Advances in Colloid and Interface Science

79 1999. 81]103

Characterization of association phenomena in

aqueous systems of chitosan of different
hydrophobicity q
Bo Nystrom
U , Anna-Lena Kjniksen, Christian Iversen
Department of Chemistry, Uni ersity of Oslo, P.O. Box 1033, Blindern N-0315, Oslo, Norway

Abstract
Rheological, dynamical and structural properties of aqueous systems of chitosan UMchitosan. and hydrophobically-modified chitosans HM-chitosan. are briefly reviewed. The
effects of pH, level of surfactant addition, polymer concentration, and temperature on the
rheological behavior, both in the linear and non-linear viscoelastic regime, have been
scrutinized. These variables have the strongest impact on the rheological properties of the
hydrophobically-modified chitosans. We observe the formation of concentration-induced
gels for systems of UM-chitosan and HM-chitosans. Incipient gels are evolved at lower
concentrations as the hydrophobicity of the polymer increases. Non-linear shear thinning
behavior is found in semidilute solutions of UM-chitosan and HM-chitosan at higher shear
rates. The magnitude of this effect depends on factors, such as pH, amount of surfactant,
polymer concentration, and hydrophobicity of the polymer. The dynamic light scattering
results from semidilute solutions of UM-chitosan and HM-chitosan show that the intermolecular association phenomena in the polymer solutions are promoted by decreasing
temperature and increasing polymer concentration and hydrophobicity. The intensity light
scattering measurements on semidilute solutions of UM-chitosan and HM-chitosans suggest
that the systems have a fractal structure and the fractal dimension is approx. 2. Q 1999
Elsevier Science B.V. All rights reserved.
Keywords: Aqueous solutions; Hydrophobically associating; Chitosan; Rheology; Light scattering
q

Part of this paper was presented at the conference on Associating Polymer, Fontevraud, France,
November 1997.
U
Corresponding author. Tel.: q47 22 855522; fax: q47 22 855542; e-mail: bo.nystrom@kjemi.uio.no
0001-8686r99r$ - see front matter Q 1999 Elsever Science B.V. All rights reserved.
P I I: S 0 0 0 1 - 8 6 8 6 9 8 . 0 0 0 6 9 - 4

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Contents
1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 82
2. Properties of chitosan and hydrophobically-modified chitosan systems . . . . . . . . . . . 83
3. Rheology . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 84
3.1. Linear viscoelasticity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 84
3.1.1. Effects of pH and surfactant concentration . . . . . . . . . . . . . . . . . . . . 85
3.1.2. Concentration-induced gelation . . . . . . . . . . . . . . . . . . . . . . . . . . . 88
3.2. Non-linear viscoelasticity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 91
4. Dynamic light scattering . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 94
5. Static light scattering . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 97
6. Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 100
Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 101
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 101

1. Introduction
Hydrophobically-modified water-soluble polymers or so-called associating polymers are important in a number of areas including enhanced oil recovery, drag
reduction, and for formulation in coatings and personal care items w1]5x. These
new materials are water-soluble polymers containing a small amount of highly
hydrophobic groups. Typically, less than 2% incorporation of the hydrophobic
monomer into the polymer backbone is necessary to yield associative behavior. In
semidilute aqueous solution the hydrophobic moieties associate, and this results in
network formation and a rapid increase in solution viscosity. In this process,
aggregates, presumably of micellar type, are formed and act as reversible cross-links
between the polymer chains. From these systems, very viscous solutions or gels
displaying a shear-thinning behavior can be obtained.
The regions of intermolecular hydrophobic association represent areas of high
affinity for surfactant interaction, and consequently, the addition of surfactant has
been observed to have a dramatic effect on the structural, dynamic, and rheological
features of solutions containing hydrophobically-associating polymers. Several papers have been devoted to the study of physical properties of hydrophobically
modified water-soluble polysaccharides w6]12x, especially the non-ionic cellulose
ether ethylhydroxyethyl.cellulose in the presence of an ionic surfactant has been
thoroughly investigated w13]23x, and a number of review articles w24,25x have
already appeared. Much less attention has been devoted to the static and dynamical behavior of solutions and gels of the polysaccharide chitosan, which is a
hydrophilic cationic copolymer produced by deacetylation of chitin. This polymer
exhibits interesting association and gelling properties w26]32x in aqueous solution
under various conditions.
Many effects reported here are of a quite general nature, characteristic of
associating polysaccharide systems, but emphasis in this brief review will be on
aqueous systems of chitosan, which we have recently studied w31,34,35x in some
detail. The effects of polymer concentration, surfactant addition, pH, temperature,
and hydrophobicity on the linear and non-linear rheological properties for systems

