) and annealed (b, blue) ...
Figure 15.3 Temperature‐dependent FTIR spectra of P3BT Form I (a), Form I′ (...
Figure 15.4 (a) Resonance Raman spectra of the
ν
s
(C = C) mode for as‐ca...
Figure 15.5 (a) Raman spectra of electrochemically doped PBTTT depending on ...
Figure 15.6 (a) FTIR spectral changes in the C–H stretching vibration region...
Figure 15.7 (a) Spectral changes in the region of 850 to 800 cm
−1
durin...
Figure 15.8 (a) Valence‐bond Structures of the Quinoidal Excited State of P3...
Figure 15.9 Raman (a) and SERS (b) spectra for an as‐cast sample of quartz (...
Figure 15.10 (a) Raman spectra of PCPDTBT collected at two excitation wavele...
Figure 15.11 (A) Schematic of the SA Raman interface used to collect the dat...
Figure 15.12 (a‐1) Sketch of the considered interface and of the set‐up geom...
Figure 15.13 (a) IR response of P3HT film modified by electrostatic doping i...
Figure 15.14 (A) Schematic of the polarization dependence of charge conducti...
Figure 15.15 (a) The steady‐state near‐IR inverse Raman spectrum of a pristi...
Figure 15.16 Pulse energy density dependence of transient inverse Raman spec...
Figure 15.17 (a) Schematic diagram of the thin‐film transistor configuration...
Figure 15.18 (a) Device structure and the schematic drawing of the in situ R...
Chapter 16
Figure 16.1 Chemical structure and its intermolecular hydrogen bonding of po...
Figure 16.2 (a)Temperature‐dependent IR spectral variations in the C = O str...
Figure 16.3 Temperature‐dependent IR spectra variations and its second deriv...
Figure 16.4 Weak hydrogen bonding of PHB and N—H⋯O C hydrogen bonding networ...
Figure 16.5 Comparison of (a) C–H stretching and (b) C–H deformation band re...
Figure 16.6 Intermolecular hydrogen bondings of P(HB‐
co
‐HV).
Figure 16.7 Schematic illustration of the lamella for PHB and P(HB‐
co
‐HV). *...
Figure 16.8 Decomposed elemental WAXD profiles of (020), (110), and multiple...
Figure 16.9 A schematic illustration of the multistep crystallization proces...
Figure 16.10 Plots of the wavenumbers of the (a) C–O–C (1092 cm
−1
), (b...
Figure 16.11 Chemical structure and the model of these intermolecular hydrog...
Figure 16.12 Chemical structure of PCL. “A” is the CH
2
adjacent to methylene...
Figure 16.13 (a) IR spectra of PGA, PHB, and PCL cast film in the C = O stre...
Guide
Cover
Table of Contents
Title Page
Copyright
List of Contributors
Preface
General Introduction
Begin Reading
Index
WILEY END USER LICENSE AGREEMENT
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Spectroscopic Techniques for Polymer Characterization
Methods, Instrumentation, Applications
Edited by Yukihiro Ozaki and Harumi Sato
Editors
Professor Yukihiro OzakiKwansei Gakuin UniversitySchool of Biological andEnvironmental Sciences2‐1 Gakuen, Sanda669‐1337 Sanda, HyogoJapan
Professor Harumi SatoKobe UniversityGraduate School of HumanDevelopment and Environment3‐11 Tsurukabuto, Nada‐ku657‐8501 Hyogo, KobeJapan
Cover Image: © Harumi Sato
All books published by WILEY‐VCH are carefully produced. Nevertheless, authors, editors, and publisher do not warrant the information contained in these books, including this book, to be free of errors. Readers are advised to keep in mind that statements, data, illustrations, procedural details or other items may inadvertently be inaccurate.
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© 2022 WILEY‐VCH GmbH, Boschstr. 12, 69469 Weinheim, Germany
All rights reserved (including those of translation into other languages). No part of this book may be reproduced in any form – by photoprinting, microfilm, or any other means – nor transmitted or translated into a machine language without written permission from the publishers. Registered names, trademarks, etc. used in this book, even when not specifically marked as such, are not to be considered unprotected by law.
