TY - JOUR
T1 - Determination of the interaction parameter and topological scaling features of symmetric star polymers in dilute solution
AU - Rai, Durgesh K.
AU - Beaucage, Gregory
AU - Ratkanthwar, Kedar
AU - Beaucage, Peter
AU - Ramachandran, Ramnath
AU - Hadjichristidis, Nikos
N1 - KAUST Repository Item: Exported on 2020-10-01
PY - 2015/7/15
Y1 - 2015/7/15
N2 - Star polymers provide model architectures to understand the dynamic and rheological effects of chain confinement for a range of complex topological structures like branched polymers, colloids, and micelles. It is important to describe the structure of such macromolecular topologies using small-angle neutron and x-ray scattering to facilitate understanding of their structure-property relationships. Modeling of scattering from linear, Gaussian polymers, such as in the melt, has applied the random phase approximation using the Debye polymer scattering function. The Flory-Huggins interaction parameter can be obtained using neutron scattering by this method. Gaussian scaling no longer applies for more complicated chain topologies or when chains are in good solvents. For symmetric star polymers, chain scaling can differ from ν=0.5(df=2) due to excluded volume, steric interaction between arms, and enhanced density due to branching. Further, correlation between arms in a symmetric star leads to an interference term in the scattering function first described by Benoit for Gaussian chains. In this work, a scattering function is derived which accounts for interarm correlations in symmetric star polymers as well as the polymer-solvent interaction parameter for chains of arbitrary scaling dimension using a hybrid Unified scattering function. The approach is demonstrated for linear, four-arm and eight-arm polyisoprene stars in deuterated p-xylene.
AB - Star polymers provide model architectures to understand the dynamic and rheological effects of chain confinement for a range of complex topological structures like branched polymers, colloids, and micelles. It is important to describe the structure of such macromolecular topologies using small-angle neutron and x-ray scattering to facilitate understanding of their structure-property relationships. Modeling of scattering from linear, Gaussian polymers, such as in the melt, has applied the random phase approximation using the Debye polymer scattering function. The Flory-Huggins interaction parameter can be obtained using neutron scattering by this method. Gaussian scaling no longer applies for more complicated chain topologies or when chains are in good solvents. For symmetric star polymers, chain scaling can differ from ν=0.5(df=2) due to excluded volume, steric interaction between arms, and enhanced density due to branching. Further, correlation between arms in a symmetric star leads to an interference term in the scattering function first described by Benoit for Gaussian chains. In this work, a scattering function is derived which accounts for interarm correlations in symmetric star polymers as well as the polymer-solvent interaction parameter for chains of arbitrary scaling dimension using a hybrid Unified scattering function. The approach is demonstrated for linear, four-arm and eight-arm polyisoprene stars in deuterated p-xylene.
UR - http://hdl.handle.net/10754/575987
UR - http://link.aps.org/doi/10.1103/PhysRevE.92.012602
UR - http://www.scopus.com/inward/record.url?scp=84938774510&partnerID=8YFLogxK
U2 - 10.1103/PhysRevE.92.012602
DO - 10.1103/PhysRevE.92.012602
M3 - Article
C2 - 26274195
SN - 1539-3755
VL - 92
JO - Physical Review E
JF - Physical Review E
IS - 1
ER -