LIQUID CRYSTAL

POLYMERS
RHEOLOGY
Rheology is the branch of science which deals with study of deformation and
flow of visco elastic materials.

Liquid-viscosity; solid-elasticity; viscoelastic-rheology.

We will study two types of rheological behavior:

1. Lyotropic liquid crystalline polymers and their rheological behavior

2.Thermotropic liquid crystalline polymers and their rheological behavior

Lyotropic liquid  In LLCPs viscosity increases with an increase
in polymer concentration, and achieves a
crystalline critical point, and then a slight decrease in
viscosity of LLCPs is observed.
polymers and  Changes in viscosity at the critical
concentration of the polymer, are
their characteristic for LLCPs

rheological  The characteristic phase diagram divides LC

phases into an isotropic phase, an
behavior anisotropic LC phase and a mixture of the
two phases.
POLYMER CONCENTRATION DEPENDENCE FOR
LLCPs
Region I shows an isotropic phase that
forms for a low concentration of rods at
various temperatures.

After exceeding critical concentration

under a higher temperature, the solution
transforms into an anisotropic LC phase
(Region II).

Between these two phases, at a higher

temperature, there exists a thin range of
concentrations in which the solution
creates a two-phase mixture called
isotropic and anisotropic LC (Region III).
 Region I usually occurs at low shear rates
and characterizes shear thinning. It is
prompted by the alignment of liquid crystal
domains along the shear direction.
 Region II appears at intermediate shear
rates and is assigned to a plateau in which
all LC domains are oriented along the shear
direction.
 Region III, occurs at the highest shear rates,
in which LC domains are destroyed by over
scale shear stress and free crystals are
layered along the shear direction, leading to
shear thinning.
MARTIN EQUATION

 The relation between the viscosity of the polymer solution and the polymer
concentration can be described by modified Martin equation
  TLCPs are a class of high-performance
Rheology of engineering thermoplastic polymers.
compared with standard polymers, TLCPs
Thermotropic have low or no dye swell during extrusion.
 They have high glass temperature, low
liquid coefficient of thermal expansion, good
dielectric properties, and good resistance to
crystalline weather conditions.

polymers  Rheology of TLCPs exhibit unique behaviors

that arise from complex interactions
between crystals and flow.
 TLCP

01 02 03
TLCPs are classified Types II and III are the Type II are
into three categories: easiest to process characterized by
Types I, II, and III, because they have a better mechanical
distinguished from relatively low melting properties compared
each other in terms of temperature and low with Type III.
thermal performance. melt viscosity,
 TLCPs are usually built from aromatic
polyesters or co polyesters characterized by
high symmetry in the chemical structure
and give extremely high stiffness and
strength, yet have sufficient flexibility.
BLENDS

Knowledge about the rheological behavior of TLCP polymers is useful

for their further processing .

Usually TLCP is used as a single component or part of polymer blends

with a variety of conventional isotropic polymers.

The most commonly used and industrial important TLCPs are co

polyester of 4-hydroxy-benzoic acid (HBA) and 2- hydroxy-6-naphthoic
acid, well-known as Vectra A950 and Vectran
Vectra A950 of 4-hydroxybenzoic acid(73%)
and 2-hydroxy-6- naphthoic acid(27%)
VISCOSITY-SHEAR CURVE OF ANISOTROPIC
AND ISOTROPIC MELT
 In the case of polymer blends, TLCPs combine miscible or
immiscible blends with other polymers.
 Adding a small amount of a TLCP to a polymer blend is
advantageous because its low melt viscosity can reduce the
melt viscosity of polymer blends, simplifying processing.
 Determination of rheological characteristics including
viscosity, the flow shear rate, and viscosity curves of TLCPs
have an important role in predicting their behavior during
various processing methods such injection molding, extrusion,
or spinning, during which shear forces at different rates of
shear are applied.
THE THREE-REGION LOGARITHMIC VISCOSITY
CURVE OF TLCPs
 The three-region viscosity curve proposed by Onogi and
Asada is often used to consider thermotropic liquid crystal
polymer rheology
 At Regions I and III, the range of the low and high shear
rate, the viscosity is shear thinning
 At Region II the region of the Newtonian plateau is assigned.
 The rheological properties of TLCPs strongly depend on the temperature and can be
determined in theoretical and experimental ways.
 Measurements for this kind of LCP are taken using instruments such as capillary
rheometers.
 To understand the rheological behavior of LCPs it is necessary to use various structure
probing techniques to study their molecular and supermolecular structural levels.
 These techniques include microscopic, rheological, rheooptical, and small angle light
scattering, , and small angle x-ray scattering