Print ISBN: 978‐3‐527‐34833‐6ePDF ISBN: 978‐3‐527‐83030‐5ePub ISBN: 978‐3‐527‐83032‐9oBook ISBN: 978‐3‐527‐83031‐2
List of Contributors
Marek Boczar
Jagiellonian University
Faculty of Chemistry
Gronostajowa 2, Krakow 30‐387
Poland
Liliane Bokobza
Former Professor at ESPCI
92200 Neuilly‐Sur‐Seine
France
Mateusz Z. Brela
Jagiellonian University
Faculty of Chemistry
Gronostajowa 2, Krakow 30‐387
Poland
Sara Catalini
European Laboratory for Non‐Linear Spectroscopy, LENS
50019 Sesto
Fiorentino, Firenze
Italy
Andrew V. Ewing
Imperial College London, South Kensington Campus
Department of Chemical Engineering
London SW7 2AZ
UK
Yukio Furukawa
Waseda University
Graduate School of Advanced Science and Engineering, Department of Chemistry and Biochemistry
Shinjuku‐ku, Tokyo 169‐8555
Japan
Alessandro Gessini
Elettra Sincrotrone Trieste
Trieste 34149
Italy
Takeshi Hasegawa
Kyoto University
Institute for Chemical Research
Uji, Kyoto 611‐0011
Japan
Yuta Hikima
Kyoto University
Graduate School of Engineering
Nishikyo‐ku, Kyoto 615‐8510
Japan
Shaw L. Hsu
University of Massachusetts (Amherst)
Department of Polymer Science and Engineering
Amherst, MA 01003
USA
Daitaro Ishikawa
Fukushima University
Faculty of Food and Agricultural Sciences
1 Kanayagawa, Fukushima 960‐1296
Japan
Young Mee Jung
Kangwon National University
Chemistry, Institute for Molecular Science and Fusion Technology
Chuncheon 24341
Korea
Daisuke Kawaguchi
Kyushu University
Department of Applied Chemistry
744 Motooka, Nishi‐ku, Fukuoka 819‐0395
Japan
Sergei G. Kazarian
Imperial College London, South Kensington Campus
Department of Chemical Engineering
London SW7 2AZ
UK
Lei Li
Clemson University
Department of Materials Science and Engineering
Clemson 29634
USA
Qianhui Liu
Clemson University
Department of Materials Science and Engineering
Clemson 29634
USA
Huiqiang Lu
Imperial College London, South Kensington Campus
Department of Chemical Engineering
London SW7 2AZ
UK
Claudio Masciovecchio
Elettra Sincrotrone Trieste
Basovizza, Trieste 34149
Italy
Yusuke Morisawa
Kindai University
School of Science and Engineering
Department of Chemistry
Higashi‐Osaka 577‐8502
Japan
Isao Noda
University of Delaware
Department of Materials Science and Engineering
Newark, DE 19716
USA
Yukihiro Ozaki
Kwansei Gakuin University
School of Biological and Environmental Sciences, 2-1 Gakuen
Sanda, Hyogo 669‐1337
Japan
Yeonju Park
Kangwon National University
Kangwon Radiation Convergence Research Support Center
Chuncheon 24341
Korea
Barbara Rossi
Elettra Sincrotrone Trieste
Basovizza, Trieste 34149
Italy
Harumi Sato
Kobe University
Graduate School of Human Development and Environment
Nada, Kobe 657‐8501
Japan
Keiji Tanaka
Kyushu University
Department of Applied Chemistry
Faculty of Engineering
744 Motooka, Nishi‐ku, Fukuoka 819‐0395
Japan
Mariagrazia Tortora
Elettra Sincrotrone Trieste
S.S. 114 km 163.5, Basovizza, Trieste 34149
Italy
Nami Ueno
University of Innsbruck
Institute of Analytical Chemistry and Radiochemistry
Innrain 80‐82, 6020 Innsbruck, Austria
Marek W. Urban
Clemson University
Department of Materials Science and Engineering
Clemson 29634
USA
Marek J. Wójcik
Jagiellonian University
Faculty of Chemistry
Gronostajowa 2, Krakow 30‐387
Poland
Xiaozhen Yang
Institute of Chemistry
Chinese Academy of Sciences
Beijing 100080
China
Yuan Yuan
Qingdao University of Science & Technology, Key Laboratory of Rubber‐Plastics
Ministry of Education/Shandong Provincial Key Laboratory of Rubber‐plastics
School of Polymer Science and Engineering
53 Zhengzhou Road, Qingdao 266042
China
Jianming Zhang
Qingdao University of Science & Technology, Key Laboratory of Rubber‐Plastics
Ministry of Education/Shandong Provincial Key Laboratory of Rubber‐plastics
School of Polymer Science and Engineering
53 Zhengzhou Road, Qingdao 266042
China
Preface
It was our great honor and pleasure to publish this book on the special occasion of the 101st anniversary of the polymer hypothesis of Herman Staudinger. Polymer spectroscopy has a history of 80 years or so. Professor Shaw Ling Hsu of the University of Massachusetts kindly provided a general introduction to polymer spectroscopy for this book.