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83

of unmodified chitosan UM-chitosan. and hydrophobically-modified chitosans

HM-chitosan. will be reviewed. Furthermore, some preliminary results from
intensity light scattering and dynamic light scattering on solutions of chitosan and
hydrophobically-modified chitosans will be presented.
The paper is organized as follows. In Section 2, we will give some general aspects
on the properties of the investigated chitosan systems. In Section 3, we will discuss
the rheological features in the linear and non-linear viscoelastic regime for
chitosan systems of different hydrophobicity at different conditions of pH, surfactant addition, polymer concentration, and temperature. Section 4 presents some
recent results from dynamic light scattering DLS. on solutions of UM-chitosan
and HM-chitosan. The effects of polymer concentration, hydrophobicity, and
temperature on the dynamics will be scrutinized. The structural features, in the
light of preliminary static light scattering SLS. experiments, of UM-chitosan and
HM-chitosan solutions are reviewed in Section 5. Finally, in Section 6, we summarize our main conclusions.

2. Properties of chitosan and hydrophobically-modified chitosan systems

Chitosans are a family of linear, cationic polymers w36,37x obtained by deacylating the biopolymer chitin, which is found in the skin or shell of anthropods. As the
degree of deacetylation DD. of chitinous material exceeds 50%, it becomes
soluble in acidic aqueous solution and is called chitosan. It is a random copolymer,
containing 1 4. linked 2-acetamide-2-deoxy-b-D-glucopyranose and 2-amino-2deoxy-b-D-glucopyranose residues. Chitosan is water-soluble at an acidic pH and
has numerous applications in industry, pharmacy, and biotechnology.
This biopolymer is polycationic, i.e. positively charged at pH - 6. Due to the
presence of protonated amino groups the amino group in chitosan has a p K a of
approx. 6.5 w38,39x., chitosan in dilute acid aqueous solution exhibits a polyelectrolyte character at low pH, and its hydrodynamic and rheological behavior in solution
is intricate w40]42x. The physicochemical properties of solutions of chitosan are
expected to be governed by factors, such as temperature, pH, ionic strength,
surfactant concentration, and DD. It is known w43,44x that the charge density along
the chain increases with an increase in the DD, and that chain flexibility of
chitosan molecules can be manipulated by changing the DD. In addition, the
hydrophobicity of chitosan should also play an important role for the dynamic and
rheological behavior of this polymer. This biopolymer can be chemically modified
w45,46x on the free amino groups or the hydroxyl groups present along the main
chain to obtain a hydrophobically-modified polymer. In this review, chitosan
samples with hydrophobic substitution degrees of 2.5, 5, and 10 mol% C12aldehyde chains grafted to the polymer backbone will be discussed. An illustration
of the structure of chitosan is depicted in Fig. 1. The chitosan samples considered
in this review have a degree of N-deacetylation of 84%, and they have been
dissolved in 1% acetic acid, yielding a pH of approx. 3. The weight-average
molecular weight of the samples is approx. 4 = 10 5 and the polydispersity index
Mw rMn s 2.7.

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Fig. 1. A schematic illustration of the structure of UM-chitosan and the hydrophobically-modified

chitosan HM-chitosan..

3. Rheology
3.1. Linear iscoelasticity
In this section we will examine the effects of pH, temperature, polymer concentration, and addition of surfactant on the linear viscoelastic properties of systems
of chitosan of different degrees of hydrophobicity. The effect of hydrophobic
substitution is displayed in Fig. 2, where the viscosity at a low shear rate in the
zero-shear-rate Newtonian plateau. is plotted as a function of polymer concentration for systems of UM-chitosan and HM-chitosans in 1% acetic acid. In all cases,
the viscosity rises with increasing polymer concentration, but the viscosity enhancement is stronger as the hydrophobicity of the polymer increases. The hydrophobic
effect becomes more accentuated with increasing polymer concentration. The
rather restricted concentration range covered by the most hydrophobic sample 10

Fig. 2. Concentraion dependence of the viscosity in the zero-shear-rate Newtonian plateau. of

semidilute acid aqueous solutions of UM-chitosan and HM-chitosans of different hydrophobicity at the
temperature indicated. From w35x.

