Cellulose (2008) 15:361–370
DOI 10.1007/s10570-007-9185-1
The dissolution of microcrystalline cellulose in sodium
hydroxide-urea aqueous solutions
Magali Egal Æ Tatiana Budtova Æ Patrick Navard
Received: 23 April 2007 / Accepted: 10 October 2007 / Published online: 31 October 2007
Ó Springer Science+Business Media B.V. 2007
Abstract It has been reported that cellulose is better
dissolved in NaOH-water when a certain amount of
urea is added. In order to understand the mechanisms
of this dissolution and the interactions between the
components, the binary phase diagram of urea/water,
the ternary urea/NaOH/water phase diagram and the
influence of the addition of microcrystalline cellulose
in urea/NaOH/water solutions were studied by DSC.
Urea/water solutions have a simple eutectic behav-
iour with a eutectic compound formed by pure urea
and ice (one urea per eight water moles), melting at -
12.5 °C. In the urea/NaOH/water solutions, urea and
NaOH do not interact, each forming their own
eutectic mixtures, (NaOH + 5H2O, 4H2O) and (urea,
8H2O), as found in their binary mixtures. When the
amount of water is too low to form the two eutectic
mixtures, NaOH is attracting water at the expense of
Member of the European Polysaccharide Network of
Excellence (EPNOE), www.epnoe.eu
M. Egal
T. Budtova (&)
P. Navard (&)
Centre de Mise en Forme des Matériaux (CEMEF), Ecole
des Mines de Paris, UMR CNRS/Ecole des Mines de Paris
7635, BP 207, 06904 Sophia Antipolis, France
e-mail: Tatiana.Budtova@ensmp.fr
P. Navard
e-mail: Patrick.Navard@ensmp.fr
M. Egal
Spontex, 74, rue de St-Just-des-Marais, BP 207, 60026
Beauvais, France
urea. In the presence of microcrystalline cellulose,
the interactions between cellulose and NaOH/water
are exactly the same as without urea, and urea is not
interacting with cellulose. A tentative explanation of
the role of urea is to bind water, making cellulose-
NaOH links more stable.
Keywords Cellulose
Dissolution in aqueous
NaOH and urea
Phase diagram
Eutectic

