Cellulose 9: 327–335, 2002.

327
© 2002 Kluwer Academic Publishers. Printed in the Netherlands.

Synthesis and characterization of carboxymethylcelluloses from non-wood

pulps II. Rheological behavior of CMC in aqueous solution

Claudia Barba 1, Daniel Montané 1,*, Xavier Farriol 1, Jacques Desbrières 2 and Marguerite
Rinaudo 2
1
Department of Chemical Engineering, Rovira i Virgili University, Avinguda dels Països Catalans 26, E-43007
Tarragona (Catalunya), Spain; 2Centre de Recherches sur les Macromolécules Végétales (CERMAV-CNRS),
Joseph Fourier University, BP53, F-38041 Grenoble Cedex 9, France; *Author for correspondence (e-mail:
dmontane@etseq.urv.es)
Received 9 October 2001; accepted in revised form 25 March 2002

Key words: Carboxymethylcellulose, Degree of substitution (DS), Gel-like behavior, Rheology

Abstract

This paper concerns the rheological behavior of carboxymethylcelulloses (CMC) derived after one and two suc-
cessive steps from different non-wood bleached cellulose pulps. CMC rheological characterization was achieved
in 0.1M NaCl solution, as a function of polymer concentration. The evidence of a critical concentration (C* < 1
g/L) is discussed from steady shear and dynamic experiments. Rheological properties of the CMC were found to
depend on the cellulose source reactivity and on their degree of substitution (DS). Higher molecular weight of
initial cellulose was accompanied by higher apparent intrinsic viscosity of the CMC produced. Depending on the
CMC concentration and on the degree of etherification, the system behaves as a solution or as a gel. In the case
of abaca CMC sample, it is shown that after only one step of chemical modification and above a polymer con-
centration of 20 g/L, the system behaves as a gel. The gel behavior was studied as a function of temperature. In
the temperature range from 25 to 45 °C, the rheological behavior was found to remain almost constant due to the
existence of dispersed swollen aggregates. This unusual characteristic represents an advantage for applications
such as oil recovery in the petroleum industry, where viscosity of the recovered fluid should not diminish with
temperature.

Introduction The viscosity of CMC aqueous solution is directly

Carboxymethylcellulose (CMC) is a cellulose-derived
ether widely used as an additive in industrial applica-
tions due to its rheological properties in aqueous so-
lution. The wide range of carboxymethylcellulose ap-
plications (for example in the food industry,
detergency, coating technology, pharmaceuticals, and
drilling muds) involves a broad variety of processes
such a storing, mixing, pumping, heating, cooling,
separation, etc. (Bartdorf and Rossman 1973). For a
better understanding of these processes, it is impor-
tant to characterize the cellulose derivative by know-
ing the rheological behavior of CMCs solutions under
different effects such as polymer concentration, tem-
perature and external rheological conditions.
related with the polymer stiffness, its molar mass and
concentration, temperature, ionic strength, and shear
stress adopted for measurements (Greenway 1994). In
a wide range of polymer concentrations, one observes
a Newtonian behavior followed by a shear thinning
regime when the viscosity is tested as a function of
shear rate; this transition will be later discussed as
well as the comparison between the viscosity deter-
mination from dynamic (oscillatory) and flow experi-
ments.
Solution properties and rheological characteristics
depend largely on the CMC degree of substitution
(DS) but also on the morphology of the original plant
used to isolate the cellulose and on the pulp charac-
teristics such as intrinsic viscosity in given condi-
328

tions. Generally at low DS, most of the chemical Table 1. CMC degree of substitution and intrinsic viscosity.
modification reaction has occurred in amorphous re- Sample a DS [␩] (mL/g) k⬘
gions or on surfaces of residual crystalline domains,
where aggregates of unsubstituted or poorly substi- Abaca-1 (ABE1) 0.95 601 0.51
tuted regions may appear as highly swollen opaque Abaca-2 (ABE2) 2.4 410 0.49
or transparent macrogel particles, resulting in differ- Sisal-1 (CSB1) 0.93 396 0.34
Sisal-2 (CSB2) 2.25 327 0.52
ent rheological properties and solution behavior
Jute-1 (JB1) 1.04 311 0.71
(Rinaudo et al. 2000).
Jute-2 (JB2) 2.3 202 0.78
In this work we have explored the non-wood CMC
Line-1 (LB1) 0.92 456 0.56
rheological properties in relation with the accessibil-
Line-2 (LB2) 2.0 268 0.68
ity and physico-chemical characteristics of pulp raw
Miscanthus-1 (MI1) 0.73 192 —
material described in the first part of this series (Barba Miscanthus-2 (MI2) 1.45 403 0.55
et al. 2002). Miscanthus enzyme-1 (MIX1) 0.75 165 —
Miscanthus enzyme-2 (MIX2) 1.43 451 0.55
a
After one or two etherifications.
Experimental