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85

mol%. is due to the fact that this sample cannot be dissolved in this solvent above
0.3 wt.%. We should note that even for the solution of UM-chitosan, a strong
viscosification effect is registered at elevated concentration. At high concentrations, it is likely that the entanglement couplings will play an important role for the
viscosity. However, it has been argued w47,48x that as the polymer concentration
increases, unmodified chitosan self-associates through intermolecular hydrophobic
interactions between the acetyl groups. Hence, the effect of hydrophobic associations may also come into play for the unmodified polymer at higher concentrations.
3.1.1. Effects of pH and surfactant concentration
Before we present and discuss the results, it may be instructive to give a brief
background on how the solution properties of chitosan are influenced by pH and
surfactant interaction. It is known that the association behavior of semidilute
systems of chitosan and HM-chitosan can be affected by pH and the level of
surfactant addition. As a linear polyelectrolyte, chitosan has both reactive amino
groups and hydroxyl groups, and in addition HM-chitosan also contains hydrophobic groups that can interact with the surrounding. Thus, we expect that the
physical and solution properties of UM-chitosan and HM-chitosan change with the
surrounding chemical environment. When the pH value is less than approx. 6.5,
chitosan in solution carries a positive charge along its backbone. At pH values
below 4, most of the amino groups of chitosan are supposed to be protonated, and
since this effect promotes electrostatic repelling between charged groups of the
same sign, it leads to enhanced swelling w49,50x of the polymer network. At
pH-values greater than 6.5, which is approximately the p K a of the amino group in
chitosan, chitosan solutions exhibit phase separation.
The association behavior of chitosan systems can also be influenced by
polymer]surfactant interactions. In a recent viscosity study w51x on semidilute
solutions of unmodified chitosan, an interaction between chitosan and a non-ionic
surfactant was observed. In general, the polymer]surfactant interaction is stronger
in the presence of an ionic surfactant, and this effect is usually further strengthened in solutions of a hydrophobically-modified polymer. However, as was mentioned above, signs of enhanced intermolecular hydrophobic interactions with
increasing concentration have also been reported for solutions of unmodified
chitosan. The general picture that emerges for this type of system w7,10,11,52x is
that the surfactant molecules interact with polymers at a critical aggregation
concentration cac . and the surfactant molecules will bind to the existing hydrophobic substituents or microdomains. After saturation, the surfactant will start
to associate to form mixed micelles involving substituents from one or more
polymer chains. In the semidilute polymer concentration regime, association of
surfactant will tend to bring polymer chains together up to a maximum in
surfactant concentration csurf.,max , at which the optimum number of intermolecular
cross-links has been formed. This should correspond to a maximum in the viscosity
of the system. At levels of surfactant addition above csurf.,max , additional surfactant
aggregates are available for the solubilization of the polymer-bound hydrophobes.

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As a result, the average number of bound hydrophobes per surfactant aggregate

will decrease, thereby reducing the number of effective micellar-like cross-links.
This effect should result in a drop in the viscosity of the system.
Fig. 3 shows the effect of pH w31x on the storage G9. and loss G0 . modulus and
the complex viscosity hU whU s G9 2 q G0 2 .1r2r2pv .x, where v is the frequency
of oscillation. for 1 wt.% solutions of UM-chitosan and HM-chitosan 5 mol%. in
the presence of 5 mmolal of the cationic surfactant cetyltrimethylammonium
bromide CTAB.. We should mention that similar trends in the rheological
parameters were also observed at other moderate surfactant concentrations. The
overlap concentration cU , estimated from cU s 1rwh x wh x is the intrinsic viscosity.,
is approx. 0.05 wt.% w34x, i.e. these solutions are well located in the semidilute
concentration regime. For the solution of UM-chitosan, practically no pH dependence on the rheological quantities is observed. In the case of the HM-chitosan,
the rheological parameters pass through minima, located at a pH around 4. When
a 1 wt.% solution of chitosan is prepared in 1% aqueous acetic acid, the solution
assumes a pH value of 3]4. The pH value is raised by addition of base KOH. to
the solution and neutralization of the excess acetic acid present in the solution
takes place, and as a consequence the ionic strength of the chitosan solution
increases. This effect may lead to screening of the charges on the HM-chitosan
chains and poorer thermodynamic conditions, which will promote enhanced intermolecular hydrophobic contacts and hence the complex viscosity and the dynamic
moduli are expected to rise as the value of pH increases. In the range 5.8 F pH 6.4, a gel zone evolves w31x at this stage the sample experiences no flow when a test
tube is turned upside-down for a longer time. and at still higher values of pH an
incipient phase separation takes place. In an analogous way, the ionic strength will
also increase when an acid wHCl aq.x is added to the original chitosan solution,

Fig. 3. Effect of pH on the complex viscosity hU ., storage G9. and loss G0 . moduli v s 1.5 Hz. of 1
wt.% solutions of UM-chitosan and HM-chitosan 5 mol%. in the presence of 5 mmolal CTAB at 258C.
From w31x.

