Nanoscale Particle Motion Reveals Polymer Mobility Gradient in Nanocomposites
- Erkan Senses*Erkan Senses*E-mail: [email protected]Department of Chemical and Biological Engineering, Koç University, Istanbul 34450, TurkeyMore by Erkan Senses
- ,
- Suresh NarayananSuresh NarayananAdvanced Photon Source, Argonne National Laboratory, Argonne, Illinois 60439, United StatesMore by Suresh Narayanan
- , and
- Antonio FaraoneAntonio FaraoneNIST Center for Neutron Research, Gaithersburg, Maryland 20899, United StatesMore by Antonio Faraone
Abstract

Polymer mobility near nanoparticle surfaces has been extensively discussed; however, direct experimental observation in the nanocomposite melts has been a difficult task. Here, by taking advantage of large dynamical asymmetry between the miscible matrix and surface-bound polymers, we highlighted their interphases and studied the resulting effect on the nanoparticle relaxation using X-ray photon correlation spectroscopy. The local mobility gradient is signified by an unprecedented increase in the relaxation time at length scales on the order of polymer radius of gyration. The effect is accompanied by a transition from simple diffusive to subdiffusive behavior in accord with viscous and entangled dynamics of polymers in the matrix and in the interphase, respectively. Our results demonstrate that the nanoparticle-induced polymer mobility changes in the interphases of nanocomposite melts can be extracted from the length-scale-dependent slow particle motion.
Cited By
This article is cited by 18 publications.
- Ming Hu, Hongbo Chen, Hongru Wang, Stanislav Burov, Eli Barkai, Dapeng Wang. Triggering Gaussian-to-Exponential Transition of Displacement Distribution in Polymer Nanocomposites via Adsorption-Induced Trapping. ACS Nano 2023, 17
(21)
, 21708-21718. https://doi.org/10.1021/acsnano.3c06897
- Mayank Jhalaria, Andrew M. Jimenez, Reha Mathur, Marshall C. Tekell, Yucheng Huang, Suresh Narayanan, Brian C. Benicewicz, Sanat K. Kumar. Long-Term Aging in Miscible Polymer Nanocomposites. Macromolecules 2022, 55
(11)
, 4502-4515. https://doi.org/10.1021/acs.macromol.2c00332
- Saeid Darvishi, Muhammad Anwaar Nazeer, Madhusudan Tyagi, Qingteng Zhang, Suresh Narayanan, Seda Kizilel, Erkan Senses. Nonlinear Architectures Can Alter the Dynamics of Polymer–Nanoparticle Composites. Macromolecules 2021, 54
(21)
, 10118-10125. https://doi.org/10.1021/acs.macromol.1c01382
- Erkan Senses, Saeid Darvishi, Madhu Sudan Tyagi, Antonio Faraone. Entangled Polymer Dynamics in Attractive Nanocomposite Melts. Macromolecules 2020, 53
(12)
, 4982-4989. https://doi.org/10.1021/acs.macromol.9b02545
- Yulong Chen, Rui Ma, Xin Qian, Ruoyu Zhang, Xifu Huang, Haohao Xu, Mi Zhou, Jun Liu. Nanoparticle Mobility within Permanently Cross-Linked Polymer Networks. Macromolecules 2020, 53
(11)
, 4172-4184. https://doi.org/10.1021/acs.macromol.0c00334
- Vladimir A. Bershtein, Pavel N. Yakushev. Nano- and Subnanocomposites with Silica Units Introduced by a Sol–gel Method. 2023, 61-83. https://doi.org/10.1007/978-3-031-32943-2_4
- A.-M. Philippe, C. Sill, S. Westermann, J. Allgaier, M. Staropoli, M. Monkenbusch, D. Gerstner, Y. Fleming, A. Wischnewski, I. Hoffmann, P. Zolnierczuk, C. Do, W. Pyckhout-Hintzen. Quantifying structure and dynamics of bound and bulk polymer in tailor-made rubber-silica nanocomposites. Frontiers in Physics 2022, 10 https://doi.org/10.3389/fphy.2022.1023234
- Xue-Zheng Cao, Holger Merlitz, Chen-Xu Wu, M. Gregory Forest. Screening confinement of entanglements: Role of a self-propelling end inducing ballistic chain reptation. Physical Review E 2022, 106
(2)
https://doi.org/10.1103/PhysRevE.106.L022501
- Yulong Chen, Haohao Xu, Yangwei Ma, Jun Liu, Liqun Zhang. Diffusion of polymer-grafted nanoparticles with dynamical fluctuations in unentangled polymer melts. Physical Chemistry Chemical Physics 2022, 24
(18)
, 11322-11335. https://doi.org/10.1039/D2CP00002D
- Erkan Senses, Christopher L. Kitchens, Antonio Faraone. Viscosity reduction in polymer nanocomposites: Insights from dynamic neutron and X‐ray scattering. Journal of Polymer Science 2022, 60
(7)
, 1130-1150. https://doi.org/10.1002/pol.20210320
- Husam Alkhodairi, Connor Bilchak, Sophia Y. Chan, Mayank Jhalaria, Sanat K. Kumar, Robert J. Tannenbaum. Polymer Nanocomposites. 2022, 1-45. https://doi.org/10.1002/9783527815562.mme0061
- Panagiotis A. Klonos, Dimitrios N. Bikiaris, Apostolos Kyritsis. Molecular Mobility in Nanocomposites Based on Renewable Semicrystalline Polyesters. 2022, 87-121. https://doi.org/10.1007/978-3-030-89723-9_4
- Vladimir A. Bershtein, Olga P. Grigoryeva, Pavel N. Yakushev, Alexander M. Fainleib. The nature of the exceptional impact of ultra‐low silica contents on the properties of cyanate ester
resin‐based
nano‐ and subnanocomposites. Polymer Composites 2021, 42
(12)
, 6777-6784. https://doi.org/10.1002/pc.26338
- Cheng-Hung Lin, Karol Dyro, Olivia Chen, Dean Yen, Bingqian Zheng, Maria Torres Arango, Surita Bhatia, Ke Sun, Qingkun Meng, Lutz Wiegart, Yu-chen Karen Chen-Wiegart. Revealing meso-structure dynamics in additive manufacturing of energy storage via operando coherent X-ray scattering. Applied Materials Today 2021, 24 , 101075. https://doi.org/10.1016/j.apmt.2021.101075
- Ahmad Moghimikheirabadi, Martin Kröger, Argyrios V. Karatrantos. Insights from modeling into structure, entanglements, and dynamics in attractive polymer nanocomposites. Soft Matter 2021, 17
(26)
, 6362-6373. https://doi.org/10.1039/D1SM00683E
- Argyrios V. Karatrantos, Nigel Clarke. Polymer Dynamics in Polymer-Nanoparticle Interface. 2021, 81-100. https://doi.org/10.1007/978-3-030-60443-1_4
- Yukari Oda, Daisuke Kawaguchi, Yuma Morimitsu, Satoru Yamamoto, Keiji Tanaka. Direct observation of morphological transition for an adsorbed single polymer chain. Scientific Reports 2020, 10
(1)
https://doi.org/10.1038/s41598-020-77761-0
- Eric J. Bailey, Karen I. Winey. Dynamics of polymer segments, polymer chains, and nanoparticles in polymer nanocomposite melts: A review. Progress in Polymer Science 2020, 105 , 101242. https://doi.org/10.1016/j.progpolymsci.2020.101242