2364 Ind. Eng. Chem. Res.

1994,33, 2364-2367

Rheology of Shear Thinning Polymer Solutions

Frans L. Muller7 and John F. Davidson'
Department of Chemical Engineering, Pembroke Street, Cambridge CB2 3RA, England

A viscometer was used to measure power law parameters K and n for aqueous solutions of
(carboxymethy1)cellulose(CMC), taken from a bubble column. The results were analyzed by plotting
n as a function of Log K. Literature data and the present experiments show that dilution gives a
slope of -0.147 on the Log K-n plot. Results with different molecular weights show, by contrast,
a slope of -0.345. Results from the bubble column are consistent with (i) change of CMC molecular
weight due to shear, the slope of the Log K-n plot being -0.345, and (ii) change of CMC molecular
weight due to oxidation by hydrogen peroxide when this was added: the slope of the Log K-n plot
was -0.223. That this was less than -0.345 is believed to be due to dilution. The effect of moderate
temperature changes was also summarized. An important conclusion is that when CMC solutions
are used in bubble columns or stirred tanks for mass or heat transfer studies, attention must be given
to changes of properties due to shear, oxidation, dilution, and temperature.

Introduction 1000-

Over the past 10 years much effort has been put into
measuring gas-liquid mass and heat transfer coefficients
q 0 800-
in agitated tanks and bubble columns containing highly 3
0

viscous aqueous polymer solutions, with effective viscosi-

ties between 0.1 and 3 Pa s. These liquids are usually 0 600
shear thinning and have rheological properties similar to
"real" industrial media like (i) fermentation broths and
(ii) liquid suspensions of small particles (Shah, 1982).The b
hydrodynamical behavior of gas-liquid contactors con- 2 0400
c
taining highly viscous liquids is characterized by the
Slopes -0 147
presence of very large bubbles (up to 15 cm). This is I
because turbulence is strongly reduced, diminishing the 0200 ' " '"'1 ' """' " "" ' _y

