European Polymer Journal 43 (2007) 17441753

EUROPEAN
POLYMER
JOURNAL
www.elsevier.com/locate/europolj

Aqueous solutions of amphiphilic polysaccharides:

Concentration and temperature eect on viscosity
A. Durand

Laboratoire de Chimie Physique Macromoleculaire, UMR 7568, CNRS-Nancy-University, ENSIC, BP 20451, 54001 Nancy Cedex, France
Received 1 February 2007; received in revised form 19 February 2007; accepted 21 February 2007
Available online 28 February 2007

Abstract
Amphiphilic polymers have been prepared by chemical modication of a neutral bacterial polysaccharide, dextran, consisting of a-1,6 linked glucose units. Various amounts of aliphatic hydrocarbon groups with six carbon atoms are attached
along the dextran chains by ether links. The viscosities of their aqueous solutions in the dilute domain and in the beginning
of the semi-dilute domain are considered with particular interest for the variation with temperature and polymer
concentration.
The equations of Fedors and Martin are shown to conveniently depict the eect of polymer concentration over the
whole investigated range. A semi-empirical equation is established between the critical concentration deduced from Fedors
equation and both the Huggins coecient and the intrinsic viscosity (parameters deduced from the results in the dilute
domain).
The variation of solution viscosity with temperature is also examined. Andrade equation, combined with Martin or
Fedors equation, is shown to account for the temperature eect. Particularly, the variation of the activation energy with
polymer concentration is conveniently depicted. The validity of the derived semi-empirical equations is extended to other
polymer solutions using literature data.
 2007 Elsevier Ltd. All rights reserved.
Keywords: Dextran; Amphiphilic polymers; Viscosity; Fedors equation; Andrade equation

1. Introduction
Polymeric surfactants can be synthesized by
chemical modication of pre-existing polymers.
One usual way is to attach hydrocarbon groups (aliphatic or aromatic) onto a highly hydrophilic polymer (synthetic or natural, neutral or ionized). The
increasing interest for biocompatible and biode*

Tel.: +33 (0)3 83 17 52 92; fax: +33 (0)3 83 37 99 77.

E-mail address: alain.durand@ensic.inpl-nancy.fr

gradable materials makes polysaccharides attractive

raw materials for the preparation of polymeric surfactants [16]. The chemical modication of polysaccharides has been well-documented since the
pioneering work of Landoll [7].
Aqueous solutions of amphiphilic polymers are
involved in many processes. It is important to be
able to estimate the viscosity of aqueous solutions
as a function of polymer concentration and structure. Many equations have been proposed but the
large majority hold for dilute solutions, in which

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A. Durand / European Polymer Journal 43 (2007) 17441753

polymer concentration is low enough to neglect

intermolecular interactions [8]. Consequently, these
equations allow the determination of structural
characteristics of individual macromolecules (intrinsic viscosity and constants describing the thermodynamic interactions with solvent molecules). For
semi-dilute solutions a few equations are available.
Moreover, these equations involve empirical parameters that cannot be deduced directly from dened
structural characteristics of macromolecules.
Recently, we investigated the viscosity of aqueous
solutions of amphiphilic polysaccharides prepared
from dextran. It was shown that Fedors equation
conveniently depicted the viscosity behaviour up
to moderately concentrated solutions [9]. Furthermore, the concentration parameter contained in this
equation was related to a dened viscometric characteristic (i.e. the upper limit of the dilute domain).
Nevertheless, this correlation was established on a
purely empirical basis.
The temperature eect on the viscosity of polymer solutions has been well-documented for dilute
solutions. A great deal of experimental data is available for dilute solutions of polymers in good solvent
conditions [1017]. On the contrary, few studies deal
with amphiphilic polymers even in dilute solutions.
Similarly, few data are available for semi-dilute
polymer solutions [5,1825]. Considering the number of industrial applications where relatively concentrated polymer solutions are submitted to
signicant temperature variations (heat exchangers,
drilling uids, etc.) it seems still a scientic challenge
to obtain experimental and semi-quantitative correlations about temperature eect on viscosity.
In that work, we want to analyze the viscosity
behaviour of dilute and semi-dilute solutions of
amphiphilic polysaccharides. More specically, the
eects of polymer concentration and solution temperature on viscosity will be detailed. We will try
to derive semi-empirical equations which account
for the observed correlations. Furthermore, we will
attempt to describe the results obtained over the
whole concentration range on the basis of structural
parameters obtained in the dilute domain.