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87

and this favor enhanced hydrophobic association of the HM-chitosan at low values
of pH. In this context it should be mentioned that at pH f 0.7, a transparent gel is
formed w31x, while at pH values - 0.5 a phase separation occurs. These findings
suggest that the effect of pH on the rheological parameters is related to pH-induced hydrophobic associations.
The evolution of the viscoelasticity during the pH-induced gelation process for 1
wt.% HM-chitosan 5 mol%. in 5 mmolal CTAB is depicted in Fig. 4. The curves
are shifted horizontally by a factor 10 B of the value listed in the insert to avoid
overlap. The general trend is that at low frequencies, a viscous behavior with
G0 ) G9 is observed, while at higher frequencies, depending on the value of pH,
G9 increases to cross G0, and above this frequency, G9 exceeds G0, which suggests
that the elastic response dominates. These results indicate that the HM-chitosan
solutions become more elastic at higher frequencies, which is typical for networks
containing entangled or crosslinked polymer chains. At pH s 6.1 in the gel zone.
G9 ) G0 over the considered frequency domain.
The frequency of intersection v U G9 s G0 ., may be determined from G9 and
G0 data. In the inset plot of Fig. 4, the equivalent quantity, the time of intersection
t U t U s 1rv U . is plotted as a function of pH. The value of t U is at its minimum
at pH f 4 and increases toward lower and higher pH values. The quantity t U can
be considered as a relaxation time for chain disengagement of the network. The
increase of t U at low and high values of pH is probably another manifestation of
enhanced hydrophobic associations at these values of pH.

Fig. 4. Frequency dependences of the storage modulus G9 and the loss modulus G0 at different pH
values of 1 wt.% solutions of UM-chitosan and HM-chitosan 5 mol%. in the presence of 5 mmolal
CTAB at 258C. The curves have been shifted horizontally by a factor 10 B of the value listed in the inset.
The inset plot shows the pH dependence of the time of intersection t U see text.. From w31x.

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In Fig. 5, the effect of addition of CTAB on hU is illustrated for 1 wt.% solutions

of UM-chitosan and HM-chitosan at different values of pH. The complex viscosity
is virtually independent of the level of surfactant addition for the UM-chitosan,
while a significant polymer]surfactant interaction is observed for the HM-chitosan-CTAB system, at all the pH values, with at first an increase and then a
decrease in the value of hU . The maximum of hU is always located at a surfactant
concentration of approx. 1 mmolal, close to the critical micelle concentration for
CTAB in water. This surfactant concentration, probably corresponds to csurf.,max cf.
the discussion above., where the optimum number of intermolecular cross-links has
been formed. The decrease in hU at higher surfactant concentrations can be
attributed to a disruption of the polymer network. Similar trends in the viscosity
have recently been reported for other types of hydrophobically-modified polymers.
3.1.2. Concentration-induced gelation
Hydrogels of chitosan and the rheological behavior of chitosan systems under
various gelling conditions have attracted a great deal of interest in recent years. In
most studies, the chitosan gels were chemically cross-linked by utilizing different
cross-linking techniques w26,28]30,32,33,49,53]58x. The effects of factors, such as
the type and concentration of cross-linking agent w26,29,30,56x, cosolvent, concentration and molecular weight of chitosan w26,27,30,56,57x, degree of deacetylation
w26,29,30,57x, pH w30,31,49,55x, and temperature w26,32,55,57,58x on the gelation
process have been reported.
It has recently been observed w27,35x that physical gels of chitosan can be formed

Fig. 5. Effect of surfactant addition and pH on the complex viscosity hU v s 1.5 Hz. of 1 wt.%
solutions of UM-chitosan and HM-chitosan 5 mol%. at 258C. From w31x.