Material cm with an angle of 4°. The measurements were per-

Carboxymethylcelluloses (CMCs) were synthesized
one and two successive times from different bleached
pulps described previously (Barba et al. 2002; this is-
sue). The pulps were obtained by ordinary and steam
explosion procedures from different initial materials:
abaca (ABE), sisal (CSB), linen (LB), jute (JB), Mis-
canthus sinensis (MI) and enzymatic bleached treated
Miscanthus sinensis pulps (MIX).
formed in the frequency range of 0.01 to 100 Hz at a
fixed temperature of 20 °C. Temperature can vary us-
ing a Peltier plate. All carboxymethylcellulose solu-
tions were prepared in 0.1M NaCl. The linear regime
was checked and dynamic experiments were per-
formed within this linear viscoelastic region.
Results and discussion

Analytical methods CMCs prepared from bleached pulps of abaca, jute,

Intrinsic viscosity
A vertical Ubbelohde viscometer of 0.5 mm diameter
(at 25 °C) coupled to a FICA Viscomat automatic
counter were used to measure the intrinsic viscosity
of CMC samples in a range of concentrations from
0.016 g/L to 1 g/L.
The initial solution was prepared from 10 ml of the
CMC sample in water (2 g/L) to assure best solubil-
ity, mixed with 10 ml of 0.2M NaCl in order to ob-
tain a solution of 1 g/L in 0.1M NaCl. For further
concentrations, automatic dilutions in 0.1M NaCl
from the first solution were achieved obtaining 0.66,
0.5, 0.33, 0.25 and 0.16 g/L.
sisal, linen and Miscanthus sinensis were analyzed for
degree of substitution, intrinsic viscosity and rheolog-
ical characteristics. Table 1 shows the CMC degree
of substitution after one and two successive etherifi-
cations. After the first reaction, abaca, sisal, jute and
linen CMC samples presented a DS close to 1, while
after the second etherification, they present a DS
around 2. Miscanthus sinensis CMC samples display
a DS of 0.75 and 1.45 after one and two etherified
reactions, respectively. The lower DS found in Mis-
canthus sinensis CMC might be caused by the large
fraction of low molar mass components and cellulose
accessibility.
Rheological characterization of the CMC solutions

Dynamic viscosity As reported in the Introduction, CMC is used in a

Dynamic measurements were performed with a Rhe-
ometer AR1000 from TA Instruments (frequency
from 10 −2 to 10 2 Hz and strain from 1 to 100%) us-
ing cone-plate geometry with two diameters: 2 and 6
wide range of applications; however, each individual
field of applications is so complex as to rule out a di-
rect correlation with molecular data for optimization
purposes. Rheological investigations allow material
functions to be directly determined quantitatively and
 329

Table 2. Characteristics of CMC samples in dilute solutions.

Sample M w (g/mol) C* [␩] M va (g/mol)

ABE2 277900 0.53 200700

MIX2 232700 0.51 218000
a
With K = 1.65 × 10 −2 and a = 0.83, [␩] being in mL/g.

to demonstrate the role of polymer concentration, mo-

lar mass and DS.