Recently, polymer spectroscopy has demonstrated remarkable progress in many aspects. For example, a couple of new spectroscopies joined the family of polymer spectroscopy, including far‐ultraviolet (FUV) spectroscopy, tip‐enhanced Raman scattering (TERS), and terahertz (THz) spectroscopy. Nowadays, spectroscopic techniques of polymers range from FUV to far‐infrared/THz and Raman spectroscopy. IR, Raman, near‐infrared (NIR), and FIR/THz spectroscopy have all made significant progress. You can find the progress of these spectroscopies detailed in this book. Of particular interest is the development of imaging techniques in IR, Raman, NIR, and THz spectroscopies. Three‐dimensional imaging also emerged. Spectral analysis and data treatment methods have also advanced significantly. It is noted that the quantum chemistry approach has been introduced not only to polymer vibrational spectroscopy but also polymer electronic spectroscopy.
Currently, several important textbooks on spectroscopic techniques for polymers are available; they are all important books, but some of them are not new. We thought there was strong demand for a state‐of‐the‐art textbook on polymer spectroscopy. Therefore, we have decided to prepare a modern book on polymer spectroscopy for a wide variety of readers. We have aimed at writing a book, which will find a place in history. This book consists of two major parts: Recent Progress on Spectroscopic Techniques and Topical Polymers Studied by Spectroscopy. The first part starts with an overview of polymer spectroscopy and then introduces seven kinds of modern spectroscopic techniques for polymer characterization. Two spectral analysis methods, two‐dimensional correlation spectroscopy and molecular dynamics are also reviewed. In the second part, we have six reviews on polymers studied by spectroscopic techniques, which currently receive keen interest: biodegradable polymers, self‐healable polymers, conducting polymers, and fluoropolymers. We attempted to prepare a book that is well balanced between basic science and applications. One of the goals of this book is to make a strong bridge between spectroscopists, polymer scientists, and engineers in academia and industry.
We succeeded in inviting active front runners in modern spectroscopic techniques for polymers from many countries. This book is useful for scientists, engineers, and graduate students in numerous areas of science and engineering. One can use this book as a text, for example, at a graduate school seminar.
We hope that many readers can learn much about spectroscopic techniques for polymers from this book, and that this book can inspire readers to utilize various kinds of spectroscopies for a variety of novel investigations.
Last but not least, we would like to thank Ms. Quraishi Sakeena of Wiley VCH for her continuous efforts in publishing this exciting book.
July 2021
Yukihiro Ozaki
Harumi Sato
General Introduction
On the special occasion of the 101th anniversary of the Polymer Theory by Hermann Staudinger.
2020 marks one hundred years of recognition of polymers as a branch of the materials discipline. During this period, polymers have moved from an amorphous concept first enunciated by Hermann Staudinger to one of the most important platforms for technology development. Coinciding with the development of polymer science and engineering are marked advancements in our understanding of the physics of spectroscopic transitions and incredible developments of associated instrumentations. This book shows how a segment of these spectroscopic advances have supported the advancement of polymer science as a whole. It intends to highlight the contributions of vibrational spectroscopy to the advances of polymer development.