B. Nystrom
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89

by increasing the polymer concentration. The general feature observed for the
gelling UM-chitosan and HM-chitosan systems in Fig. 6 is that the loss tangent, tan
d s G0rG 9, decreases during the gel formation, indicating that the solutions
become more and more elastic. This type of behavior is frequently observed for
gelling systems of both physical and chemical natures. The concentration-induced
gel point is determined by observation of a frequency independent value w59,60x of
tan d obtained from a multifrequency plot of tan d vs. polymer concentration. It is
evident from Fig. 6 that the value of the gel concentration decreases with
increasing hydrophobicity of the polymer see also Table 1.. We should mention
that the gel concentrations obtained by this procedure are consistent with those
observed with the test tube tilting method w61,62x, where the gelation concentration was determined by tilting the test tube containing the solution. In this
approach the concentration at which the solution no longer flows is taken as the
concentration of gelation. These results suggest that the hydrophobicity of the
polymer plays an important role in the gel-forming process. Our conjecture is that
the gel network is controlled by an intricate interplay between entanglement
couplings and crosslinks formed by hydrophobic associations.
At the gel point, G9 and G0 curves are expected to become parallel to each
other, and a power law behavior G9 ; G0 ; v n . in frequency should be observed
see Fig. 7.. The value of the viscoelastic exponent n is virtually the same for the

Fig. 6. Viscoelastic loss tangent as a function of polymer concentration for the systems and frequencies
indicated. From w35x.

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Table 1
Characteristic data for incipient chitosan and HM-chitosan gels
Hydrophobicity
mol%.

cU s lrwh x
wt.%.

Gel conc.
wt.%.

SPasn .
calculated from
Eq. 2..

df
calculated from
Eq. 1..

0
2.5
5.0

0.044
0.024
0.027

3.9
3.0
1.75

0.36
0.46
0.46

232
83
24

2.2
2.0
2.0

HM-chitosans, but somewhat smaller for the UM-chitosan system see Table 1..
Since the gel concentration is higher for UM-chitosan than for the HM-chitosans,
it is possible that this system possesses stronger entanglement couplings than the
hydrophobically-modified samples. It has been argued w63x that an increasing
entanglement density may give rise to lower values of n.
The values of n reported for these chitosan systems are considerably smaller
than that 0.7. predicted for percolating networks w64,65x. Recently, Muthukumar
w66x developed a theoretical model to rationalize values of n deviating from the
percolation value. In this approach it is assumed that the variations in the strand
length between cross-linking points of the incipient gel network give rise to
changes in the excluded volume interactions and the value of the power law
exponent. The hypothesis is that increasing strand length will enhance the excluded
volume effect. If the excluded volume interaction is fully screened, the relaxation
exponent for a polydisperse system w66x can be written as
n s d d q 2 y 2 d f . r2 d q 2 y d f .

1.

Fig. 7. Plot of G9 and G0 vs. frequency for the indicated systems at the gel point, showing the power
law behavior. From w35x.

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91

where d d s 3. is the spatial dimension and d f is the fractal dimension that

relates the mass of a molecular cluster to its radius of gyration by R d f ; M. In the
framework of Eq. 1., all the values of the exponent 0 - n - 1 are possible for a
fractal in the physically realizable domain 1 F d f F 3. The value of the fractal
dimension, calculated with the aid of Eq. 1., for the UM-chitosan is higher than
those of the hydrophobically-modified chitosans see Table 1.. These findings
indicate w66,67x that the incipient network of the UM-chitosan is more dense, with
a higher value of d f , than those of the HM-chitosans. In this context we should
note that recent intrinsic viscosity results w34x on dilute solutions of the same
polymer samples, suggest that the molecules of UM-chitosan are more compact
than those of HM-chitosans. It is possible that the introduction of hydrophobic
groups produces a gel structure with some branches, leading to a more open
network structure.
The linear viscoelastic properties of incipient gels can be characterized by the gel
strength parameter S w59,60x, that depends on the cross-linking density and the
molecular chain flexibility. This material parameter can be defined by means of the
following relationship
G9 s S v nG 1 y n . cos d

2.

where G 1 y n. is the gamma function. An inspection of Table 1, reveals that S

increases significantly with decreasing degree of hydrophobic substitution. This
may be an indication that the entanglement couplings have a stronger impact on
the formation of the gel network than the specific interactions in form of hydrophobic associations.
Temperature is a variable that in many cases affects the viscoelasticity of
associating polymer systems. The effect of temperature on the dynamic viscosity h 9
for solutions of chitosan of different hydrophobicity is shown in Fig. 8. A comparison of the temperature dependence of h 9 for solutions of a fixed concentration of
1.5 wt.%, and for concentrations corresponding to the same value 18.5. of the
ratio crcU is displayed. In both cases, the value of h 9 drops with increasing
temperature, and this effect is practically the same independent of hydrophobic
substitution. These results suggest weakening of the networks at elevated temperatures. In this context we may note a recent NMR study w57x on gelling chitosan
systems, where an increase in temperature was found to favor the molecular
mobility of the chains.
3.2. Non-linear iscoelasticity
A typical feature of many associating polymer systems is the strong shear rate
dependence of the viscosity. In many cases, the shear thinning phenomenon is
observed at higher shear rates. Shear thinning begins at the shear rates at which
shear forces disrupt the network by reducing the number of interchain bonds,
lowering the resistance to the flow as well as the viscosity. The effect of shear rate
on the measured viscosity is depicted in Fig. 9 for 1 wt.% solutions of UM-chitosan