Limit of cellulose dissolution
Interactions between
cellulose NaOH and urea
Introduction
Aqueous solutions of sodium hydroxide are interest-
ing cellulose solvents because of the easiness of
solution preparation and their low cost. One of the
drawbacks of this solvent is that cellulose dissolution
strongly decreases with the increase of the degree of
polymerisation and polymer concentrations (Yamane
et al 1996a). NaOH/water is not a thermodynamically
good solvent of cellulose and it has the disadvantage
of inducing the gelation of the solution with time and
temperature increase, unless specific pulp treatment
and dissolution procedure is used (Yamane et al
1996b, c).
Cellulose can be dissolved in a narrow range of
NaOH concentrations (from 7% to 10%) and tem-
peratures (-4 °C to -8 °C). Several studies describe
the dissolution process and the ways cellulose objects
123
362
can be shaped from such solutions (Sobue et al. 1939;
Yamane et al 1996a–c; Laszkiewicz 1998; Isogai and
Atalla 1998 ; Yamashiki et al. 1988 ; Roy 2002 ;
Roy at al. 2003, 2001 ; Kuo and Hong 2005;
Cuissinat and Navard 2007; Egal 2006; Egal et al.
2007). The interactions between cellulose and NaOH
in cellulose/NaOH/water mixtures and the limit of
microcrystalline cellulose dissolution in this solvent
are given in (Egal et al. 2007). It has been reported in
literature that the addition of components like urea,
thiourea or zinc oxide are helping cellulose dissolu-
tion (Zhou and Zhang 2000 ; Zhou et al. 2002, 2004 ;
Zhang et al. 2002 ; Weng et al. 2004). The dissolu-
tion in NaOH/water with the addition of urea is rather
well documented from a practical point of view
(dissolution procedures, shaping methods). But the
reasons why urea is helping the cellulose dissolution
are not well understood. The objective of the present
paper is to contribute to the understanding of the
interactions between cellulose, NaOH, urea and water
when they are mixed together, at 7–10% NaOH.
In 1998, Laszkiewicz 1998, reported that the
addition of 1% urea in 8.5% NaOH at -5 °C improves
the solubility of bacterial cellulose having an initial DP
of 680. The fraction of dissolved cellulose is 48.6%
with 1% urea and 17.8% without urea. Some years
later, a research group in Wuhan University in China
reported that cellulose is ‘‘totally dissolved’’ in NaOH
with urea (Zhou and Zhang 2000, Zhou et al. 2002,
2004) or thiourea (Zhang et al. 2002 ; Weng et al.
2004) and that both additives are removed out
completely from the cellulose during the coagulation
and washing steps. Zhou and Zhang 2000, investigated
the influence of the NaOH/urea solvent composition on
cotton linter dissolution. They concluded that the
optimal NaOH/urea/water ratios to dissolve cellulose
are 6/4/90 and 8/2/90, but that the solubility of
cellulose decreases when its DP increases. Some years
later (Cai and Zhang 2005), they investigated the
influence of the type of alkali hydroxide and of the
process to dissolve cellulose. They classified the
solvents according to their dissolution power on cotton
linter: LiOH/urea/water [ NaOH/urea/water  KOH/
urea/water. The best NaOH/urea/water solvent com-
position was then found to be 7/12/81. Using 13C
NMR, they showed (Zhou et al. 2004; Cai and Zhang
2005) that NaOH/urea/water is a direct solvent of
cellulose and that urea and NaOH interact, this
interaction playing probably an important role in the
123
Cellulose (2008) 15:361–370
solvation of cellulose. On the other hand, in the same
article (Cai and Zhang 2005), they only mentioned the
presence of urea hydrates and NaOH hydrates as seen
by DSC without concluding on any interaction
between urea and NaOH. Based on DSC results, they
wrote that NaOH hydrates are linked to cellulose and
that the interactions between urea and cellulose
decrease the self-association of cellulose chains and
thus enhance the stability of solution. From viscomet-
ric studies in dilute state, they concluded that in such
aqueous solutions, cellulose exists as semi-flexible
chains (Zhou et al. 2004). The group of Fink (Kunze
and Fink 2005) reported that a specific insoluble urea–
NaOH–cellulose complex is formed at high urea and
NaOH concentrations, using NMR results.
Weng et al. 2004, studied the gelation of 4–
6%cellulose/6%NaOH/5%thiourea aqueous solu-
tions, as a function of temperature. They noted that
after gelation, G0 always increases and never reaches
a plateau, as was also reported for cellulose/
9%NaOH/water systems (Roy 2002; Roy et al.
2003). The gelation process does not involve chem-
ical cross-linking but probably results from the
formation of cellulose-cellulose network accompa-
nied by a micro-phase separation. The understanding
of the interactions between cellulose and solvent
molecules (NaOH, urea and water) is a necessary step
for predicting the properties of cellulose solutions.
The present paper is structured in the following
way. After a description of the methods and materials
