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Comparing polarized Raman spectroscopy and birefringence as probes of molecular scale alignment in 3D printed thermoplastics

  • Polymers for Additive Manufacturing Prospective
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Abstract

Polymer chain orientation is crucial to understanding the polymer dynamics at interfaces formed during thermoplastic material extrusion additive manufacturing. The flow field and rapid cooling produced during material extrusion can result in chains which are oriented and stretched, which has implications for interdiffusion and crystallization. Polarized Raman spectroscopy offers a non-destructive and surface sensitive method to quantify chain orientation. To study orientation and alignment of chains in 3D printed polycarbonate filaments, we used a combination of polarized Raman spectroscopy and birefringence (\(\Delta n\)) measurements. By changing the orientation of the sample with respect to polarization of incident radiation, we probe changes in the ratio between orientation-dependent vibration modes and orientation-independent modes. We used principal component analysis (PCA) and partial least squares (PLS) regression to develop correlations for birefringence and Raman measurements in samples that were pulled at different draw ratios (DRs). PCA was used to differentiate between orientation-dependent and orientation-independent modes, while PLS regression was used to calculate birefringence from Raman measurements of 3D printed samples. Birefringence measurements were compared to the polycarbonate intrinsic birefringence of 0.2, to estimate the degree of orientation. We find that measured values of birefringence underestimate orientation compared to Raman measurements.

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Data availability

The data that support the findings of this study are available from the corresponding author upon reasonable request.

Notes

  1. Material extrusion is the ASTM definition for this process; however, it is also known as fused deposition modeling (FDM)® or fused filament fabrication (FFF).

  2. Certain commercial equipment, instruments, or materials are identified in this paper to specify the experimental procedure adequately. Such identification is not intended to imply recommendation or endorsement by the National Institute of Standards and Technology, nor is it intended to imply that the materials or equipment identified are necessarily the best available for the purpose.

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Acknowledgments

The authors would like to thank Marco A. G. Cunha and the late Mark O. Robbins for their invaluable discussions on relaxation processes during flow. This work was supported by the National Institute of Standards and Technology (NIST) Scientific and Technical Research and Services (STRS) and by the National Science Foundation (NSF) under Grant Number NSF DMREF-90069795.

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Authors and Affiliations

  1. Hopkins Extreme Materials Institute, Johns Hopkins University, Baltimore, MD, USA

    Nora M. Hassan

  2. Material Measurement Laboratory, National Institute of Standards and Technology, Gaithersburg, MD, USA

    Nora M. Hassan, Kalman B. Migler, Anthony P. Kotula & Jonathan E. Seppala

  3. Physical Measurement Laboratory, National Institute of Standards and Technology, Gaithersburg, MD, USA

    Nora M. Hassan & Angela R. Hight Walker

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  1. Nora M. Hassan
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  2. Kalman B. Migler
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Correspondence to Anthony P. Kotula or Jonathan E. Seppala.

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Hassan, N.M., Migler, K.B., Hight Walker, A.R. et al. Comparing polarized Raman spectroscopy and birefringence as probes of molecular scale alignment in 3D printed thermoplastics. MRS Communications 11, 157–167 (2021). https://doi.org/10.1557/s43579-021-00025-z

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