1745

M n 26; 000 g=mol, M w 40; 000 g=mol, Ip = 1.6.

The other chemicals were from Aldrich (St. Quentin
Fallavier, France) and were used as received. MilliQ
water was used for all the experiments.
2.2. Synthesis of amphiphilic dextrans
The followed procedure for hydrophobic modication of dextran was already described in a previous paper [26]. Briey, 1 g of dextran T40 is
dissolved in 20 mL dimethylsulfoxide (DMSO) at
40 C. Then, 5 mL of a 1 M aqueous solution tetrabutyl ammonium hydroxide is added followed by
the required amount of epoxyoctane. The reaction
is allowed to proceed at room temperature during
several days according to the expected degree of
substitution. The reaction medium was dialysed
against a water/ethanol mixture (50/50 v/v) and
nally pure water. The polymer was recovered by
freeze-drying the resulting aqueous solution.
The amount of attached epoxyoctane was determined by the integrations of 1H NMR spectra performed in deuterated DMSO using a BRUKER
300 MHz spectrometer.
2.3. Viscometry
Viscometric measurements with polymer solutions
were carried-out using an Ostwald-type capillary viscometer (0.46 mm diameter). The temperature was
regulated by a circulating bath. Prior to measurements, the aqueous solutions were ltered through
0.2 lm lters. Polymer concentration was checked
by weighting dry extracts obtained after letting the
solutions 24 h in an oven at 110 C. The found values
were always about 90% of the calculated ones. No
kinetic corrections were required since we veried
that the ow time was proportional to the kinematic
viscosity. For experiments at dierent temperatures,
the variation of the ow time of water was consistent
with the literature data. The densities of the polymer
solutions were assumed to be identical to that of pure
water within the concentration range explored (up to
80 g/L).

2. Experimental
3. Results and discussion
2.1. Materials
3.1. Chemical structure of the investigated polymers
The native dextran sample, T40, was obtained
from Pharmacia (Uppsala, Sweden). It, has been
characterized by size exclusion chromatography:

Polysaccharide surfactants have been synthesized

from dextran, a neutral bacterial polysaccharide

1746

A. Durand / European Polymer Journal 43 (2007) 17441753

OH
HO

O
O
OH x

OH

HO
O

CH2 CH (CH2 )n CH3

OH
Scheme 1. The detailed study of the position modied by the
aliphatic epoxide (among the three possible ones) has not been
performed yet. The existence of di- or tri-substituted glucose units
is not excluded even if only a monosubstituted unit is represented.

composed of glucose units with a-1,6 linkages

[27,28].
Various amounts of aliphatic hydrocarbon
groups have been attached onto the glucose units
(Scheme 1) by reacting dextran with epoxyoctane.
The degree of hydrophobic modication, s, is
dened as the molar ratio of attached hydrocarbon
groups to glucose units. In what follows, s will be
expressed in percents and will be determined from
1
H NMR spectra (see Section 2). The polymers will
be named DexC6s.
Amphiphilic dextran derivatives were prepared
from a commercial dextran sample T40 (see Section 2). Details about the procedure of chemical
modication of dextran can be found elsewhere [26].
3.2. Aqueous solutions: concentration and
temperature eects
3.2.1. Viscosityconcentration relationship
3.2.1.1. Semi-empirical equations. The viscosity of
dilute polymer solutions is conveniently depicted
by Huggins equation (Eq. (1)) which contains both
polymer concentration (C in g/L) and two physico-chemical parameters related to the polymersolvent system ([g] and kH) [29]. The rst one is the
intrinsic viscosity ([g] in L/g) which is related to
the specic volume of the macromolecular species
present in the solution (isolated macromolecules or
aggregates). The second parameter is the Huggins
coecient (kH) which is an indication of the interactions between solvent molecules and the macromolecular species in solution.
gred g k H g2 C

In Eq. (1), gred is the reduced viscosity (in L/g)

g
s
which is dened by gred Csp gg
where g and gs
gs C

are the viscosity of the polymer solution and that

of the pure solvent (Pa s), respectively.
For a polymer in good solvent, Huggins coecient is lower than 0.5. On the contrary in bad solvent conditions, Huggins coecient can reach
values as high as 6.
An alternative equation to Huggins equation is
the Kraemer equation (Eq. (2)) [30]. This second
equation allows the determination of the intrinsic
viscosity and that of the Kraemer constant, kK. This
equation is sometimes used in combination with
Huggins equation for characterization of polymer
solutions including amphiphilic polymers [31].
ln gr
2
g  k K g C
C