used, the full or partial phase diagrams of urea/water,
NaOH/urea/water and micro-crystalline cellulose/
NaOH/urea/water will be plotted from the DSC
thermograms and the interactions between the com-
ponents will be deduced.
Experimental
Materials and solution preparation
The cellulose used was Avicel1PH-101 micro-crys-
talline cellulose, called ‘‘cellulose’’ in the following,
from FMC Corporation. It is purified, partially de-
polymerized alpha cellulose, with a mean degree of
polymerization of 170, as given by the manufacturer.
Before use, cellulose was dried in an oven at 60 °C in
order to remove the remaining water. This type of
cellulose was used to have a low DP to ensure a good
Cellulose (2008) 15:361–370
solubility and to avoid complications with other than
cellulose components (traces of hemicellulose or
lignin, for example).
Sodium hydroxide was purchased from Prolabo, in
pellets, with purity higher than 98%. Urea pellets were
purchased from Fisher, with purity higher than 99%.
Both compounds were dissolved in distilled water.
For the binary solutions like NaOH/water and urea/
water, the concentration of the given compound refers
to its weight concentration in solution. For all the
other cases, what is shown is the amount in gram of
the given compound in 100 g of the total mixture. For
example, Xcellulose/YNaOH/Zurea/water means that
in 100 g of total mixture, there is X g of cellulose, Y g
of NaOH, Z g of urea and (100-X-Y-Z) g of water.
Preparation of solutions
A 20%NaOH/water solution and a 50%urea/water
solution were prepared separately. In another vessel,
water was added to dry micro-crystalline cellulose to
make fibres slightly swollen. Solvents and swollen-
in-water cellulose were cooled down: cellulose/water
and urea/water to +5 °C and NaOH/water to -6 °C.
When cellulose is present, NaOH/water was added to
the swollen-in-water cellulose and mixed with a
spatula. In the case when urea was added, the
50%urea/water solution was added to cellulose/
NaOH/water mixture. Mixtures were placed into a
bath at -6 °C and mixed at *1000 RPM using a
rotary overhead mixer, for two hours. The prepared
solutions were stored at +5 °C.
Methods
Differential Scanning Calorimetry (DSC) experi-
ments were carried out on a PERKIN-ELMER1
DSC-7, composed of two thermally insulated ovens.
Stainless steel gold-plated screwed caps (PERKIN-
ELMER1 B0182902) were used instead of typical
aluminium or stainless steel ones because of corro-
sion induced by NaOH. Samples were cooled down
from room temperature to -60 °C, kept at -60 °C
for 15 h and then heated up to +10 °C. Cooling and
heating rates in all cases were 1 °C/min. This rate
was chosen because of the high heat capacity of gold-
plated stainless steel caps. The melting temperatures
363
were corrected from the influence of the sample
weight by extrapolating the temperatures to zero
mass. The experimental errors of temperatures and
enthalpies are below 10%.
In the cases where DSC melting peaks were
overlapping, the PeakFit 4.12 (Systat corporation)
deconvolution program was used.
X-ray scattering was performed on a XPERT-PRO
from PANanalytical. The voltage to speed up elec-
trons was 40 kV, the current was 30 mA and the
anticathode was made of Cu, so the wavelength Ka1
was 1.5406 Å. The diffraction patterns were obtained
by a continuous single scan from 5° to 60° with a
0.04° step size.
Results and discussion
Recall of the NaOH/water phase diagram and its
interactions with cellulose
A complete study of the interactions of cellulose with
NaOH and water in the area of the phase diagram
where cellulose is dissolving is reported in (Egal
et al. 2007). The mixture of sodium hydroxide and
water in the 0–20% NaOH range is a simple solution.
NaOH and water are miscible in the liquid state and
immiscible in the solid state. Sodium hydroxide and
water form a metastable eutectic mixture in the
conditions of heating and cooling rates used in this
study; it is composed of a sodium pentahydrate and
ice in the following proportions: NaOH
5H2O + 4
H2O. This eutectic mixture melts around -33.4 °C.
When cellulose is added to a NaOH/water solution in
the range of NaOH concentrations from 7 to 10% and
at temperatures in the range of -5 °C to -8 °C,
cellulose of low molar mass is dissolving. The major
effect seen by DSC is the decrease of the peak of
NaOH/water eutectic mixture when increasing the
amount of dissolved cellulose. From the analysis of
(i) the decrease of the eutectic peak enthalpy and (ii)
the invariance of the ice peak melting at higher
temperatures, it was possible to calculate the limit of
cellulose dissolution in NaOH/water as being at least
four NaOH molecules per one anhydroglucose unit
(corresponding to equal cellulose and NaOH concen-
trations in weight). Nine water molecules are around
each of the NaOH ions linked to the cellulose
backbone. The temperature of NaOH/water eutectic
123
364 Cellulose (2008) 15:361–370

