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Viscosity of Polymers

Viscosity of Polymers

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Published by sevanth

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Published by: sevanth on Feb 20, 2010
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02/22/2011

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Chapter 6
Viscosity
6.1 Introduction
Viscosity of a polymer solution depends on concentration and size (
i.e.
, molecular weight) of thedissolved polymer. By measuring the solution viscosity we should be able to get an idea aboutmolecular weight. Viscosity techniques are very popular because they are experimentally simple.They are, however less accurate and the determined molecular weight, the viscosity average molec-ular weight, is less precise. For example,
v
depends on a parameter which depends on the solventused to measure the viscosity. Therefore the measured molecular weight depends on the solventused. Despite these drawbacks, viscosity techniques are very valuable. This chapter discusses thetheory and methods for determining polymer molecular weight by measuring solution viscosity
6.2 Viscosity and Viscosity Nomenclature
Figure 6.1 shows a piece of a liquid moving at a strain rate ˙
γ 
under an applied shear stress of 
τ 
.The viscosity of the liquid is the ratio of the applied shear stress to the resulting strain rate (orequivalently, the ratio of the shear stress required to move the solution at a fixed strain rate to thatstrain rate). The shear strain in Fig. 6.1 is
γ 
=
dudy
(6.1)where
u
is displacement in the
x
direction. The strain rate is therefore˙
γ 
=
ddtdudy
=
ddydudt
=
dv
x
dy
(6.2)where
v
x
is velocity in the
x
direction. The relations between viscosity (
η
), shear stress (
τ 
), andshear rate (˙
γ 
) are
τ 
=
η
˙
γ 
or ˙
γ 
=
τ η
or
η
=
τ 
˙
γ 
(6.3)77
 
78
CHAPTER 6. VISCOSITY 
F
τ
=FAd
γ 
dt
γ 
=
γ 
Figure 6.1: A piece of a liquid moving at shear rate ˙
γ 
under an applied shear stress of 
τ 
.
A Newtonian fluid is one in which the viscosity is independent of the shear rate. In other wordsa plot of shear stress versus shear strain rate is linear with slope
η
. In Newtonian fluids all theenergy goes into sliding molecules by each other. In non-Newtonian fluids, the shear stress/strainrate relation is not linear. Typically the viscosity drops at high shear rates — a phenomenon knownas shear thinning. Although the following development will not discuss shear rate effects in detail,the possibility of experimental results being affected by the shear rate of the measurement shouldbe kept in mind. Plots of shear force
vs.
shear rate for Newtonian and non-Newtonian fluids aregiven in Fig. 6.2.We let
η
0
be the viscosity of the pure solvent and
η
be the viscosity of a solution using thatsolvent. Several methods exist for characterizing the solution viscosity, or more specifically, thecapacity of the solute to increase the viscosity of the solution. That capacity is quantified by usingone of several different measures of solution viscosity. The most common solution viscosity termsare:1. Relative viscosity
η
r
=
ηη
0
(6.4)2. Specific viscosity
η
sp
=
η
η
0
η
0
=
η
r
1 (6.5)3. Inherent Viscosity
η
i
=ln
η
r
c
(6.6)4. Intrinsic Viscosity[
η
] = lim
c
0
η
sp
c
(6.7)
 
6.2. VISCOSITY AND VISCOSITY NOMENCLATUR
79
 
Non-NewtonianNewtonianShear Rate
   S   h  e  a  r   F  o  r  c  e
Figure 6.2: Schematic plots of shear force
vs.
shear rate for Newtonian and non-Newtonian fluids.
In these equations,
η
is solution viscosity,
η
0
is viscosity of the pure solvent, and
c
is concentration.Relative viscosity is self-explanatory. Specific viscosity expresses the incremental viscosity dueto the presence of the polymer in the solution. Normalizing
η
sp
to concentration gives
η
sp
/c
whichexpresses the capacity of a polymer to cause the solution viscosity to increase;
i.e.
, the incrementalviscosity per unit concentration of polymer. As with other polymer solution properties, the solutionsused for viscosity measurements will be nonideal and therefore
η
sp
/c
will depend on
c
. As withosmotic pressure, it will probably be useful to extrapolate to zero concentration. The extrapolatedvalue of 
η
sp
/c
at zero concentration is known as the intrinsic viscosity — [
η
]. [
η
] will be shown tobe a unique function of molecular weight (for a given polymer-solvent pair) and measurements of [
η
] can be used to measure molecular weight.The remaining form for the viscosity is the inherent viscosity. Like
η
sp
, ln
η
r
is zero for puresolvent and increases with increasing concentration, thus ln
η
r
also expresses the incremental vis-cosity due to the presence of the polymer in the solution. Normalizing ln
η
r
to concentration orln
η
r
/c
gives the inherent viscosity In the limit of zero concentration,
η
i
extrapolates the same as
η
sp
/c
and becomes equal to the intrinsic viscosity. This can be proved by:lim
c
0
ln
η
r
c
= lim
c
0
ln(1 +
η
sp
)
c
= lim
c
0
η
sp
c
= [
η
] (6.8)We can thus find [
η
] be extrapolating either
η
sp
/c
or
η
i
to zero concentration. When
c
is not equalto zero the specific viscosity and inherent viscosities will be different, even for an ideal solution. Inideal solutions
η
sp
/c
will be independent of concentration, but
n
i
will depend on concentration.

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