In Eq. (2), gr is the relative viscosity which is dened

by gr 1 gsp ggs .
In the semi-dilute domain, the rise of viscosity
with polymer concentration is much sharper than
in the dilute domain. This sharp viscosity increase
is linked with hydrodynamic and thermodynamic
interactions between macromolecules or aggregates
in solution. Hydrocarbon groups aggregation leads
to intermolecular associations and gives rise to a
much sharper viscosity increase than in the case of
native dextran sample. Several semi-empirical equations have been proposed to depict that variation
for polymers in good solvent conditions (0.3 6
kH 6 0.7). A complete review of these equations is
far above the scope of that work [8].
Martin proposed an exponential equation (Eq.
(3)) which includes an empirical parameter, KM,
called the Martin constant [32].
gsp CgeK M Cg

Although Eq. (3) has been shown to agree with

experimental data, a few studies dealt with amphiphilic polymers in aqueous solutions, for which
the Huggins coecient can rise up to 5 or more.
Starting from results about latex suspensions,
Fedors derived an equation for dilute and semidilute polymer solutions (Eq. (4)) [33].
1
1=2
2gr

 1

1
1

Cg C max g

In Eq. (4) Cmax is a concentration parameter (in

g/L). Contrary to Eqs. (1)(3), Fedors equation
does not contain any interaction constant (like kH
or KM) but a concentration parameter, Cmax, analogous to the volume fraction corresponding to maximum packing of solid particles.

A. Durand / European Polymer Journal 43 (2007) 17441753

1747

Table 1
Viscometric parameters determined for native and hydrophobically modied dextran samples
Polymer

Solvent

Huggins

Martin

Fedors

[g] (cm3/g)

Clim (g/L)

kH

[g]M (cm3/g)

KM

[g]F (cm3/g)

Cmax (g/L)

T40

Water, 25 C
Water, 45 C
Water, 65 C

20.0
16.5
15.3

60
65
80

0.55
0.60
0.67

20.5
17.0
16.4

0.40
0.43
0.44

20.3
16.9
16.7

309
353
461

DexC612

Water, 25 C
Water, 45 C
Water, 65 C

16.8
10.1
9.9

55
38
41

1.1
4.0
3.5

16.5
11.3
10.9

1.0
1.9
1.8

17.2
11.5
11.3

127
80
91

DexC621

Water, 25 C
Water, 65 C

9.2
7.6

54
43

2.7
6.1

8.8
8.0

2.9
3.7

9.7
10.3

85
96

DexC638

Water, 25 C
Water, 45 C
Water, 65 C

8.0
8.0

48
55
58

3.7
2.8

7.3
7.3
7.3

4.2
3.3
3.0

8.7
8.5
9.5

80
98
116

Three equations were considered for curve tting (for symbols see text). Huggins equation was applied only to data of the dilute domain
(C < Clim).

3.2.1.2. Results. The domain in which the viscosity

follows Eq. (1) is the dilute domain. Applying Huggins equation to dilute solutions of amphiphilic polysaccharides allows the determination of [g] and kH in
aqueous solution and at various temperatures
(Table 1). Using Eq. (2) for this series of data leads
to similar values of intrinsic viscosity (data not
shown).
For DexC6s polymers, [g] decreases when the
degree of modication is increased while the variation of kH is opposite (Table 1). This result can be
explained by the decrease of solvent quality by
grafting hydrocarbon groups along polysaccharide
backbone. The species present in dilution solutions
become more compact ([g] is lowered) and exhibit
a higher tendency to interact with each other (kH
is increased). The latter tendency can lead to the formation of macromolecular aggregates even in dilute
solutions. Static and dynamic light scattering experiments were performed with aqueous solutions of
amphiphilic dextrans and showed that such aggregates were formed in dilute domain with DexC621
and DexC638 while DexC612 remained under the
form of isolated macromolecules [26]. The average
molecular weights as well as the hydrodynamic radii
obtained by light scattering led to estimated intrinsic viscosities of aggregates that were fully consistent with those deduced from viscometric
experiments [26]. According to the degree of hydrophobic modication, dextran derivatives lead to
aqueous solutions of isolated macromolecules or
to suspensions of macromolecular aggregates.
The upper concentration limit of the dilute
domain will be noted Clim (in g/L). For native dex-