There is little doubt that vibrational spectroscopy has developed into one of the most crucial characterization tools, complementing other techniques. Spectroscopy started with William Herschel discovery of infrared in 1800, long before any concept of quantum mechanics was established, and even before the recognition of molecular vibrational transitions in the early 1900s. It is difficult to imagine the incredible developments of infrared spectroscopy since the review first published by R. Bowling Barnes and Lyman G. Bonner in 1936. Even when I went to University of Michigan to study polymer spectroscopy with Professor Sam Krimm in the late 1960s, I remember looking incredulously at the large brackets outside the Randall Physics Laboratory that were used to hold the lens guiding sunlight into the basement as excitation for infrared spectroscopy. Nowadays almost all laboratories have a very reliable and accurate infrared spectrometer to analyze chemical compositions and polymeric structures. We now also treat the incredible Fourier transform technique as being an inherent part of any infrared instrument. The speed with which we gather data has also improved tremendously, allowing for routine kinetics experiments with temporal resolution in milliseconds or faster. There are numerous attachments, which make polymer surface analysis rather mundane in nature. It can be said if there is a need, infrared spectroscopy can fulfill it.
Raman spectroscopy has a shorter history, since the Raman effect was not reported until 1928 when Chandrasekhara Venkata Raman did, also using focused sunlight. The effect of having scattered radiation different from the excitation frequency was first predicted by theoretician Adolf Smekal in 1923. After a lull of several decades, there was a tremendous surge of interest in this sector of spectroscopy due to the development in 1964 of a laser that could provide intense and polarized radiation for excitation. Only then could the Raman effect be observed expediently with the use of multiplier tubes. Furthermore, the observation and developments of various Raman‐associated phenomena, such as surface‐enhanced spectroscopy, coherent anti‐Stokes spectroscopy (named for Sir George Gabriel Stokes, a nineteenth‐century British physicist), and the Fourier transform multiplex advantage, have made Raman spectroscopy a common technique in many laboratories, along with infrared spectroscopy. The weak Raman scattering associated with water makes structural analysis of biological samples quite routine in nature.
It is not an exaggeration to state that vibrational spectroscopy, including infrared absorption and Raman scattering, is now one of the most widely used characterization techniques in polymer studies. This book comprises studies that describe various applications that have benefitted significantly from the use of vibrational spectroscopy. These spectroscopic studies focus on examples such as molecular interpretation of adhesive properties, measurement of crystalline domain size, analysis of phase‐separated structures and their formation kinetics, aging/phase transformation of polymers, surface studies, orientation behavior of polymers, and examples in which imaging properties have proven to be crucial. In the last one hundred years, advances in synthesis have provided numerous fascinating new structures that need to be characterized. Polymers confined to interface or interphase that dominate physical properties need to be differentiated from the ones in the three‐dimensional state. The conformation and orientation of deformed polymers in processed goods need to be elucidated. The aging behavior and changes in physical properties of polymers have often been defined using macroscopic techniques. Vibrational spectroscopy is a versatile and appropriate tool for the analysis of polymers undergoing changes as a function of time, temperature, and environment. Chemical and physical systems undergoing change display spectral signatures from the radio frequency to the X‐ray region of the electromagnetic spectrum. This has led to the development of time‐resolved tetrahertz (THz) spectroscopy, which has added to the measurements of transient phenomena in the subpicosecond range. These developments are described further in later chapters.
The astronomical increase in computational power just in the last fifty years has changed the landscape of vibrational spectroscopy significantly. In the earlier days, the use of finite groups to analyze equilibrium molecular structures not only clarified the optical activities of Raman and infrared transitions, but also provided a means to calculate normal coordinates. This formed a basis for analyzing the active vibrations. Wilson and his coworkers provided the rigorous, elegant treatment of the mathematics involved in detailed vibrational analyses of polyatomic molecules that is still being practiced today with much higher speed. Because of the enormous computational capabilities commonly available nowadays, those earlier studies solving the diagonalization of secular determinants have evolved into sophisticated calculations capable of analyzing not only the optical activities but also the quantum mechanical calculations necessary to determine the frequency and intensities of optical transitions. Some of those advances in molecular dynamics and density‐functional theory calculations will be described in this book. The lower‐lying transitions can now also be used to analyze the thermal properties of polymers. These computational developments have also enhanced the capabilities of two‐dimensional correlation spectroscopy, allowing for a better understanding of the intermolecular interactions.