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92

Fig. 8. Temperature dependence of the dynamic viscosity for the systems indicated see text..

and HM-chitosan at different conditions of pH and CTAB concentration. A

practically Newtonian behavior is observed for the UM-chitosan at the considered
conditions in the shear rate range examined. For solutions of HM-chitosan, on the
other hand, a non-Newtonian shear thinning effect is found at higher shear rates.
This effect is most pronounced at low surfactant concentrations in solutions of pH
values of 1.2 and 5.0, while shear thinning is less dominant at pH s 4.0 and in
solutions of high surfactant concentrations disruption of the network..
Fig. 10 shows the effect of shear rate on the measured viscosity for solutions of
UM-chitosan and HM-chitosans in 1% acetic acid at different polymer concentrations. At low concentrations, all the systems exhibit Newtonian behavior, but as the
concentration raises a feature of non-Newtonian shear thinning is observed at
higher shear rates, and this effect is first visible for the most hydrophobically-modified polymer. These results reveal an augmentation of the shear thinning effect
with increasing polymer concentration and hydrophobicity. The observation that
shear thinning becomes stronger as the concentration increases has previously
been reported w27,68,69x for different chitosan systems.
The relative degree of shear thinning for the UM-chitosan and HM-chitosan
systems can be characterized in the framework of a simple power law relationship,
which can be expressed as

h ; g ay1.

3.

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Fig. 9. Shear rate dependence of the viscosity for 1 wt.% solutions of UM-chitosan and HM-chitosan 5
mol%. at 258C and at the conditions indicated. From w31x.

where g is the shear rate and a is the power law index. The values of a ,
determined from the shear thinning parts of the curves, for the solutions of
UM-chitosan and HM-chitosans under different conditions have been collected in
Table 2. For the systems discussed here, no disturbing hysterises effects were
observed when the shear-rate was first increased and then decreased back to its
initial value. The results in Table 2 reveal that at pH values favoring intermolecu-

Fig. 10. Shear rate dependence of the viscosity for the concentrations and systems indicated. From w35x.

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Table 2
Values of the characteristic exponent a . describing the non-Newtonian behavior of chitosan and
HM-chitosans
CTAB concentration s 0 mmolal, pH ( 3.5
Hydrophobicity
mol%.

Polymer concentration
wt.%.

a
see Eq. 3..

3.00
3.75

0.47
0.20

2.5

1.50
2.25
3.25

0.56
0.50
0.25

5.0

1.50
1.75
2.25

0.39
0.31
0.11

Polymer concentration s 1.00 wt.%

Hydrophobicity s 5.0 mol%
pH
1.2
4.0
5.0

CTAB concentration
mmolal.
5.0
5.0
5.0

a
see Eq. 3..
0.28
0.58
0.34

1.2
4.0
5.0

30.0
30.0
30.0

0.46
0.56
0.46

lar association, low CTAB concentrations, increasing polymer concentration and

hydrophobicity all promote the shear thinning effect of these systems at elevated
shear rate. The picture that emerges is that the decrease in viscosity with increasing shear rate can be attributed to the disruption of the network junctions, that is,
the rate of junction disruption exceeds the rate at which hydrophobic associations
or entanglement couplings can be re-formed.

4. Dynamic light scattering

A dynamic light scattering DLS. experiment probes the relaxation times of
processes which relax on some length scale qy1 , where q is the wave vector defined
as q s 4p nrl.sin ur2., here l is the wavelength of the incident light in a
vacuum, u is the scattering angle, and n is the refractive index of the medium.
When the scattering light obeys Gaussian statistics, the measured homodyne
intensity autocorrelation function g 2 q,t . is related to the theoretically amenable
first-order electric field correlation function g 1 q,t . through the Siegert relation
g 2 q,t . s 1 q B < g 1 q,t . < 2

4.

B. Nystrom
et al. r Ad . Colloid Interface Sci. 79 (1999) 81]103

95

where B F 1. is the coherence factor that depends on the experimental geometry.

This DLS study on semidilute solutions of UM-chitosan and HM-chitosan
revealed the existence of two relaxation modes. Initially, the decay of the correlation function is described by a single exponential, followed at longer times by a
stretched exponential
g 1 t . s A f exp y1rt f . q A s exp y trts e .