tran samples, Clim is called the overlap concentration

(usually noted C*) and is inversely proportional to
[g] as predicted by theoretical considerations. On
the contrary, with amphiphilic dextrans, Clim
depends mainly on the hydrophobic modication
(Table 1). For amphiphilic polymers, Clim is generally called the association concentration.
The equation proposed by Martin appears to
depict conveniently the viscosity data relative to
dilute and semi-dilute domains, up to C[g] = 2. This
equation ts conveniently the experimental data of
both native and hydrophobically modied dextran
samples (Fig. 1). The values of intrinsic viscosity
deduced from Eq. (3) are consistent with those
obtained from Huggins equation. Generally KM is
equal to or lower than kH (Table 1).
The equation derived by Fedors depicts conveniently the viscosity results for both dilute and moderately concentrated polymer solutions (Figs. 2 and
3). The found values of intrinsic viscosity are
slightly higher than those obtained from Huggins
equation (Table 1).

3.2.2. Eect of temperature on the viscosity

of polymer solutions
3.2.2.1. Semi-empirical equations. Within a limited
temperature range, the viscosity of a polymer solution varies generally following a relation similar to
that of usual liquids (Eq. (5)) provided that polymer
concentration is not too high and that temperature
remains far enough from glass transition [18].
Ea

g AeRT

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A. Durand / European Polymer Journal 43 (2007) 17441753

Fig. 1. Specic viscosity of aqueous solutions at 25 C as a

function of overlap parameter: s, dextran T40; d, DexC612; m,
DexC621; j, DexC638. The lines are curve ttings by Martin
equation.

Fig. 3. Specic viscosity of aqueous solutions of amphiphilic

dextran derivatives at 25 C (open symbols) and 65 C (bold
symbols) as a function of overlap parameter: (s, d) DexC612,
(h, j) DexC638. The lines are curve ttings by Fedors equation.

tions of polymers [3640]. No systematic study of

semi-dilute solutions is available either for polymers
in good solvent conditions or for amphiphilic polymers. Monkos proposed to modify Eq. (5) introducing other semi-empirical parameters in the
exponential function. His modication appeared
ecient for aqueous solutions of various proteins
[25,4143]. In that work, within the studied range
of temperature, Eq. (5) is convenient.

Fig. 2. Specic viscosity of dextran T40 aqueous solutions at

various temperatures as a function of overlap parameter: s,
25 C; d, 45 C; m, 65 C. The lines are curve ttings by Fedors
equation.

In Eq. (5), g is the viscosity of the polymer solution

(Pa s), A is a pre-exponential factor (Pa s), R is the
gas constant (8.314 J/K mol), T is the thermodynamic temperature (K) and Ea is the activation energy (J/mol). This relation has been initially
introduced by Andrade for simple liquids [34,35]
and has been shown to hold for dilute aqueous solu-

3.2.2.2. Results. For native dextran, varying temperature between 25 and 65 C has almost no eect on
the variation of the specic viscosity with the overlap parameter (Fig. 2). Although the strength of
hydrogen bonds is decreased at higher temperatures, the consequence on the Huggins coecient
is not strong enough to induce a signicant eect
in the explored ranges of temperature and concentration. A similar behaviour has been reported for
chitosan [18].
On the contrary, with hydrophobically modied
dextrans, this curve is signicantly displaced as a
function of temperature (Fig. 3). This eect is
clearly linked with the magnitude of the hydrophobic eect. For DexC612 and DexC621, higher temperatures lead to a reinforcement of intermolecular
interactions and thus to higher specic viscosities.
On the contrary, for DexC638, it seems that intramolecular interactions and consequently aggrega-

A. Durand / European Polymer Journal 43 (2007) 17441753

1749

tion more or less sharply depending on polymer

structure.

Fig. 4. Linearized Arrhenius plots for aqueous solutions of

DexC638 between 25 and 65 C at various concentrations: s,
18.5 g/L; , 27.6 g/L; m, 46.8 g/L; j, 58.7 g/L; d, 71.7 g/L.