1 IO loo loo0 lo000

bubble breakup rate (Philip et al., 1990).
Many experiments are performed using (carboxymeth-
y1)cellulose (CMC) solutions in water; see for instance
Schumpe and Deckwer (1987). CMC is shear thinning
and the rheological behavior is usually characterized by
the Ostwald-deWaele (or power law) model:
n-1
= -WYI
* *
7 Y peff = W+eftin-'
This empirical relationship describes the shear stress 7 as
a function of the shear rate i. = aular, the consistency
index K (Pa sn), and the flow behavior index n (dimen-
sionless).
The parameters of a gas-liquid contactor like mass and
heat transfer coefficients are usually correlated with
respect to viscosity by use of the effective viscosity (eq 1).
The local shear rate in such systems cannot be calculated,
and in the literature effective viscosity is calculated from
a characteristic (effective) shear rate of the system; for a
bubble column (tubular geometry) the effective shear rate
is the ratio of the center line liquid velocity and the
radius: qeff = uJR.
The rheological properties of CMC are strongly related
to the molecular weight and concentration. CMC is
available in a low-, a medium-, and a high-viscosity form,
viscosity increasingwith molecular weight. CMC solutions
(0-8 % ) have in general effective viscosities peff between
1and 3000 mPa s. The physical properties of the CMC
solutions differ only slightly from those of water: for the
quoted range of peff, density varies from 1000 to 1004 kgJ
m3 and the surface tension is between 0.065 and 0.072
* Author to whom correspondence should be addressed.
+ Departement de GBnie Chimique, Centre de Recherche de
Royallieu, B P 649, 60206 Compiegne, France.
Ossa-5885/94/2633-2364~04.50JO 0 1994 American Chemical Society
K (m Pas")
The consistency index
Figure 1. Consistency index K and flow behavior index n: plot of
published data.The changes in K and n arose from changes in
concentration of CMC and PAA. References for the plotted data are
as follows: low-ukcosity CMC (A)from Buchholtz etal. (1978),Voigt
et al. (1980), Deckwer et al. (1982), Schumpe and Deckwer (1982,
198'0, Vatai and Tekic (1986), Philip et al. (1990); high-viscosity
(1)
CMC (0) from Godbole et al. (1982,1984), Kelkar and Shah (1985),
Divine et al. (1986), Haque et al. (1986), Kawase and Moo-Young
(1986),Kawase et al. (1987);polyacrylamide (PAA, 0)from Hecht
et al. (1980), Nakanoh and Yoshida (1980), Kawase et al. (1987).
NJm (Godbole et al., 1984; Schumpe and Deckwer, 1987;
Zhao, 1989).
In mass transfer experiments, the viscosity parameters
(K, n ) are often considered to be constant system proper-
ties, as system temperature and polymer concentration
are assumed to vary only slightly (seefor instance Schumpe
and Deckwer (1982, 1987). However, strong changes in
the viscosity parameters were observed during mass
transfer experiments in a bubble column (Muller and
Davidson, 1992),which made a closer study of the viscosity
parameters necessary. The effects on K and n of (i)
molecular weight, (ii) concentration, (iii)temperature, and
(iv) polymer degradation were evaluated using a new
method of viscosity data analysis.
The Log K-n Plot. In the literature, the polymer
concentrations are often not given. To investigate the
experimental parameters found in the literature, the flow
behavior index n is plotted versus Log K (Figure 1). The
three polymers plotted, low- and high-viscosity CMC and
polyacrylamide (PAA), are frequently cited in mass
transfer literature. The figure shows a linear dependence
of the flow behavior index (n)on Log K, with a slope
(-0.147) for all three polymers.
 Alternatively phrased: due to CMC concentration the
viscosity parameters move over a line in the Log K-nplane
with slope -0.147. The Log K-n plot is a powerful way
of analyzing the effect of various parameters on the
rheological behavior of power law solutions. The results
in Figure 1show that the consistency index K is a useful
indicator in considering changes in the viscosity of power
law solutions, but not for comparing different types of
liquid. A decrease in the (effective) viscosity of a CMC
solution is caused by a decrease in the consistency index
( K ) and is always coupled to an increase of the flow
behavior index (n);i.e., for a certain polymer, solutions of
various concentrations and temperatures behave more
Newtonian for lower consistency indices.
Experimental Section
In this work only high-viscosity CMC was used. The
CMC purchased (BHDProduct No. 27929) originated from
three different production batches: CMC1, batch no.
2451460, CMC2, no. 4268280; and CMC3, no. 4498100.
The CMC solutions used to analyze the effect of concen-
tration were made in batches of 250 mL. Most of the
CMC solutions were made in batches of 20-25 L by adding
CMC to hot "Cambridge" tap water (-60 "C), while stirring
vigorously. Using hot water speeded up the dissolving
process considerably. The 25-L batches, characterized by
their date of formation, are not necessarily made from
CMC out of a single batch.
The viscosity parameters were measured using a Haake
Couette viscometer (VT-24). The effective viscosity of
the solution was determined at six different shear rates
between 10 and 400 s-l; K and n were obtained by plotting
the logarithm of the measured peff against the logarithm
of measured Teff;linear regression then gave K and n from
eq 1. The correlation coefficient was usually 0.99,
indicating a good fit of the power law model. Each run
was usually repeated. The range of shear rates for the
measurements corresponds with the shear rates expected
in a bubble column (50-250 8-1). The temperature of the
liquid analyzed was measured by immersing a thermo-
couple in the liquid immediately after the viscosity
measurement. The viscosity parameters were converted
to the parameters as for 20 "C using eqs 2 and 3 given
below.
Rssults
Effect of Concentration of CMC. The viscosity
parameters of the different CMC batches (CMC1, CMC2,
CMC3) are plotted at several concentrations on a Log K-n
plot (Figure 2), which is similar to Figure 1. The
dependence of the flow behavior index on K is fairly well
described, for a given batch, by lines with a slope of -0.147,
the value deduced from published data (Figure 1). Note
that the three CMC batches have different characteristics.
This is most likely caused by their different molecular
weights, CMCl having the highest molecular weight and
CMC 3 the lowest.
The alternate plot is for solutions of equal concentration
(1wt 7% ); i.e., changing the molecular weight. The viscosity
parameters move in the Log K-n plane along a line of
slope -0.345.
Effect of Temperature. Increasing the temperature
of a solution decreases its viscosity. The effect of
temperature was investigated by changing the viscometer
temperature (Tr) between 18 and 32 "C, a range cor-
responding to the change in "room temperature". Figure
3 shows the results for the three CMC batches. Within
Numbers next to the points
The consistency index
Figure 2. Effect of concentration from present experiments. Each
set of points for a given batch of CMC are reasonably well correlated
by a line of slope -0.147, the value deduced from published data,
Figure 1. The alternate plot is for a fixed concentration of CMC (1
wt %) but for different batch numbers of decreasing molecular
weight: the slope is-0.345. Data are for CMCl (A),CMC2 ( O ) ,CMC3
( O ) ,and the initial values of K and p for 25-Lbatches of 1.0 wt %
CMC solutions used for the bubble column experiments ( 0 ) .
this narrow temperature interval, Log K and n are linearly
related to temperature, with proportionality constants
independent of CMC concentration and batch numbers
(i.e., molecular weight). It follows that due to temperature
change, the viscosity parameters move in the Log K-n
plane along a line with slope -0.294.
The temperature a t which an experiment is performed,
Te, is usually different from the temperature Tr at which
the viscosity parameters are measured. From Figure 3 it
follows that the measured viscosity parameters can be
corrected for temperature to give (K,n) at the operating
temperatures during the experiment:
Log K(Te) = Log K(T,) - 0.0187(Te- T,) (2)
n(Te) = n(T,) + 5.50 X 103(Te - T,)
(3)
The effects of the temperature corrections are consider-
able: if the temperature difference (T,- Tr) is 5 "C, the
differences in experimental and measured viscosity pa-
rameters are up to 25% for K and up to 5% for n.
An exponential decay of the viscosity (consistencyindex)
with temperature is noted for many liquids. This can be
explained by the theory of Eyring and co-workers, which
shows that the relation between viscosity and temperature
can be approximated by an Arrhenius equation (Glasstone
et al., 1941; Bird et al., 1960):
p = KoeEdRT (4)
Expanding the power of e to a series around Tr:
Applying eq 5 to K for a temperature Tr = 20 OC gives an
activation energy of 13.4 kJ/mol for CMC solutions,
Effect of CMC Degradation. The viscosity data, on
which the following discussion is based, were obtained
during a series of mass transfer experiments. The
degradation occurred in a 14-cm-diameter bubble column,
from which samples were taken, from time to time, for
measurement in the viscometer. The changes of K and n
were achieved over a total of about 20 h of bubbling air
through the column. The superficial gas velocities ranged
from 2 to 11cmls, and the liquid depth was between 1.5-
1.8 m (see Muller and Davidson (1992) and also Muller
2366 Ind. Eng. Chem. Res., Vol. 33, No. 10, 1994
io5:# ' l
: Temperature effect on K
F 'lopes
'