Flow measurements

The intrinsic viscosity [␩] determined in the Newto- Figure 1. Normalization of the specific viscosity in the Newtonian
nian regime and the Huggins constant k⬘ are given in domain, ␩ sp against the overlap parameter C[␩]. ‰ ABE2, 䡬 ABE1
and 䉲 model.
Table 1. Except for Miscanthus sinensis, all substrates
have similar trends. As usually found, the intrinsic
viscosity is lower for the CMC obtained after two function of the overlap parameter C[␩] (Morris et al.
successive treatments than after the first treatment 1981; Rinaudo 1990).
(Rinaudo and Hudry-Clergeon 1967). This behavior As discussed previously (Milas et al. 1985;
reveals the degradation of the cellulose derivative Grigescu and Kulicke 2000) a unique curve is ob-
during the second step of etherification. On the other tained corresponding to the development:
hand, in both M. sinensis cases, viscosity increases
␩ sp ␥ → 0 ⫽ C关␩兴 ⫹ k ⬘共C关␩兴兲 2 ⫹ B共C关␩兴兲 n (2)
after the second step due to an improvement in the
etherification and solubility of the fibers that have not
When C[␩] increases, the transition between dilute
reacted well during the first step reaction. In fact, the
and semi-dilute regimes is characterized by a critical
physical aspect of the sample changes from turbid to
concentration C*; this transition is well characterized
clear solution in the same time.
by the departure of the curve from the slope 1 when
The viscosity-average molar mass can be calcu-
the ␩ sp values are plotted against C[␩]+k⬘(C[␩]) 2,
lated using the Mark Houwink Equation (relation 1)
characterizing the dilute regime (not shown). The val-
established for CMC in 0.1M NaCl at 25 °C by Ku-
ues obtained for C* are given in Table 2. They are in
rata and Tsunashima (1989). Typical values of param-
the range C*[␩] ⬃ 0.5.
eter K for CMC range from 1.0×10 −4 to 4.3×10 −2
Recently, a general development was proposed
when salt concentration varies with C expressed in
which allows to draw the log–log plot ␩ sp (C[␩])
g/ml:
without any difficulty for a polymer in a good solvent
关␩兴共mL/g兲 ⫽ 1.65 ⫻ 10 ⫺ 2M 0.83 (1) (Cowman et al. 2002), as displayed in Figure 1:

␩ sp ⫽ C关␩兴共1 ⫹ k 1共C关␩兴兲 ⫹ k 2共C关␩兴兲 2 ⫹ k 3共C关␩兴兲 3兲

Nevertheless, due to the structure of CMC solution
(existence of insoluble particles), only an apparent (3)
molar mass should be determined from the intrinsic
with k 1 = 0.4, k 2 = k 12/2!, and k 3 = k 13/3!
viscosity value. In Table 2, M w values for ABE2 and
Figure 1 shows the specific viscosities in the New-
MIX2 obtained by GPC equipped with a light scat-
tonian regime as a function of the overlap parameter
tering detector are given. These values are slightly
C[␩] in a logarithmic plot. The results obtained with
lower than the M v values obtained from Equation 1.
ABE2 fit with the theoretical prediction (Equation 3).
For any given polymer–solvent system the molar
For ABE1, the curve deviates in relation with the ex-
mass of the dissolved macromolecules and their con-
istence of interchain interactions. Viscosities in the
centration in the solutions are crucial parameters for
Newtonian region and their dependence on shear rate
influencing the rheological properties. In moderately
were determined in the range of polymer concentra-
concentrated solution, as used in many applications,
tion from 10 to 100 g/L; a few experimental results
the thermodynamic solvent quality affects the viscos-
obtained for the viscosity are given in Figure 2. The
ity and the zero-shear viscosity can be described as a
330
Figure 2. Viscosity as function of the shear rate for different poly-
mer concentrations. (a) abaca two times etherified CMC ‰ 7.5, 䡬
15, 䉲 20, 䉮 30, ™ 50, © 100, ⽧ 150 and 〫 200 g/L. (b) Mis-
canthus sinensis two times etherified CMC ‰ 10, 䡬 20, 䉲 30, 䉮
50, ™ 100 g/L in 0.1M NaCl at 20 °C. The dotted line represents
the evolution of ␥ crit.
plots are characterized by three parameters (Milas et
al. 1990):
– The Newtonian viscosity (␩ 0) is independent of the
shear rate.
– The critical shear rate (␥ c) corresponds to the vis-
Figure 3. Storage and loss moduli as a function of the frequency for Miscanthus sinensis (MIX2) CMC with different concentrations in 0.1M
NaCl at 20 °C.
cosity decrease when ␥ increases corresponding to the
shear thinning behavior, and it is roughly related to
the longest relaxation time of the polymer in solution,
␶ r.
– The slope p in the right side of ␥ c, in the region
where the viscosity decreases as a function of the
shear rate (in a log–log plot).
We have determined the critical shear rate value
(␥ c) by the extrapolation of the Newtonian plateau
and the variation of log ␩ as a function of log ␥ (see
Figure 2).
Nevertheless, for the same C[␩] value, we ob-
tained lower values of ␥ c for the abaca CMC than
those for Miscanthus sinensis; then, it means that the
shear thinning behavior of CMC solutions is caused
not only by the high molar mass; swollen aggregates
may have an important role in this rheological behav-
ior.
Dynamic measurements
It is well known that in addition to their viscous prop-
erties, polymers also display elastic characteristics, as
expressed by viscoelastic behavior. The viscoelastic
properties of polymer systems can be determined by
mechanical oscillatory measurements which are car-
ried out with variable frequency and very low ampli-
tude (in the linear viscoelastic region) and can be used
as a more or less non-destructive measuring method
even for investigating sensitive superstructures. The
elastic part of the material is described by the storage
 331