peak and its known behaviour with or without Table 1 Temperatures of solidus and liquidus at various
cellulose will be used in the following to investigate concentrations of urea. ‘‘DSC’’ values correspond to the
melting temperatures obtained from DSC experiments
the effect of urea on the NaOH/water and the
cellulose/NaOH/water/urea phase diagrams. Urea Solidus Liquidus temperature (°C)
concentration temperature (°C)
(wt%) DSC data DSC Data from
Binary urea/water phase diagram data handbooks

6 -12.4 -2.2 -1.9

The full urea/water phase diagram has been plotted 8 -12.4 -2.8 -2.6
using DSC experiments and X-ray scattering. DSC 12 -12.5 -4.2 -4.0
melting thermograms of 0–30% urea aqueous solu- 16 -12.3 -5.1 -5.4
tions are given on Fig. 1. The melting temperatures 20 -12.7 -7.4 -7.0
and enthalpies of the peaks are reported in Tables 1 30 -12.3 – -11.4
and 2. In Table 1, the term ‘‘solidus (DSC data)’’
40 -12.5 – 0
corresponds to the onset of the peak at low temper-
50 -12.5 – –
ature and the term ‘‘liquidus (DSC data)’’ to the end
60 -12.5 39 35
of the peak at higher temperature. The ‘‘Handbook’’
70 -12.5 64 56
data of the liquidus are from (Weast et al. 1983;
80 – 86 80
Rabinovich and Khavin 1978).
100 – 137 135
Apart for 30% urea where only one peak is
present, all DSC thermograms reveal two melting ‘‘Handbook’’ values correspond to solubility temperatures
peaks more or less well-separated. The first one, at reported in Weast et al. (1983) and Rabinovich and Khavin
(1978)
low temperature, has the same position whatever the
urea concentration from 6% to 30% is. At the onset of urea. As the molar masses of urea—CO(NH2)2—and
the peak, the temperature is about -12.5 °C. This water are 60 and 18 g/mol respectively, 30% of urea
peak corresponds to the melting of urea-water in weight corresponds to about a molar ratio
eutectic mixture. The second one, at higher temper- nH2 O =nurea ¼ 7:8. Thus, the total urea-water eutectic
atures, is shifted towards lower temperatures when mixture consists of 1 urea and 8 H2O molecules. This
the urea content increases. This peak corresponds to is confirmed by X-ray scattering that shows that at
the gradual melting of free ice. The peak of free ice higher urea concentrations, above 30%, only two
disappears at about 30% of urea. This means that the types of crystals are present, ice and crystalline urea.
urea-water eutectic mixture corresponds to 30% of The melting enthalpies of the eutectic compound and
ice are reported in Table 2. From the level rule, the
Heat Flow
30% fractions of the eutectic and free ice can be calculated
directly from the phase diagram. They coincide
1.5 within 10% with the ones measured by DSC.
20% 6% DSC analysis was also performed on 30–100%urea/
8% water solutions. Two peaks were seen. The first one is
still at -12.5 °C, as in the case of 0–30%urea/water
1
12% solutions, thus corresponding to the melting of the same
16%
eutectic mixture. The second one is shifted towards
higher temperature. Pure urea gives a single melting
0.5
peak at 137 °C. In order to check the crystalline
structure of the component which melts at high
temperature for an aqueous solution containing more
0 than 30% of urea, pure urea and the 70%urea/water
-16 -12 -8 -4 0 T°C
system, both brought at room temperature, were
Fig. 1 DSC melting thermograms for urea/water solutions; analyzed by X-ray scattering. The X-ray diffractograms
Curea = 6, 8, 12, 16, 20 and 30 wt% show that only ice and crystalline urea are present at

