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Title: Effects of Hairy Nanoparticles on Polymer Crystallization Kinetics

Abstract

We previously showed that nanoparticles (NPs) could be ordered into structures by using the growth rate of polymer crystals as the control variable. In particular, for slow enough spherulitic growth fronts, the NPs grafted with amorphous polymer chains are selectively moved into the interlamellar, interfibrillar, and interspherulitic zones of a lamellar morphology, specifically going from interlamellar to interspherulitic with progressively decreasing crystal growth rates. Here, we examine the effect of NP polymer grafting density on crystallization kinetics. We find that while crystal nucleation is practically unaffected by the presence of the NPs, spherulitic growth, final crystallinity, and melting point values decrease uniformly as the volume fraction of the crystallizable polymer, poly(ethylene oxide) or PEO, Φ PEO, decreases. A surprising aspect here is that these results are apparently unaffected by variations in the relative amounts of the amorphous polymer graft and silica NPs at constant Φ, implying that chemical details of the amorphous defect apparently only play a secondary role. We therefore propose that the grafted NPs in this size range only provide geometrical confinement effects which serve to set the crystal growth rates and melting point depressions without causing any changes to crystallization mechanisms.

Authors:
ORCiD logo [1]; ORCiD logo [1];  [2];  [1]; ORCiD logo [3]; ORCiD logo [4]; ORCiD logo [3]; ORCiD logo [5]; ORCiD logo [1]
  1. Columbia Univ., New York, NY (United States). Dept. of Chemical Engineering
  2. Univ. of the Basque Country, Donostia (Spain). Dept. of Polymer Science and Technology; Molecular and Supramolecular Materials Laboratories (POLYMAT), Gipuzkoa (Spain)
  3. Univ. of South Carolina, Columbia, SC (United States). Dept. of Chemistry and Biochemistry
  4. Saclay Nuclear Research Center (CEA), Gif-Sur-Yvette (France)
  5. Univ. of the Basque Country, Donostia (Spain). Dept. of Polymer Science and Technology; Molecular and Supramolecular Materials Laboratories (POLYMAT), Gipuzkoa (Spain); Basque Science Foundation, Bilbao (Spain)
Publication Date:
Research Org.:
Columbia Univ., New York, NY (United States); Brookhaven National Laboratory (BNL), Upton, NY (United States). National Synchrotron Light Source-II (NSLS-II); Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Materials Sciences & Engineering Division
OSTI Identifier:
1595742
Grant/Contract Number:  
SC0018111; SC0012704; GU-303362; GUP-62379
Resource Type:
Accepted Manuscript
Journal Name:
Macromolecules
Additional Journal Information:
Journal Volume: 52; Journal Issue: 23; Journal ID: ISSN 0024-9297
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Crystals; Crystallization; Silica; Organic compounds; Polymers

Citation Formats

Jimenez, Andrew M., Krauskopf, Alejandro A., Pérez-Camargo, Ricardo A., Zhao, Dan, Pribyl, Julia, Jestin, Jacques, Benicewicz, Brian C., Müller, Alejandro J., and Kumar, Sanat K. Effects of Hairy Nanoparticles on Polymer Crystallization Kinetics. United States: N. p., 2019. Web. doi:10.1021/acs.macromol.9b01380.
Jimenez, Andrew M., Krauskopf, Alejandro A., Pérez-Camargo, Ricardo A., Zhao, Dan, Pribyl, Julia, Jestin, Jacques, Benicewicz, Brian C., Müller, Alejandro J., & Kumar, Sanat K. Effects of Hairy Nanoparticles on Polymer Crystallization Kinetics. United States. doi:10.1021/acs.macromol.9b01380.
Jimenez, Andrew M., Krauskopf, Alejandro A., Pérez-Camargo, Ricardo A., Zhao, Dan, Pribyl, Julia, Jestin, Jacques, Benicewicz, Brian C., Müller, Alejandro J., and Kumar, Sanat K. Fri . "Effects of Hairy Nanoparticles on Polymer Crystallization Kinetics". United States. doi:10.1021/acs.macromol.9b01380. https://www.osti.gov/servlets/purl/1595742.
@article{osti_1595742,
title = {Effects of Hairy Nanoparticles on Polymer Crystallization Kinetics},
author = {Jimenez, Andrew M. and Krauskopf, Alejandro A. and Pérez-Camargo, Ricardo A. and Zhao, Dan and Pribyl, Julia and Jestin, Jacques and Benicewicz, Brian C. and Müller, Alejandro J. and Kumar, Sanat K.},
abstractNote = {We previously showed that nanoparticles (NPs) could be ordered into structures by using the growth rate of polymer crystals as the control variable. In particular, for slow enough spherulitic growth fronts, the NPs grafted with amorphous polymer chains are selectively moved into the interlamellar, interfibrillar, and interspherulitic zones of a lamellar morphology, specifically going from interlamellar to interspherulitic with progressively decreasing crystal growth rates. Here, we examine the effect of NP polymer grafting density on crystallization kinetics. We find that while crystal nucleation is practically unaffected by the presence of the NPs, spherulitic growth, final crystallinity, and melting point values decrease uniformly as the volume fraction of the crystallizable polymer, poly(ethylene oxide) or PEO, ΦPEO, decreases. A surprising aspect here is that these results are apparently unaffected by variations in the relative amounts of the amorphous polymer graft and silica NPs at constant Φ, implying that chemical details of the amorphous defect apparently only play a secondary role. We therefore propose that the grafted NPs in this size range only provide geometrical confinement effects which serve to set the crystal growth rates and melting point depressions without causing any changes to crystallization mechanisms.},
doi = {10.1021/acs.macromol.9b01380},
journal = {Macromolecules},
number = 23,
volume = 52,
place = {United States},
year = {2019},
month = {11}
}

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