Anomalous anti-Stokes Raman scattering during epoxy-amine polymerization

In thermal equilibrium the Stokes Raman scatter should always be greater than the anti-Stokes; however, in some rare cases anomalous anti-Stokes Raman scattering (AASR) has been observed. This work presents the first observations of AASR during epoxy-amine polymerization and demonstrates the potenti...

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Main Authors: Robert V. Chimenti, Samuel E. Lofland
Format: Article
Language:English
Published: Elsevier 2025-10-01
Series:Polymer Testing
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Online Access:http://www.sciencedirect.com/science/article/pii/S0142941825002570
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author Robert V. Chimenti
Samuel E. Lofland
author_facet Robert V. Chimenti
Samuel E. Lofland
author_sort Robert V. Chimenti
collection DOAJ
description In thermal equilibrium the Stokes Raman scatter should always be greater than the anti-Stokes; however, in some rare cases anomalous anti-Stokes Raman scattering (AASR) has been observed. This work presents the first observations of AASR during epoxy-amine polymerization and demonstrates the potential to utilize this phenomenon as a means of noncontact heat flow measurement. Even though the phonon population is unbounded, experimental evidence shows that the AASR can be phenomenologically explained from an entropic perspective as negative-absolute-temperature-like behavior. Furthermore, since polymerization is a non-equilibrium thermodynamic process, a statistical physics-based heat flow kinetics model was developed which simultaneously describes the observed AASR and allows for the extraction of the excess phonon population. This excess phonon population was combined with a simplified Debye model for the phonon density of states to calculate an effective heat flow, which closely corresponds to the heat flow measured by isothermal differential scanning calorimetry.
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spelling doaj-art-c7842e2c1deb44b0bcdcd7e924d88e882025-08-20T02:57:08ZengElsevierPolymer Testing1873-23482025-10-0115110894310.1016/j.polymertesting.2025.108943Anomalous anti-Stokes Raman scattering during epoxy-amine polymerizationRobert V. Chimenti0Samuel E. Lofland1Department of Physics & Astronomy, Rowan University, 201 Mullica Hill Rd., Glassboro, NJ, 08028, United States; Advanced Materials & Manufacturing Institute (AMMI), Rowan University, 201 Mullica Hill Rd., Glassboro, NJ, 08028, United States; Corresponding author. Department of Physics & Astronomy, Rowan University, 201 Mullica Hill Rd., Glassboro, NJ, 08028, United States.Department of Physics & Astronomy, Rowan University, 201 Mullica Hill Rd., Glassboro, NJ, 08028, United States; Advanced Materials & Manufacturing Institute (AMMI), Rowan University, 201 Mullica Hill Rd., Glassboro, NJ, 08028, United StatesIn thermal equilibrium the Stokes Raman scatter should always be greater than the anti-Stokes; however, in some rare cases anomalous anti-Stokes Raman scattering (AASR) has been observed. This work presents the first observations of AASR during epoxy-amine polymerization and demonstrates the potential to utilize this phenomenon as a means of noncontact heat flow measurement. Even though the phonon population is unbounded, experimental evidence shows that the AASR can be phenomenologically explained from an entropic perspective as negative-absolute-temperature-like behavior. Furthermore, since polymerization is a non-equilibrium thermodynamic process, a statistical physics-based heat flow kinetics model was developed which simultaneously describes the observed AASR and allows for the extraction of the excess phonon population. This excess phonon population was combined with a simplified Debye model for the phonon density of states to calculate an effective heat flow, which closely corresponds to the heat flow measured by isothermal differential scanning calorimetry.http://www.sciencedirect.com/science/article/pii/S0142941825002570Raman thermometryLow-frequency Raman spectroscopyEpoxy polymerizationNon-equilibrium heat flow kinetics
spellingShingle Robert V. Chimenti
Samuel E. Lofland
Anomalous anti-Stokes Raman scattering during epoxy-amine polymerization
Polymer Testing
Raman thermometry
Low-frequency Raman spectroscopy
Epoxy polymerization
Non-equilibrium heat flow kinetics
title Anomalous anti-Stokes Raman scattering during epoxy-amine polymerization
title_full Anomalous anti-Stokes Raman scattering during epoxy-amine polymerization
title_fullStr Anomalous anti-Stokes Raman scattering during epoxy-amine polymerization
title_full_unstemmed Anomalous anti-Stokes Raman scattering during epoxy-amine polymerization
title_short Anomalous anti-Stokes Raman scattering during epoxy-amine polymerization
title_sort anomalous anti stokes raman scattering during epoxy amine polymerization
topic Raman thermometry
Low-frequency Raman spectroscopy
Epoxy polymerization
Non-equilibrium heat flow kinetics
url http://www.sciencedirect.com/science/article/pii/S0142941825002570
work_keys_str_mv AT robertvchimenti anomalousantistokesramanscatteringduringepoxyaminepolymerization
AT samuelelofland anomalousantistokesramanscatteringduringepoxyaminepolymerization