The detailed analysis of the magnitude and specificity of intermolecular interactions in polymeric systems is extremely important. Though these interactions are weak in nature, they are important because all molecules in the condensed state possess such pairwise interactions. Their changes as a function of temperature and time are essential in determining changes in the physical properties of macroscopic polymers. Few explicit spectroscopic features are explicitly associated with the condensed state. However, when these features are found, vibrational spectroscopy provides the molecular interpretation of these intermolecular interactions, whether they are hydrogen bonding, electroscopic, dipolar, or van der Waals interactions. It is these interactions that determine miscibility behavior in blends, adhesive behavior associated with interface, engineering modulus or impact strength, and other properties. On the other extreme of frequency space associated with low‐lying intermolecular vibrations are the high‐frequency, more isolated near‐infrared spectroscopy (NIR) bands. These NIR vibrations have proven useful to follow chemical reactions, permeation behavior of moisture into polymers, and chemical composition analysis.
An area of great interest in polymer studies is the application of vibrational spectroscopy, particularly Raman, to the analysis of disordered chains, which include polymers in solution and melt, as well as amorphous polymers in the condensed state. As virtually all commercial polymers are carbon‐based, the change in polarizability along the backbone is large. Raman scattering is, therefore, particularly suitable for the characterization of polymer backbone conformation. Disordered chains lack long‐range order but may contain short ordered sequences because of significant differences in the relative energy of different rotational isomeric states along the polymer chain. For disordered structures, the vibrational spectra observed may be complex due to changes in both band frequency and shape. In these cases, the vibrational mode can be quite complicated because the contribution of various internal coordinates to the vibration (the character of the vibration) may change significantly, unlike that of an ordered crystalline chain. In addition, these disordered chains may adopt a specific conformational distribution depending on geometric constraints such as surfaces, clathrates, or interfaces. Amorphous chains thus require a completely different treatment. Changing the frequency and character of several vibrations provides tremendous insight into the structure of polymers in solution or melt, or the disordered regions of semicrystalline polymers. Rather than analyzing one specific chain conformation for an ordered chain, the analysis of vibrational spectra arising from disordered chains requires the vibrational spectrum of a conformational distribution. An extremely large number of possible conformers exist, each with a unique spectrum often only slightly different from one another. However, the isotropic Raman spectrum for the disordered state can be simulated as a composite of contributions from the ensemble of chains generated by a Monte Carlo procedure that assigns both a conformation and a total probability for each chain. These calculations can only be carried out using the modern computational techniques.
In many cases, it is important to assess the spatial distribution of various chemical species or morphological structures in polymers. Based on their spectroscopic features, infrared and Raman techniques are useful for mapping the distribution of structural variations within polymer samples. This information is quite different from the exact atomic placements available from techniques such as scanning electron microscopy. However, in many applications, such as in polymer blends and composites, vibrational spectroscopy provides valuable information regarding the spatial distribution of individual components that simply cannot be obtained using other techniques. Since the mapping capability of spectroscopic techniques depends on specific signals from molecular entities, even the distribution of functional groups can be differentiated within each sample, in contrast to techniques like microscopy. In addition to the differentiation of chemical species, it is also possible to assess other differences, such as segmental orientation or different degrees of crystallinity in various polymer samples. Imaging capability is needed in many polymer applications where multilayered thin films are necessary. Mapping the structure of individual layers can be accomplished using a confocal technique. Different segmental orientations as a function of cooling profile (surface versus bulk) can be differentiated using vibrational spectroscopy. Thus, the fracture of composites can be analyzed.