tion behaviour is favoured. Consequently, lower

specic viscosities are observed for a given overlap
parameter. A similar eect is observed, when changing the nature of hydrocarbon groups from C6 to
more hydrophobic ones, at a given temperature [26].
For native dextran as well as for its amphiphilic
derivatives, intrinsic viscosity decreases when temperature rises. This fact indicates that polymer coils
or aggregates are more compact and can be
explained by a decrease of the strength of hydrogen
bonds which reduces the hydration of polysaccharide backbone and reinforces the hydrophobic
eect. The solvent quality is signicantly decreased
when raising temperature. A similar behaviour has
been mentioned for hydrophobic derivatives of
another neutral polysaccharide, inulin [2]. In the
case of cellulose ethers carrying hydrocarbon
groups with a limited number of carbon atoms the
same phenomenon leads to the well-known thermothickening eect [44]. With the dextran derivatives
depicted here, the reinforcement of the compactness
of the macromolecular species is dominant and the
viscosity decreases monotonically upon heating.
When the solution viscosity is considered as a
function of temperature over the whole concentration domain, the experimental results are consistent
with Eq. (5) (Fig. 4). It is possible to deduce the activation energy from the slope of the curves. This
activation energy increases with polymer concentra-

3.2.3. Discussion
3.2.3.1. Concentration eect on viscosity. The equation proposed by Fedors appears consistent with
the viscosity results, either for the concentration
eect of for the temperature eect. This equation
was rst proposed for suspensions of solid spheres
and then extended to solutions of macromolecules
[33,45,46]. Contrary to other semi-empirical equations for solution viscosity, it contains no interaction constant but a concentration parameter,
noted Cmax. Fedors equation has been applied to
solutions of non-associative polymers [4750]. Nevertheless, almost no detailed study was available
concerning associative polymers in aqueous solutions [9,51].
Since Cmax represents a concentration at which
the solution viscosity becomes extremely high (the
right-hand term of Eq. (4) tends to innity), it seems
reasonable that it is closer to Clim for amphiphilic
dextran than for native dextrans. Indeed this large
viscosity increase is due to the establishment of a
physical network in the bulk. Amphiphilic dextrans
form intermolecular associations in addition to the
macromolecular entanglements that occur with
native polysaccharides.
A semi-empirical relation between a macroscopic
parameter like Clim and molecular characteristics
like kH and [g] can be established using the preceding results. For low enough polymer concentrations,
we have the following relations:
C
1
 kHC

gsp g

and

C
1
 kKC

ln gr g

The two preceding expressions lead to the following

equation:
!
1 1
1
1
 K He

2 gsp ln gr
Cg
Eq. (6) is the Heller equation and contains an empirical constant KHe [52]. For specic viscosities up to
3, the left-hand terms of Eqs. (4) and (6) give almost
identical values. As a consequence, we could deduce
that:
C max g

1
K He

Eq. (7) establishes that the concentration parameter,

Cmax, contained in the Fedors equation, depends on

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A. Durand / European Polymer Journal 43 (2007) 17441753

both the hydrodynamic volume of the macromolecular species ([g]) and their thermodynamic interactions (KHe). Furthermore, with our data we nd:
k H  0:25 1:14K He 1:04K 2He

This empirical relation is consistent with previous

results obtained with amphiphilic derivatives of cellulose [53]. Moreover, Dort [54] established for several polymers that the relation between kH and KHe
had of the following form for associative polymers:
k H 0:25 1:14K He cK 2He

In Eq. (9) c is a parameter depending on the polymer structure. The case of non-associative polymers
corresponds to c = 0 according to Dorts results
[54].
Combining Eqs. (7) and (8) it is possible to predict the variation of Cmax[g] with kH. The calculated
curve is in rather good agreement with the experimental data over a wide range of kH values including both native and hydrophobically modied
dextrans (Fig. 5).
Recently, we showed that for native dextrans and
amphiphilic dextran derivatives, the concentration
parameter Cmax was related to the upper limit of
the dilute domain, Clim, by simple proportionality

Fig. 5. Dimensionless product Cmax[g] obtained from Fedors

equation as a function of Huggins coecient kH: d, native and
amphiphilic dextran samples at various temperatures; m,
poly(styrene) in ethyl acetate [55]; j, poly(butyl methacrylate)
in methyl ethyl ketone [49]; s, amphiphilic copolymers of
acrylamide in water [56]. The dotted line is the calculated
variation combining Eqs. (7) and (8).