Figure 4. Rheological characterization of abaca (ABE1) CMC sample (once derived) for different concentrations (C = 20 g/L, G⬘ > G⬙ for ␻
< 25 Hz; C > 20 g/L, G⬘ > G⬙ in all the ␻ range).

modulus G⬘ and the viscous properties by the loss

modulus G⬙ (Dyre et al. 1993).
The G⬘ (conservation or elastic modulus) value is
related to the energy stored during the application of
the strain, which will be liberated when the strain is
stopped; G⬙ (loss or viscous modulus) is proportional
to the dissipated energy in the form of heat in the
material.
To have a better understanding of the influence of
molar mass and concentration on viscoelasticity of
the CMC solutions and hence to be able to adjust
these properties, oscillatory measurements were car-
ried out on different CMC concentration solutions.
They were measured as function of the frequency at Figure 5. Storage and loss moduli as a function of frequency for
100 g/L abaca CMC samples derived one (ABE1) and two times
a constant percentage of strain. Measures were per-
(ABE2).
formed in a frequency range of 0.1 to 100 Hz and
temperature fixed at 20 °C.
The dynamic moduli (G⬘ and G⬙) determined on
The results are presented in Figure 3. At low fre-
abaca CMC sample (once derived) are plotted in Fig-
quency, the storage modulus G⬘ is smaller than the
ure 4. A gel-like behavior (G⬘ > G⬙ over a large range
loss modulus G⬙ in all cases; this means that viscos-
of frequencies) appears over a critical concentration
ity is the dominant property of CMC solutions under
C** ( ⬃ 20 g/L). Figure 4 shows the existence of the
low strain. As frequency increases, the elastic com-
critical concentration separating the solution behavior
ponent becomes more important until the modulus
from that of a gel-like behavior over 20 g/L.
curves eventually intercept and above this character-
Figure 5 presents a comparison between the dif-
istic frequency (f 0), the storage modulus predomi-
ferent behavior of two CMC samples at the same
nates. f 0 decreases when the polymer concentration
concentration (100 g/L), derived once and twice from
increases. Kulicke et al. (1996) also report this ten-
the same substrate (abaca).
dency in various CMC samples of molar mass rang-
We can observe for the same concentration, in
ing from 4.02×10 5 to 2.09×10 6 (g/mol). This behav-
CMC ABE2 sample, that G⬙ remains greater than G⬘
ior is characteristic of a viscous solution.
until they intercept at a frequency of 13 Hz, and fol-
lows the same tendency as shown in Figure 4. In
332
Figure 6. Effect of temperature on (a) elastic modulus (G⬘), viscous modulus (G⬙) and complex viscosity |␩*| and (b) G⬘/G⬙ ratio of abaca
CMC once derived sample. Conditions: C = 50 g/L; frequency = 1 Hz.
contrast, for ABE1 CMC sample, G⬘ > G⬙ in the
whole frequency range, presenting a gel-like behav-
ior as usually admitted. This fact could be caused by
the presence of microgel particles that increase the
storage modulus.
When the temperature of the gel-like sample is in-
creased, the viscosity slightly decreases, remaining
practically the same from 25 to 45 °C. In the whole
temperature range, G⬘ remains greater than G⬙ (Fig-
ure 6a). The G⬘/G⬙ ratio represented in Figure 6b
shows that the elastic character of the CMC sample
dominates. This is an advantageous behavior com-
pared with other physical gels such as gellan based
on H-bonds, whose performance decreases when tem-
perature increases (Rinaudo et al. 2000).
At high polymer concentrations, the complex vis-
cosity |␩*| adopts an approximate power-law depen-
dence at higher frequencies (Figure 7a). Moreover,
the curves of |␩*|(␻) and ␩(␥) can be superimposed
in the Cox–Merz model, as generally observed for
randomly coiled polymer solutions without strong in-
teractions (Cescutti et al. 1993). When the polymer
concentration is increased, the absolute value of com-
plex viscosity differs from flow viscosity, which tends
to drop rapidly. This may be caused by the disturb-
ance of the swollen gel structure dispersed in the so-
lution due to a high shear rate in the flow experiment
(Figure 7b).
The elastic modulus G⬘ increases rapidly with the
polymer concentration over 20 g/L for the abaca
CMC after first reaction. At the same time, the curve
dissociates from that obtained with CMC modified by
two successive treatments.