5.

with A f q A s s 1. The parameters A f and A s are the amplitudes for the fast and
the slow relaxation mode, respectively. Analyses of the time correlation functions
of the concentration fluctuations at long wavelengths in the semidilute concentration regime have shown that the first term short-time behavior. on the right-hand
side of Eq. 5. is related to a collective diffusion coefficient Dc ty1
s Dc q 2 ., which
f
reflects a concerted motion of the polymer chains relative to the solvent. The
second term long-time behavior. is expected to be associated with disengagement
relaxation of individual chains w70,71x or cluster relaxation w72x. The variable ts e is
some effective relaxation time, and b 0 - b F 1. is a measure of the width of the
distribution of relaxation times. The distribution of relaxation times for the present
systems is rather narrow with b s 0.8]0.9. The mean relaxation time is given by

ts '

exp y trts e .

dt s ts erb . G 1rb .

6.

where G by1 . is the gamma function of by1 .

Fig. 11 shows time correlation function data at a scattering angle of 608. at
various polymer concentrations, together with the corresponding curves fitted with
the aid of Eq. 5., for solutions of UM-chitosan and HM-chitosan 2.5 mol%.. The
time correlation function is always bimodal and can for all chitosan systems,
initially be described by a single exponential fast mode. followed by a stretched
exponential slow mode. at longer times. We note that there is a progressive
slowing down of the long-time relaxation process as the polymer concentration
increases. At a given concentration, the slowing down feature is more pronounced
for the hydrophobically-modified polymer.
The effect of hydrophobicity is depicted in Fig. 12 for two different concentrations. The shift of the relaxation process toward longer times is strong when the
degree of hydrophobic substitution is raised from 0 to 2.5 mol%, and this effect is
enhanced with increasing polymer concentration. However, when the hydrophobic
substitution is increased from 2.5 to 5 mol%, there is only a small additional effect.
The temperature dependence of the reduced collective diffusion coefficient
Dch 0rT h 0 is the solvent viscosity and T is the absolute temperature. for 1 wt.%
solutions of UM-chitosan and HM-chitosans is displayed in Fig. 13a. The reduced
diffusion coefficient has been used to eliminate trivial temperature and solvent
viscosity effects. The reduced diffusion coefficient falls off with increasing temperature for all the polymer samples, and the values of Dc seem to be higher for the
hydrophobically modified polymers. The same type of behavior is also observed for
the other polymer concentrations.

96

B. Nystrom
et al. r Ad . Colloid Interface Sci. 79 (1999) 81]103

Fig. 11. First-order electric field correlation function vs. time every second point is shown. for the
displayed systems at the scattering angle, temperature, and concentrations indicted. The solid curves are
fitted with the aid of Eq. 5..

The concentration dependence of Dc for solutions of UM-chitosan and HMchitosans at 358C the same trend is also found for the other temperatures. is
depicted in Fig. 13b. Dc is virtually independent of concentration in the considered
range.
The concentration and temperature dependences of the slow relaxation time ts
for solutions of UM-chitosan and HM-chitosans are shown in Fig. 14. An increase
of ts with concentration is observed for all the systems, but this effect is more
pronounced for the solutions of HM-chitosans. These findings suggest that increased polymer concentration and hydrophobicity promote interpolymer association, and thereby hamper the process of chain disengagement. The reduced slow
relaxation time decreases with increasing temperature for both UM-chitosan and
HM-chitosans, and this tendency is consistent with the behavior of the dynamic
viscosity in Fig. 8. A temperature rise seems to promote the disengagement of the
polymer chains.
Fig. 15 shows the q dependences, in a reduced form, of the correlation functions
for 0.5 wt.% solutions of UM-chitosan and HM-chitosans at 258C. The separation
of the curves at longer times suggests that the slow mode exhibits a stronger q
dependence approximately a q 3 dependence. than that of a diffusive process. This

B. Nystrom
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97

Fig. 12. Effect of hydrophobicity on the correlation functions at the scattering angle, temperature, and
concentrations indicated.

type of behavior of the slow relaxation mode is often observed for associating
systems. A more detailed analysis of the angular dependence of the slow relaxation
time will be presented in a forthcoming paper w73x.