It should be noted that the spatial resolution of traditional spectroscopic techniques depends on the wavelength of the probing radiation. Raman excitation generally uses lasers in the visible range (400–800 nm). In contrast, infrared generally uses radiation in the micron range. Based on the Rayleigh criterion, the spatial resolution achievable using Raman will be significantly higher than the resolution achievable using infrared. In this book, we will review the various applications in which traditional imaging techniques have played a valuable role. The confocal capability of a spectroscopic technique will be discussed using only Raman scattering as an example. Although quite different in capability, infrared spectroscopy has been used extensively to differentiate between surface functionalities and bulk structure using reflectance techniques such as attenuated total reflectance (ATR) or more specialized external reflectance spectroscopy. In these cases, the spatial resolution is a fraction of that achievable by Raman. In some specialized cases, Raman technique can provide exceptional resolutions because the signal‐to‐noise ratio can be large due to a resonance effect. In these cases, clearly identifiable Raman signals (backbone stretching vibrations) can be used to analyze the perfection of graphene used in various processes. Specialized Raman techniques have been developed for surface analysis. Surface‐enhanced Raman spectroscopy (SERS) has proven useful for analyzing monolayers of adsorbed molecules onto metallic surfaces. The study of adsorbed molecules on metal surfaces using Raman spectroscopy, at one time an almost impossible task, has rapidly developed into an area of interest in recent years. SERS has developed a limited but totally different audience and has proven useful for the analytical characterization of various polymers, with applications ranging from food packaging to analysis of water quality. The development of hybrid techniques involving sharp probing tips, as in atomic force microscopy (ATM), overcame the limited spatial resolution usually associated with traditional spectroscopic imaging techniques. These new developments can be used to measure distribution of chemical features down to a scale of less than a hundred nanometers. Vibrational spectroscopy is now used broadly in almost all polymer science and engineering laboratories, due to its ability to characterize morphological features on all scales, from the smallest to ones in the hundreds of nanometers.
January 2021
Shaw L. Hsu
Part IRecent Progress on Spectroscopic Techniques
1Polymer Spectroscopy – Spectroscopy from the Far‐Ultraviolet to Far‐Infrared/Terahertz and Raman Spectroscopy
Yukihiro Ozaki1,2 and Harumi Sato3
1Kwansei Gakuin University, School of Biological and Environmental Sciences, 2‐1 Gakuen, Sanda, Hyogo, 669‐1337, Japan
2Toyota Physical and Chemical Research Institute, Nagakute, Aichi, 480‐1192, Japan
3Kobe University, Graduate School of Human Development and Environment, Higashi‐Nada, Kobe, 659‐8501, Japan
1.1 Introduction to Polymer Spectroscopy
Polymer spectroscopy has played a very important role in the investigation of the structure, physical and chemical properties, and reactions of polymers in the last half century [1–9]. As an analytical technique, polymer spectroscopy was born just before World War II and gradually became more commonplace in the 1950s. Throughout the 1950s and 1960s, polymer spectroscopy developed significantly in parallel with the development of infrared (IR) spectroscopy, although Raman spectroscopy was also used in that period [1–4]. The brief history of polymer spectroscopy is described in Preface and this chapter later.
The purpose of this chapter is to provide an overview of polymer spectroscopy. This chapter consists of an outline of polymer spectroscopy, a brief history of polymer spectroscopy, an overview of molecular spectroscopy for polymer research, and a review of examples of studies based on polymer spectroscopy. In the last part of this chapter, we describe the perspectives for polymer spectroscopy.
1.1.1 Outline of Polymer Spectroscopy
Polymer spectroscopy is largely based on optical spectroscopy, which involves spectroscopy in the ultraviolet (UV), visible (Vis), and IR regions. The UV region ranges from 10 to 380 nm and may be divided into four regions: vacuum ultraviolet (VUV, 10–120 nm), far‐ultraviolet (FUV, 120–200 nm), deep ultraviolet (DUV, 200–300 nm), and UV (300–380 nm) [10]. Spectroscopy in the UV region is important because it provides the electronic spectra of molecules. However, compared with IR spectroscopy, UV spectroscopy has rarely been used for polymer research. Further, recently, among the UV regions, FUV spectroscopy has been applied to polymers to investigate the electronic and molecular structure and intermolecular interactions of polymers [11–14]. In Chapter 6, FUV studies of polymers are introduced. In addition, UV resonance Raman spectroscopy has also been used to investigate polymer structure and functions and will be reviewed in Chapter 7.
Figure 1.1 The region of electromagnetic wave from 200 nm to 1 mm.
