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@INPROCEEDINGS{Richter:1046464,
author = {Richter, Dieter and Kruteva, Margarita and Allgaier,
Jürgen and Monkenbusch, Michael and Hoffmann, Ingo and
Peponaki, Katerina and Vlassopoulos, Dimitri},
title = {{N}eutron {I}nvestigations on the {S}tructure and dynamics
of ring-linear polymer blends},
reportid = {FZJ-2025-03817},
year = {2025},
abstract = {Blends of ring and linear polymers pose fascinating
challenges. While in such blends the dynamics of linear
chains is hardly affected, already minute concentrations of
linear chains have a large effect on ring rheology /1/.
Blends of rings with linear chains are characterized by
strong interpenetration of the rings by the linear chains.
These threadings swell the ring conformation significantly
and alter the ring dynamics very strongly, as large scale
ring motions are only possible by constraint release of the
linear component /2/. We have performed systematic Small
Angle Neutron Scattering (SANS) investigation of such
blends, where we have varied the ring volume fraction $ϕ_R$
for a ring 40 kg/mol polyethylene-oxide (PEO) in a linear
matrix of 100 kg/mol. We found that with increasing ring
fraction the ring radius of gyration ( $R_g)$ swells by more
than $20\%$ . At the same time the fractal dimension, which
is close to a Gaussian conformation at low $ϕ_R,$ decreases
to the value of the ring melt. Following a random phase
approximation (RPA) treatment, the Flory-Huggins parameter
$(χ_F)$ is large, negative and independent of $ϕ_R,$
signifying ring-linear attraction leading to ringring
repulsion /3/. Concerning the ring dynamics in symmetric
ring/linear blends of 40kg/mol PEO as a function of $ϕ_R$
we observed a transformation of typical self-similar ring
relaxation to local reptation type dynamics at higher linear
fraction, where the motion of the ring is slaved by the
linear host. The cross-over between the two types of motions
takes place for 0.25 $<ϕ_R<0.5.$ Even though at $ϕ_R=0.5$
the characteristic spectral shape assumes the local
reptation scheme, the actual constraints expressed by the
apparent entanglement length Ne are less than those at
higher linear volume fraction $(N_e100$ compared to $N_e70$
for $ϕ_R≤0.35.$ In addition ring mode suppression is
observed: A detailed mode analysis of the neat ring melt as
well as the $ϕ_(R$ )=0.95 blend revealed a suppression of
the first ring p = 2 mode. For $ϕ_(R$ )=0.75 also the
second ring mode p = 4 is suppressed. The p = 2 mode length
scale comprises the full ring size; it suppression already
in the neat melt indicates significant constraints on the
ring motion beyond the self-similar mode structure. This
observation correlates with the non- exponential decal of
dynamic shear modulus at long times, which is attributed to
ring-ring threading. References 1 M. Kapnistos, M. Lang, D.
Vlassopoulos, W. Pyckhout-Hintzen, D. Richter, D. Cho,
T.Chang, M. Rubinstein, Nature Materials 7, 997-1002 (2008)
2 Margarita Kruteva, Jürgen Allgaier and Dieter Richter,
Macromolecules, 56, 7203 - 7229 (2023) 3 M. Kruteva, M.
Monkenbusch, J. Allgaier, L. Porcar, D. Richter,
Macromolecules, 56, 4835 – 4844 (2023)},
month = {Sep},
date = {2025-09-29},
organization = {9th International Soft Matter
Conference, Minoa Palace Hotel and
conference center, outside the city of
Chania in Western Crete (Greece), 29
Sep 2025 - 3 Oct 2025},
subtyp = {Invited},
cin = {JCNS-2 / JARA-FIT / JCNS-1},
cid = {I:(DE-Juel1)JCNS-2-20110106 / $I:(DE-82)080009_20140620$ /
I:(DE-Juel1)JCNS-1-20110106},
pnm = {632 - Materials – Quantum, Complex and Functional
Materials (POF4-632) / 6G4 - Jülich Centre for Neutron
Research (JCNS) (FZJ) (POF4-6G4)},
pid = {G:(DE-HGF)POF4-632 / G:(DE-HGF)POF4-6G4},
typ = {PUB:(DE-HGF)6},
url = {https://juser.fz-juelich.de/record/1046464},
}