Graphene Nanocomposites with High Molecular Weight Poly(ε-caprolactone) Grafts: Controlled Synthesis and Accelerated Crystallization
Abstract
Grafting of high molecular weight polymers to graphitic nanoplatelets is a critical step toward the development of high performance graphene nanocomposites. However, designing such a grafting route has remained a major impediment. Herein, we report a "grafting to" synthetic pathway by which high molecular weight polymer, poly(e-caprolactone) (PCL), is tethered, at high grafting density, to highly anisotropic graphitic nanoplatelets. The efficacy of this tethering route and the resultant structural arrangements within the composite are confirmed by neutron and X-ray scattering measurements in the melt and solution phase. In the semicrystalline state, Xray analysis indicates that chain tethering onto the graphitic nanoplatelets results in conformational changes of the polymer chains, which enhance the nucleation process and aid formation of PCL crystallites. This is corroborated by the superior thermal properties of the composite, manifested in accelerated crystallization kinetics and a significant increase in the thermal degradation temperature. Lastly, in principle, this synthesis route can be extended to a variety of high molecular weight polymers, which can open new avenues to solution-based processing of graphitic nanomaterials and the fabrication of complex 3D patterned graphitic nanocomposites.
- Authors:
-
- Indian Inst. of Technology (IIT), Bihar (India). Dept. of Chemistry; Univ. of Houston, Houston, TX (United States); Indian Inst. of Technology (IIT), West Bengal (India)
- National Inst. of Standards and Technology (NIST), Gaithersburg, MD (United States)
- National Inst. of Standards and Technology (NIST), Gaithersburg, MD (United States); Univ. of Delaware, Newark, DE (United States)
- Indian Inst. of Technology (IIT), West Bengal (India)
- Univ. of Houston, Houston, TX (United States)
- Publication Date:
- Research Org.:
- Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)
- Sponsoring Org.:
- USDOE; National Science Foundation (NSF)
- OSTI Identifier:
- 1261392
- Grant/Contract Number:
- AC05-00OR22725; in part by the National Science Foundation under Grant DMR-0944772.
- Resource Type:
- Accepted Manuscript
- Journal Name:
- ACS Macro Letters
- Additional Journal Information:
- Journal Volume: 5; Journal Issue: 3; Journal ID: ISSN 2161-1653
- Publisher:
- American Chemical Society
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 36 MATERIALS SCIENCE; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Citation Formats
Mondal, Titash, Ashkar, Rana, Butler, Paul, Bhowmick, Anil K., and Krishnamoorti, Ramanan. Graphene Nanocomposites with High Molecular Weight Poly(ε-caprolactone) Grafts: Controlled Synthesis and Accelerated Crystallization. United States: N. p., 2016.
Web. doi:10.1021/acsmacrolett.5b00930.
Mondal, Titash, Ashkar, Rana, Butler, Paul, Bhowmick, Anil K., & Krishnamoorti, Ramanan. Graphene Nanocomposites with High Molecular Weight Poly(ε-caprolactone) Grafts: Controlled Synthesis and Accelerated Crystallization. United States. https://doi.org/10.1021/acsmacrolett.5b00930
Mondal, Titash, Ashkar, Rana, Butler, Paul, Bhowmick, Anil K., and Krishnamoorti, Ramanan. Mon .
"Graphene Nanocomposites with High Molecular Weight Poly(ε-caprolactone) Grafts: Controlled Synthesis and Accelerated Crystallization". United States. https://doi.org/10.1021/acsmacrolett.5b00930. https://www.osti.gov/servlets/purl/1261392.
@article{osti_1261392,
title = {Graphene Nanocomposites with High Molecular Weight Poly(ε-caprolactone) Grafts: Controlled Synthesis and Accelerated Crystallization},
author = {Mondal, Titash and Ashkar, Rana and Butler, Paul and Bhowmick, Anil K. and Krishnamoorti, Ramanan},
abstractNote = {Grafting of high molecular weight polymers to graphitic nanoplatelets is a critical step toward the development of high performance graphene nanocomposites. However, designing such a grafting route has remained a major impediment. Herein, we report a "grafting to" synthetic pathway by which high molecular weight polymer, poly(e-caprolactone) (PCL), is tethered, at high grafting density, to highly anisotropic graphitic nanoplatelets. The efficacy of this tethering route and the resultant structural arrangements within the composite are confirmed by neutron and X-ray scattering measurements in the melt and solution phase. In the semicrystalline state, Xray analysis indicates that chain tethering onto the graphitic nanoplatelets results in conformational changes of the polymer chains, which enhance the nucleation process and aid formation of PCL crystallites. This is corroborated by the superior thermal properties of the composite, manifested in accelerated crystallization kinetics and a significant increase in the thermal degradation temperature. Lastly, in principle, this synthesis route can be extended to a variety of high molecular weight polymers, which can open new avenues to solution-based processing of graphitic nanomaterials and the fabrication of complex 3D patterned graphitic nanocomposites.},
doi = {10.1021/acsmacrolett.5b00930},
journal = {ACS Macro Letters},
number = 3,
volume = 5,
place = {United States},
year = {Mon Feb 08 00:00:00 EST 2016},
month = {Mon Feb 08 00:00:00 EST 2016}
}
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