The IR region (800 nm to 1 mm, 12 500 to 10 cm−1) is so wide in terms of energy that it is divided into three regions: near‐infrared (NIR, 800–2500 nm) [15–17], IR (or mid‐infrared; MIR, 4000 to 400 cm−1) [18–20], and far‐infrared (FIR, 400 to 10 cm−1) [21, 22], as shown in Figure 1.1. Spectroscopic techniques in these regions have developed independently over the years, although the developments of NIR and FIR spectroscopies generally remained far behind those of IR (MIR) spectroscopy. However, in the last three decades, remarkable developments have been made in NIR spectroscopy [15–17]. Recently, advances in FIR spectroscopy have also been made. For example, terahertz spectroscopy was initiated at the end of the 1990s because of developments in new light sources and detectors in the FIR region [23–25].
IR, NIR, and FIR/terahertz spectroscopies are basically vibrational spectroscopic techniques [26]. IR spectroscopy is concerned mainly with fundamental vibrational modes [18–20], NIR spectroscopy is the spectroscopy of overtones and combinations of fundamentals [15–17], and FIR/terahertz spectroscopy treats low‐frequency vibrational modes such as skeletal vibrations, torsional vibrations, and lattice vibrations [23–25]. Crucially, IR spectroscopy also involves the overtones and their combinations, NIR spectroscopy is concerned with electronic spectroscopy, and FIR/terahertz spectroscopy involves rotational spectroscopy. Thus, there is a clear border between IR and NIR spectroscopy because NIR spectroscopy is not related to the fundamentals; in contrast, the border between IR and FIR is not always clear. However, IR, NIR, and FIR spectroscopies are not three sisters; rather, IR is the mother of NIR spectroscopy because the overtones and combinations originate from the fundamentals.
Visible spectroscopy is typically only used as an ancillary tool in polymer studies, for example, to study the electronic structure of conductive polymers (Chapter 13). As an optical spectroscopic technique, fluorescence spectroscopy is also used for polymer research but is not considered in this book. In addition to the above optical spectroscopies, Raman spectroscopy is very important in polymer studies [27–30]. This is one of the key spectroscopic techniques in polymer research. In this book, normal Raman spectroscopy, resonance Raman spectroscopy, UV‐resonance Raman spectroscopy, surface‐enhanced Raman scattering (SERS) [31–33], tip‐enhanced Raman scattering (TERS) [31–33], and Raman imaging [34] are introduced as important tools for polymer science. In addition, there is no doubt that nuclear magnetic resonance (NMR) spectroscopy is very important in polymer spectroscopy, but it is beyond the scope of this account.
1.1.2 Brief History of Polymer Spectroscopy
In the second part of this chapter, we provide an overview of the history of polymer spectroscopy in relation to the 100th anniversary of polymer theory in 2020. Just before World War II, studies of polymers vibrational spectroscopy started [18–20]. For example, Kirkwood [35] and Whitcomb et al. [36] performed normal vibrational calculations on polyethylene. After World War II, developments in IR spectroscopy progressed significantly because of advances in its light sources, spectrometers, and detectors. Therefore, even in the 1940s, many polymer scientists started using IR spectroscopy for polymer studies. For example, Shimanouchi et al. [37] reported normal vibrational calculations of polyethylene. Many pioneering papers on IR studies of polymers were published in the 1950s. Shimanouchi [38], Krimm [39], Eliot [40], and Hummel [41] conducted systematic studies on the vibrational spectra of polymers. Of course, there were many other scientists who advanced polymer spectroscopy in the 1950s. In particular, several important books concerning the IR spectra of polymers were published in this period [5]. Eliot [40] wrote a very important review of polymer spectroscopy in 1960, and, in the 1960s, many research groups were involved in IR studies on the characterization of polymers [4].
In the 1960s, Schachtschneider and Snyder [42] conducted normal vibrational calculations on polyethylene; Tasumi and Shimanouchi[43] studied the vibrational spectroscopy of polyethylene using the modified Urey–Bradley force field; and Miyazawa and coworkers [44] reported IR studies of polyoxymethylene, polyethylene glycol, polypropylene, and polyethylene and also introduced neutron scattering in these studies [45]. Tadokoro and coworkers [46
