% IMPORTANT: The following is UTF-8 encoded. This means that in the presence
% of non-ASCII characters, it will not work with BibTeX 0.99 or older.
% Instead, you should use an up-to-date BibTeX implementation like “bibtex8” or
% “biber”.
@PHDTHESIS{Lang:860717,
author = {Lang, Christian},
title = {{D}ynamics and phase behavior of (non-)ideal liquid
crystals under shear},
school = {KU Leuven},
type = {Dissertation},
reportid = {FZJ-2019-01382},
pages = {162},
year = {2019},
note = {Dissertation, KU Leuven, 2019},
abstract = {As the simplest form of polymeric materials, rodlike
polymers provide a unique opportunity to test and review the
theory of polymer dynamics. Liquid crystalline solutions of
rodlike particles are of high industrial relevance and their
flow behavior during processing strongly influences the
properties of the final products.While industrially used
materials are mostly non-ideal in several aspects such as
flexibility and polydispersity of the particles, the theory
of polymer dynamics is best applicable only to ideal rods.
The attempt of this thesis is to provide new insights into
the effect of such non-ideality parameters on the flow
behavior of rodlike suspensions.Rodlike bacteriophages are
used in this work in order to formulate materials with
well-defined system characteristics, which can be alternated
in a controlled way to understand non-ideal suspensions of
rods. These rodlike viruses form various liquid-crystalline
phases in aqueous suspension. However, here we focus on
isotropic suspensions which have neither positional nor
orientational order in the equilibrium state.The dynamics
and phase behavior of suspensions in the isotropic state are
measured under flow by means of a combination of small angle
neutron scattering with rheology and heterodyne dynamic
light scattering under flow. Based on the experimental
outcome, the theory of rodlike polymers is reviewed.In
chapter 2, a revised theory for ideal rodlike particles is
derived and tested in chapter 4. In chapter 5, we test the
theory against the influence of non-ideality parameters to
gain a deeper understanding of the nature of these
influences. Particularly, new expressions for the rotational
diffusion coefficient under tube dilation and a
non-equilibrium pair-correlation function are derived to
supplement the Fokker-Planck equation for rods.In chapter 5,
it is shown theoretically as well as experimentally that
particle morphology is one of the key influences on the flow
behavior of rods. In this respect, length and flexibility
are two counteracting parameters. With increasing length,
the dynamics of the rods slow down significantly leading to
higher zero shear viscosities, while an increase of particle
flexibility has the opposite effect. Furthermore, the onset
of shear thinning depends crucially on the particle length.
An increase in length shifts the onset of shear thinning to
smaller shear-rates. In section 5.3.2, we use the
understanding of this length dependence to make our
theoretical predictions quantitative by experimentally
determining the prefactor of the rotational diffusion
coefficient in the tube model for the first time. This is
very useful, as it is the basis for the understanding of
other phenomena studied here and reported in literature. Due
to a morphological transition to a hairpin state, an
increase in flexibility causes an increase of the viscosity
in the intermediate and high shear-rate regime, such that
under strong flow, higher length and higher bending rigidity
are both promoting shear thinning.In sections 4.3.1 and 5.2,
small amplitude oscillatory shear is used to demonstrate
that the rotational diffusion and the particle flexibility
crucially influences the quasi-linear flow behavior of rods.
It is found that, not unlike polymers, rods of finite
stiffness possess a relaxation time spectrum, see section
5.5.Extensional flow measurements are conducted to
demonstrate the effect of flexibility in the highly
non-linear flow regime, see section 5.4. It is found that an
increase in particle flexibility leads to a decrease in
extensional viscosity. The Trouton ratios of rodlike systems
are shown to be comparatively large despite of low normal
stresses.In section 5.6, it is demonstrated that the zero
shear behavior of polydisperse rodlike particle suspensions
does not involve higher complexities, while the shear
thinning behavior becomes very complex and, therefore,
cannot be understood by employing linear mixing rules in the
governing equations for particle dynamics.Finally, it is
shown in section 5.7 that a high enough length of rods is
crucial for a gradient shear banding transition to occur.
Also, it is demonstrated that none of the systems under
investigation undergo stable gradient shear banding.},
cin = {ICS-3},
cid = {I:(DE-Juel1)ICS-3-20110106},
pnm = {551 - Functional Macromolecules and Complexes (POF3-551) /
DiStruc - Directed Colloidal Structure at the Meso-Scale
(641839)},
pid = {G:(DE-HGF)POF3-551 / G:(EU-Grant)641839},
experiment = {EXP:(DE-MLZ)KWS2-20140101},
typ = {PUB:(DE-HGF)11},
url = {https://juser.fz-juelich.de/record/860717},
}