5. Static light scattering

Semidilute solutions of associating systems may be viewed as transient networks
formed by more or less interpenetrating clusters. In the regime q j ) 1, the length
scale qy1 is associated with more local properties of the system one sees inside of
the clusters . and the scattering intensity depends strongly on the length scale. In a
static light scattering SLS. experiment one probes density correlations on a length
scale qy1 , and j is a length scale characteristic of the range of density fluctuations
occurring in the solution. In the regime q j ) 1, the angular dependence of the
scattered intensity or the static structure factor S q . can give us a direct access to
the fractal dimension d f of the clusters. The fractal structure of heterogeneous
systems is homologous self-similar . in a shape or a distribution of mass over a
relatively wide range of space size. From an analogy with a fractal self-avoiding
walk of randomly branched macromolecules in semidilute solutions, a percolation

98

B. Nystrom
et al. r Ad . Colloid Interface Sci. 79 (1999) 81]103

Fig. 13. Effect of temperature and concentration on the reduced collective diffusion coefficients for the
systems and conditions indicated.

Fig. 14. Effect of temperature and concentration on the reduced slow relaxation time for the systems
and conditions indicated.

B. Nystrom
et al. r Ad . Colloid Interface Sci. 79 (1999) 81]103

99

Fig. 15. Plot of the first-order electric field correlation function as a function of q 2 t every third data
point is shown. for the displayed systems at the scattering angles, temperature, and concentration
indicated.

model has been developed w74x which predicts a power law behavior of S q .
S q . ; qym

7.

where m ' d f s 2 w75x for a monodisperse solution of clusters with excluded

volume interactions. In the case of a polydisperse solution m ' d f 3 y t . s 1.6,
where t s 2.2 is the exponent that characterizes the distribution of cluster sizes in
the percolation model w76x.
The diffusion-limited cluster]cluster aggregation DLCA. and reaction-limited
cluster]cluster aggregation RLCA. models have been developed to describe
association in complex systems. The cluster]cluster aggregates of the DLCA model
have very open structures with d f s 1.75]1.80 w77,78x. If the sticking probability is
very small, the clusters will need to collide many times before they stick, and this
type of aggregation is called RLCA and yields denser aggregates with d f s 2.1 w79x.
In Fig. 16 the intensity profiles in the form of log]log plots of S q . vs. q are
displayed for solutions of UM-chitosan and HM-chitosans of different concentrations in the semidilute regime. The solid lines represent the best fit of the
experimental data with Eq. 7.. The values of m are around 2, virtually independent
of polymer concentration and hydrophobicity, and fairly close to the values determined from the oscillatory shear-results for the incipient gels of UM-chitosan
and HM-chitosans see Table 1.. However, in contrast to the values of the fractal

100

B. Nystrom
et al. r Ad . Colloid Interface Sci. 79 (1999) 81]103

Fig. 16. A log]log plot of the q dependence of the scattered intensity function for the displayed systems
at 258C and for the concentrations indicated. The solid lines represent the best fits of the experimental
data see Eq. 7...

dimension obtained from the rheological experiments, the values of d f determined

from SLS do not allow us to draw a distinction between UM-chitosan and
HM-chitosan systems. The reason for these may be that the concentrations utilized
in SLS are far below the concentrations for the formation of incipient gels. In this
context we should note that these values of d f are significantly higher than that
1.3. reported w80x from a small-angle X-ray scattering study on solutions of
chitosan with a degree of deacetylation of 79%. in 2 wt.% acetic acid aqueous
solution. Our samples have a deacetylation degree of 84%. The cause for this
difference in fractal dimension is not clear, but it was found that the heterogeneous structure was very sensitive to the degree of deacetylation of the chitosan
sample.

6. Conclusions
This review has shown that association phenomena in systems of chitosan
UM-chitosan. and hydrophobically-modified chitosan HM-chitosan. can be well
characterized by rheology and light scattering. The linear and non-linear viscoelas-

B. Nystrom
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101

ticity are affected by factors, such as pH, level of surfactant addition, polymer
concentration, and temperature. These effects have a stronger influence on systems of HM-chitosan. The concentration-induced incipient gels are characterized
by the following power-law G9 ; G0 ; v n , where n is equal to 0.36 and 0.46 for
UM-chitosan and HM-chitosans, respectively. Shear thinning behavior was observed
at higher shear rates for systems of both UM-chitosan and HM-chitosan. The
magnitude of this effect is governed by pH, surfactant and polymer concentration,
and hydrophobicity of the polymer.
The dynamic light scattering results from semidilute solutions revealed that the
association effects are promoted by decreasing temperature and increasing polymer concentration and hydrophobicity. Intensity light scattering results from
semidilute solutions of UM-chitosan and HM-chitosan indicate a fractal dimension
of approx. 2.

Acknowledgements
This work was supported by Norsk Hydro and the Norwegian Research Council
through the program PROSMAT.

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