Figure 7. Combined plot of ␩ and |␩*| plotted against shear rate (␥) and pulsation (␻) for abaca two times etherified CMC (ABE2).
The different rheological curves obtained for these
two samples are given in Figure 8a. Figure 8b shows
the elastic modulus of two solutions of CMC corre-
sponding to two different materials derived succes-
sively two times. It demonstrates that the two CMCs,
having nearly the same [␩] (Table 1), give the same
elastic modulus (as well as the same specific viscos-
ity) as a function of polymer concentration.
In fact, after the first reaction, the CMCs are het-
erogeneous and obtain a gel-like character when the
polymer concentration of the solution is larger than a
characteristic concentration C** ⬵ 20 g/L corre-
sponding to the transition for G⬘/G⬙ = 1, in all the
range of polymer concentrations tested up to 200 g/L.
On the other hand, the twice-derived CMC displays
333
viscoelastic behavior (Figure 9). These results con-
firm those given previously.
Conclusions
The results related with the rheological characteriza-
tion of abaca, jute, sisal, linen and Miscanthus sinen-
sis carboxymethylcelluloses show that it is possible
to obtain cellulose derivatives from non-wood fibers
which offer different and interesting properties from
those found in CMCs produced from common mate-
rials such as wood or cotton linters.
The degree of substitution depends on the proper-
ties of the cellulose source. Except from Miscanthus
sinensis pulp (which presented lower accessibility of
334
Figure 8. Elastic modulus (G⬘) as a function of CMC concentra-
tion. (a) abaca CMC after one (ABE1) and two (ABE2) etherifica-
tion reactions, and (b) abaca (ABE2) and Miscanthus sinensis
(MIX2) CMC after two etherifications.
Figure 9. G⬘/G⬙ moduli ratio as a function of CMC concentration
of abaca one time (ABE1) and two times etherified CMC (ABE2).
the cellulose to react), after the first etherification
treatment, CMC samples presented a DS around 1,
while after the second treatment they display a DS
near 2.
From flow curves ␩(␥), Newtonian behavior was
attained and allowed determination of intrinsic vis-
cosity and specific viscosities in a large range of C[␩]
values. In the case of two times derived CMC sam-
ples, the curve well overlaps Cowman’s curve, while
CMC samples after one etherification treatment do
not follow the same curve tendency due to swollen
aggregated particles in suspension.
From dynamic measurements, it is demonstrated
that for low frequency and polymer concentration,
␩(␥) = |␩*|(␻), but that for large values of ␥ and poly-
mer concentration, this relation is no longer valid and
we obtained |␩*|(␻) > ␩(␥), interpreted as related to
the deformation of the superstructure during higher
shear rate flow experiments.
Finally, the moduli G⬘ and G⬙ were also consid-
ered and the crossover frequency f 0 was found to vary
with C[␩]. Abaca CMC samples whose initial cellu-
losic fibers were not well carboxymethylated (after
first etherification) display a gel-like behavior
(G⬘ > G⬙ in a wide frequency range) while two times
etherified abaca CMC samples behaved as a solution,
even if some insoluble particles persist.
Overall, the present results show that non-wood
fibers exhibit potential as a new raw material for the
production of cellulose derivatives with innovated
characteristics suitable for specific and tailored indus-
trial applications (particularly temperature stability).
Acknowledgements
The authors are indebted to the Spanish Government
and the Catalan Regional Government for financial
support: projects QUI980464-CO301 and 1998SGR-
00098. C.B. is obliged to the Rovira i Virgili Univer-
sity for financial support. We greatly acknowledge the
collaboration of CELESA S.A. for supplying the
pulps of abaca, sisal, jute and linen.
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