TY - JOUR
T1 - Relaxation of polymers in 2 nm slit-pores
T2 - Confinement induced segmental dynamics and suppression of the glass transition
AU - Manias, E.
AU - Kuppa, V.
AU - Yang, D. K.
AU - Zax, D. B.
N1 - Copyright:
Copyright 2017 Elsevier B.V., All rights reserved.
PY - 2001/8/31
Y1 - 2001/8/31
N2 - Molecular Dynamics (MD) simulations are used to explore the structure and dynamics of polystyrene confined in 2 nm slit pores, between parallel, crystalline, mica-type surfaces. The systems simulated resemble experimentally studied intercalated nanocomposites, where polystyrene is inserted between layered-silicate layers. The molecular modeling perspective complements the experimental findings and provides insight into the nature of polymers in nanoscopic confinements, especially into the molecular origins of their macroscopic behavior. Namely, a comparison between simulation and NMR studies shows a coexistence of extremely faster and much slower segmental motions than the ones found in the corresponding bulk polymer at the same temperature. The origins of these dynamical inhomogeneities are traced to the confinement induced density modulations inside the 2 nm slits. Fast relaxing phenyl and backbone moieties are found in low density regions across the film, and preferentially in the center, whereas slow relaxing moieties are concentrated in denser regions in the immediate vicinity of the confining surfaces. At the same time, the temperature dependence of the segmental relaxations suggests that the glass transition is suppressed inside the confined films, an observation confirmed by scanning calorimetry.
AB - Molecular Dynamics (MD) simulations are used to explore the structure and dynamics of polystyrene confined in 2 nm slit pores, between parallel, crystalline, mica-type surfaces. The systems simulated resemble experimentally studied intercalated nanocomposites, where polystyrene is inserted between layered-silicate layers. The molecular modeling perspective complements the experimental findings and provides insight into the nature of polymers in nanoscopic confinements, especially into the molecular origins of their macroscopic behavior. Namely, a comparison between simulation and NMR studies shows a coexistence of extremely faster and much slower segmental motions than the ones found in the corresponding bulk polymer at the same temperature. The origins of these dynamical inhomogeneities are traced to the confinement induced density modulations inside the 2 nm slits. Fast relaxing phenyl and backbone moieties are found in low density regions across the film, and preferentially in the center, whereas slow relaxing moieties are concentrated in denser regions in the immediate vicinity of the confining surfaces. At the same time, the temperature dependence of the segmental relaxations suggests that the glass transition is suppressed inside the confined films, an observation confirmed by scanning calorimetry.
UR - http://www.scopus.com/inward/record.url?scp=0035979940&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=0035979940&partnerID=8YFLogxK
U2 - 10.1016/S0927-7757(01)00634-3
DO - 10.1016/S0927-7757(01)00634-3
M3 - Article
AN - SCOPUS:0035979940
SN - 0927-7757
VL - 187-188
SP - 509
EP - 521
JO - Colloids and Surfaces A: Physicochemical and Engineering Aspects
JF - Colloids and Surfaces A: Physicochemical and Engineering Aspects
ER -