relations [9]. In particular, for native dextrans we

established the empirical relation: Cmax  5 Clim
together with Clim  1.2/[g]. The calculated curve
is consistent with that previous result since it shows
that for kH  0.5, the product Cmax[g] is close to 5
which would give Cmax  6 Clim. Taking into
account the experimental accuracy of these values,
the agreement seems satisfactory.
Using the viscometric data reported by Papanagopoulos et al. for poly(styrene) and in ethyl acetate
[55] as well as those of Ioan et al. for poly(butylmethacrylate) in methyl ethyl ketone [49], we obtain
values that are fully consistent with the calculated
curve (Fig. 5).
Data for aqueous solutions of amphiphilic polymers were obtained from the works of Volpert
et al. on amphiphilic copolymers of acrylamide and
N-alkyl acrylamide [56]. The experimental points
deduced from these data are in fairly good agreement with the calculated curve (Fig. 5).
To our knowledge, it is the rst time that a semiquantitative relation is established between the concentration parameter of Fedors equation and the
viscometric characteristics of macromolecules determined in the dilute domain (kH and [g]). Moreover,
the tendency evidenced in that work extends to associative and non-associative polymers.
3.2.3.2. Temperature eect on viscosity. In that part,
we will focus on the eect of polymer concentration
on the activation energy in dilute and semi-dilute
domains. Several assumptions are made in order
to get analytical expressions. First, we will consider
that the pre-exponential factor A is invariant with
temperature, i.e. that only Ea accounts for the variation of viscosity with temperature. The second
assumption is that, within the explored concentration range, an analytical equation depicts conveniently the variation of viscosity with polymer
concentration. On the basis of the previous results,
we can use either Martin equation or the one
derived by Fedors. Finally, we will neglect, within
the explored temperature range, the variation of
polymer concentration.
With the previous assumptions, it is possible to
establish a general analytical expression for the activation energy as a function of polymer concentration and viscometric parameters (Eq. (10)).
Ea Ea solvent R



T 1T 2
g C; T 2
ln r
gr C; T 1
T1  T2

10

A. Durand / European Polymer Journal 43 (2007) 17441753

In Eq. (10), Ea solvent is the activation energy of the

pure solvent (J/mol), T1 and T2 are the lower and
upper limits of the explored temperature range.
The function gr(C, T) is the Martin or Fedors equation in which the empirical parameters have their
values at the corresponding temperature (Table 1).
Thus, the estimation of the activation energy of
polymer solutions relies on the availability of
semi-empirical equations which depicts the variation of viscosity with polymer concentration [57].
For native dextran, Eq. (10) is fairly consistent
with experimental results either from that study or
taken from the literature [58]. This equation also
gives consistent results for aqueous solutions of synthetic polymers like poly(vinylpyrrolidone) [14]
(Fig. 6).
For hydrophobically modied dextrans, the values given by Eq. (10) are consistent with experimental points but some deviations are observed (Fig. 7).
Apart from amphiphilic dextrans, Eq. (10) agrees
with the values deduced from the results of Monkos
with aqueous solutions of ovalbumin (Fig. 7) [41].
In that case, the reported results were re-analyzed
using Eq. (5) since Monkos applied another semiempirical equation involving three semi-empirical
parameters with one having the units of activation
energy [41].

Fig. 6. Activation energy of ow of aqueous solutions (Eq. (5))

as a function of polymer concentration: d, dextran T40 (this
study); s, dextran T70 (data from Ref. [58]); r, poly(vinylpyrrolidone) (data from Ref. [14]). The lines are curve ttings by
Eq. (10) using Martin equation.

1751

Fig. 7. Activation energy of ow of aqueous solutions (Eq. (5)) as

a function of polymer concentration: d, DexC612; s, DexC621; m,
DexC638; h, Ovalbumin (data calculated from Ref. [41]). The
lines are curve ttings by Eq. (10) using Fedors equation.

4. Conclusion
The viscosity of aqueous solutions of amphiphilic
polysaccharides was depicted using semi-empirical
equations involving two adjustable parameters:
one related to the specic volume of the macromolecular species and one linked to the interactions
between solvent and macromolecules. These two
parameters were related to the chemical structure
of the amphiphilic dextrans.
The concentration parameter contained in the
Fedors equation was quantitatively related to the
intrinsic viscosity and Huggins coecient of the various polymers.
The variation of viscosity with temperature was
analyzed by the Andrade equation combined with
Fedors or Martin equations. The activation energy
of dilute and semi-dilute solutions can be satisfactorily depicted by an established semi-empirical equation involving intrinsic viscosity and Huggins
coecient.
Our results demonstrate that the concentration
and temperature eects on solution viscosity can be
estimated using semi-empirical equations involving
the viscometric characteristics obtained in the dilute
domain. These correlations are useful for the
design of chemical processes for the synthesis of
polymer-covered nanoparticles (like miniemulsion

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A. Durand / European Polymer Journal 43 (2007) 17441753

polymerization for instance). Such applications will

be developed in forthcoming papers.
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