-Ools7
' ' '
- i
- Effect
[
' " ' " " "
of temperature on n
Slopes 00055
I " ' 1 100

+ Same solution
measuredon
different days

-201 ' " " ' " " ' 1 " '1 0.20
15 20 2s 30 35 15 20 25 30 35
Temperature ("C) Temperature ("C)

Figure 3. Influence of temperature on consistency index (K)and flow behavior index (n)for five CMC solutions. Note that, since both Log
K and n are proportional to the temperature, the viscosity parameters in a Log K-n plot are related by a straight line (slope -0.294), as
temperature varies. Data are for 2.0 wt % CMCl (A), 1.0 wt % (0) and 1.5 wt % ( 0 )CMC2, and 1.0 wt % (0) and 1.5 w t % (e) CMC3.
0 158
060, I
Chemical degradation by H,02 '
Mechanical degradation - 1
Slopes -0 345
-I
I

x
0 -
U
E -
L -

$ 0.65-

0 50'
2000 3000 4000
The consistency index: K (mPas")
The consistency index: K (m Pas")
Figure 4. Mechanical degradation by shear of CMC molecules due Figure 6. Degradation of viscosity of CMC solutions, due to the
to residence of up to 20 h in the bubble column. The data follow lines presence of hydrogen peroxide, added by a steady feed, to the bubble
of slope-0.345, similar to the effect of decreasingthe molecular weight column, of aqueous HzOz. The data were obtained from several
at constant weight fraction polymer (Figure2). The data were obtained batches, characterized by date of formation (day/month/year): 31/
from severalbatches, characterized by date of formation (daylmonthi 10/91 (a), 11/11/91 ( O ) , 13/11/91 (El), 20/11/91 ( 8 ) ,28/11/91 ( O ) ,
year): 19/09/91 (O),11/11/91 ( O ) , 13/11/91 (El), 20/11/91 (LP),and and 05/12/91 (A).
28/11/91 ( 0 ) .
trends. If a polymer breaks down, the average chain length
1 ''
' ' ' ' '
' ' ' ' ' '
I 1wtWhighviscosityCMC (molecularweight) is reduced therefore the chains become
3 io3
CMC degradation rates by H,O,
rate constant: -0.00392
made 25 1 batches less entangled and/or are more easily disentangled by the
h i 1 Date of the steady shear forces; Le., the liquid has less resistance to shear and
state experiment is thus less viscous. Chain breakup is caused by two main
0
0
31/10/91
11/11/91
processes: mechanical breakdown of CMC chains by shear
0 13/11/91 forces due to bubbling and chemical breakdown of the
E
o
20/11/91
28/11/91
CMC by oxidation reactions due to dissolved oxygen, or
A 05/12/91 peroxide if present.
The mechanical degradation of CMC is relatively slow,
and was most noticeable at high viscosities (K> 2000 m
Pa sn) when the number of entanglements is high, and the
viscous forces, due to a given shear rate, are large. The
0 40 80 120 160 200 change of the viscosity parameters can be observed on a
Time peroxide is flowmg into the column (mm) K-n plot (Figure 4). Note that there is no significance in
the dates given in Figure 4;they are merely labels for the
Figure 5. Degradation of viscosity of CMC solutions as function of batches. Due to degradation the viscosity decreases; the
the time hydrogen peroxide has been flowing into the column. The Log K-n plot is a straight line with a slope of -0.345,similar
data were obtained from several batches, characterized by date of
formation (day/month/year): 31/10/91 (a), 11/11/91 (a), 13/11/91 to the effect of the molecular weight of CMC (see Figure
(El), 20/11/91 (a),28/11/91 ( O ) ,and 05/12/91 (A). 2). This validates the hypothesis that shear decreases the
average CMC chain length.
(1993)). Each data series is characterized by the date of Chemical breakdown of the CMC was observed in long-
formation of the 25-L batch of liquid in the column (see standing batches of CMC solutions; oxygen concentrations
Figures 4-6). corresponding to equilibrium gas phase concentrations
During the bubbling experiments it was noted that the below 21% (as low as 10 vol % oxygen) indicated that
viscosity of the CMC solutions decreased with time: K oxygen was consumed. This might explain why very old
decreased and the flow behavior index (n)increased with (months) batches of CMC have decreased viscosities. The
time. Degradation of the CMC is the main cause of these chemical degradation of CMC solutions was speeded up