123
Cellulose (2008) 15:361–370 365

Table 2 Melting enthalpies of the eutectic mixture and free Heat Flow 1
ice 2.5
Urea Total enthalpy Enthalpy calculated 3
concentration from DSC with PeakFit 2
2
(wt%) measurements
Eutectic Ice
Z = 25
0 358 = DHice, pure 1.5 Z = 20
6 325 51 275
8 323 67 256 Z = 18
1
12 319 111 208 Z = 14
16 311 155 156 4
Z = 12
20 308 212 96 0.5
Z=6
29.4 290 = DHeut, pure – –
30 291 – – Z=0
0
The total enthalpy was determined directly from the DSC -50 -40 -30 -20 -10 0 T°C
thermograms. Eutectic and ice enthalpies were calculated with
PeakFit1 Fig. 3 DSC melting thermograms for 7.6NaOH/Zurea/water
solutions (Z = 0, 6, 12, 14, 18, 20 and 25). DSC traces are
room temperature. As a consequence, the urea/water vertically shifted for clarity
binary system has a simple eutectic behaviour. The
eutectic compound is a mixture of two crystals: pure 25urea/water (it is recalled that for 100 g of a
urea + ice. Its melting temperature is -12.5 °C and its 7.6NaOH/Zurea/water solution, there are 7.6 g of
composition is 1 urea + 8H2O, corresponding to 29.4% NaOH, Z (6–25) g of urea and [100–7.6-Z] (86.4–
of urea. The full phase diagram of urea/water solution 69.4) g of water). DSC melting thermograms were
built from DSC and X-rays data together with results plotted for several urea concentrations and are
known from literature is shown in Fig. 2. represented on the Fig. 3. Four peaks can be seen.

Ternary NaOH/water/urea phase diagram

The composition of cellulose solvents studied were in
the range from 7.6NaOH/6urea/water to 7.6NaOH/
140
Peak n°1
The peak n°1 corresponds to the melting of the
metastable eutectic mixture NaOH
5H2O + 4H2O.
Table 3 column 3 shows that as soon as urea is added,

120 Eutectic compound

"free" ice Table 3 Melting temperatures of NaOH eutectic, urea eutectic
100
"free" urea and free ice for 7.6NaOH/Z urea/water solutions (Z = 0, 6, 12,
14, 18, 20, and 25 g in 100 g solution)
80 Handbook values
T°C

Z g of DH eut, NaOH TNaOH, eut Turea, eut Tfree ice

60 urea in (J/g) (onset) (peak) (end)
7.6NaOH/Z (°C) (°C) (°C)
40 urea/water

20
0 72 -34.2 – -6.9
6 72 -35.9 -25.7 -8.6
0 12 71 -36 -20.6 -12.5
14 70 -35.5 -19.2 -12.9
-20
0 20 40 60 80 100 18 71 -35.3 -17.3
Urea concentration (%) 20 74 -35.5 -17.8
25 69 -35.6 -18.5
Fig. 2 Binary phase diagram of urea/water solution

