Influence of C-60 fullerenes on the glass formation of polystyrene
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Published version
Author(s)
Sanz, A
Wong, HC
Nedoma, AJ
Douglas, JF
Cabral, JT
Type
Journal Article
Abstract
We investigate the impact of fullerene C60 on the thermal properties and glass formation of polystyrene (PS) by differential scanning calorimetry (DSC) and dielectric spectroscopy (DS), for C60 concentrations up to 30% mass fraction. The miscibility and dispersibility thresholds of PS/C60 nanocomposites are first estimated by a combination of microscopy, small angle neutron scattering (SANS) and wide-angle X-ray scattering (WAXS) experiments, and these thresholds were found to be ≃1 mass% and ≃4 mass% C60, respectively. The addition of C60 increases the glass-transition temperature (Tg) of rapidly precipitated PS composites, up to a ‘threshold’ C60 concentration (≃4 wt%, in agreement with the dispersibility estimate). Beyond this concentration, the Tg reverts gradually towards the neat PS value. We present a comprehensive study for composites based on PS of molecular mass 270 kg/mol, and demonstrate the generality of the impact of C60 on Tg for PS matrices of 2 and 20 kg/mol. Thermal annealing or slowly evaporated composites largely reverse these effects, as the dispersion quality decreases. The dynamic fragility m of the composite is found to increase in the presence of C60, but the scaling of m with Tg for PS is retained. Similarly, physical ageing experiments show a reduction of relaxation enthalpy in the glass regime, which is largely accounted for by the increase of Tg with C60. The slowing down of the PS α-relaxation with C60 contrasts with the local ‘softening’ indicated by former Debye-Waller measurements and increase in fragility m. This effect is opposite to that of antiplasticizer additives, which both stiffen the material in the glassy state and reduce Tg, and simulations suggest this could be due to an increase in packing frustration. Finally, we review observations on the effect of nanoparticles on the Tg of PS and discuss the non-universal nature of Tg shifts by various types of nanoparticles.
Date Issued
2015-05-12
Date Acceptance
2015-05-01
Citation
Polymer, 2015, 68, pp.47-56
ISSN
0032-3861
Publisher
ELSEVIER SCI LTD
Start Page
47
End Page
56
Journal / Book Title
Polymer
Volume
68
Copyright Statement
© 2015 The Authors. This is an open access article under the CC BY license
(http://creativecommons.org/licenses/by/4.0/).
(http://creativecommons.org/licenses/by/4.0/).
License URL
Subjects
Science & Technology
Physical Sciences
Polymer Science
Fullerenes
Polystyrene
Nanocomposites
TRANSITION TEMPERATURE
POLYMER NANOCOMPOSITES
ENTHALPY RELAXATION
MIXTURES
DYNAMICS
FRAGILITY
RECOVERY
BEHAVIOR
FILMS
SIZE
Publication Status
Published