considerably when hydrogen peroxide was added to the
liquid. During steady state mass transfer experiments, a
peroxide feed solution was continuously decomposed in
the column. The feed solution (0.3 wt % H202 and 1 wt
?Ti CMC in water) decayed overnight from K = 2 P a sn to
K = 0.003 Pa sn. Figure 5 shows that, during steady state
experiments, K decays exponentially with the time
peroxide solution was flowing into the column. The rate
constant is about 3.92 X 103 min-1 and is independent of
the batch number. The peroxide concentration in the
column could not be measured. The data were obtained
by sampling liquid from the column and making mea-
surements in the viscometer.
The same data plotted in a Log K-n plot (Figure 6 )
show that the viscosity decrease due to chemical degrada-
tion of CMC by peroxide is described by a line with slope
-0.223. This value lies between that of mechanical
degradation (chain breaking only, slope -0.345, Figure 4)
and that of dilution of the CMC solution (concentration
effect, -0.147, Figure 2), indicating that the effect of the
peroxide addition must be attributed not only to (i)
degradation of the CMC chain length but also to (ii)
dilution of the solution or (iii) chemical modification of
the polymer.
Conclusions
For shear thinning power law liquids it is found that the
flow behavior index (n)is strongly related to Log K (the
consistency index). Changing various parameters showed
the relation n-Log K to be linear, the slope of the line
being an indication of the type of process that affects the
polymer solutions. For CMC solutions, dilution gives rise
to a slope of -0.147, whereas changes in molecular weight
cause the slope to be -0.345 on the Log K-n plot. Effects
on CMC solutions were observed as follows:
(i) The plot of Log K-n, arising from temperature
change, has a slope of -0.294. This may indicate the effect
of increased mobility of the polymer chains.
(ii) The plot of Log K-n, generated by shear due to
bubbling, has a slope of -0.345. This is consistent with
the slope due to the change of molecular weight, -0.345,
and suggestsbreakdown of polymer molecules due to shear.
(iii)Oxidation by hydrogen peroxide, with some dilution,
gives a slope of -0.223 on the Log K-n plot, suggestive of
polymer breakdown by oxidation allied to a dilution effect;
as noted above, the dilution effect alone gives a smaller
slope, -0.147 on the Log K-n plot.
The analysis of viscosity data using a Log K-n plot gives
a useful way of summarizing the data. The slope of a
series of ( K , n) points gives an indication of the process
affecting the system's rheological behavior. Further it
allows the interpolation of the viscosity parameters ( K ,
n),which is necessary if for instance mass or heat transfer
measurements are to be related to viscosity. In addition,
the plot is very useful for a more complete comparison of
the rheological behavior of polymer solutions.
Finally, the results show that extreme care is needed
when relating heat and mass transfer data for gas-liquid
contactors containing polymer solutions to viscosity
parameters, because these parameters may change during
the experiment on account of (i) shear degradation of
polymers, (ii) oxidation of polymers, (iii) temperature
changes, and (iv) dilution.
Ind. Eng. Chem. Res., Vol. 33, No. 10,1994 2367
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Received for review December 29, 1993
Revised manuscript received May 25, 1994
Accepted June 22, 1994.
Abstract published in Advance ACS Abstracts, August 15,
1994.