123
366
the melting temperature is slightly depressed: from
about -34 °C in binary NaOH/water solution without
urea, to about -35.6 °C with urea. This slight
decrease of eutectic melting temperature in ternary
system compared with a binary system is most
probably due to the presence of a third component,
urea, that is changing the interface interactions
between the crystal and its outside environment,
and thus changing the melting temperature. This new
melting peak remains at the same temperature for all
the studied urea concentrations because the NaOH/
water eutectic mixture is never crystallizing in
presence of a liquid.
Peak n°2
This peak appears at about -30 °C but it is not always
present. It corresponds to the melting of the stable
eutectic mixture NaOH
7H2O + 2H2O that was not
present in NaOH/water solution when heated/cooled
with a low temperature rate (Pickering 1893; Cohen-
Adad et al. 1960). It seems that the presence of urea in a
7.6NaOH/water is favouring the crystallization of this
stable eutectic, while this is not occurring in the same
conditions of cooling and heating rates without urea.
Since we have no access to conditions where only the
stable eutectic compound is present without urea, we do
not know its pure melting enthalpy. In the following, we
will use the same specific enthalpy for the stable
eutectic compound as the known one of the metastable
eutectic compound (187 J/g). This approximation is not
bringing any sensible effect on the following calcula-
tions due to the low amount of the stable compound,
when present. The melting temperature of the NaOH
eutectic is taken at the onset of the peak, the one of the
urea eutectic at the maximum of the peak (the onset is
impossible to be measured) and the one of ice at the end
of the peak to determine the liquidus. As the melting
temperature and the melting enthalpy of NaOH eutectic
mixtures remain constant with an increase of urea
concentration, we can conclude that urea neither
disrupts the formation of NaOH eutectic nor modifies
its composition (1NaOH + 9H2O). During the time of
experiment, urea does not react with NaOH. Conse-
quently, the species in solution are the NaOH eutectic
compound, in metastable and/or stable states, some urea
compounds (will be determined in the following) and
water.
123
Cellulose (2008) 15:361–370
Peaks n°3 and n°4
The peak n°3 appears as soon as urea is added but its
position depends on urea concentration. This peak
should correspond to the melting of a urea compound.
As will be seen below, peak n°3 represents the
melting of urea eutectic mixture and peak n°4 - the
melting of free ice.
The temperature of the melting peak n°4 decreases
when urea concentration increases from 0 to 14 g of
urea in 100 g of solution. This peak corresponds to the
gradual melting of free ice. We have shown that urea
does not react with NaOH molecules and does not
modify the NaOH eutectic. Thus we assume that in the
presence of NaOH, urea and water behave as if they
were alone: they should form the eutectic mixture
containing one urea and eight water molecules, as
determined for the binary urea/water solution.
Thus, peaks n°3 and n°4 should represent the
melting of urea eutectic mixture and the melting of
free ice, respectively. The fact that peak n°3 corre-
sponds to the melting of the urea eutectic mixture can
be checked by plotting the melting temperature of
both peaks as a function of urea concentration
(Fig. 4). It shows that peaks n°3 and n°4 are joining
at a composition corresponding at 7.6NaOH/18urea/
water. If the assumption of non-interaction between
NaOH and urea is correct, this means that at this
composition, there should be two independent, coex-
isting eutectic compounds, NaOH + water and
urea + water, with no more free water in solution.
In a 100 g solution containing 7.6 g NaOH + 18 g
0
free ice liquidus
liquid (composed of urea,
-10 NaOH & water)
ice + liquid (composed of urea,
NaOH & water)
-20
urea eutectic
ice + eutectic crystals urea eutectic crystals
T°C
-30 + liquid (composed of +liquid (composed of urea,
NaOH & water) NaOH & water)
-40
NaOH eutectic
urea eutectic crystals
-50 ice + urea eutectic crystals + NaOH eutectic crystals
+ NaOH eutectic crystals + uncondensed urea
-60
0 5 10 15 20 25
mass of urea in 100g of solution
Fig. 4 Ternary phase diagram for 7.6NaOH/(0–25)urea/water
solution
Cellulose (2008) 15:361–370
urea + 74.4 g water, there are 4.13 mol of water,
0.19 mol of NaOH which corresponds to 0.19 mol of
NaOH eutectic mixture (there is one NaOH mole per
mole of the NaOH eutectic compound) and 0.3 mol
of urea. The NaOH eutectic mixture is not modified
by the addition of urea and it contains 1NaOH and
9H2O molecules. 1.71 mol of water are thus trapped
in the NaOH eutectic mixture and it remains 4.13–
1.71 = 2.42 mol of water. The urea eutectic mixture
is composed of 1urea and 8H2O molecules and thus,
0.3 9 8 = 2.4 mol of water are trapped in the urea
eutectic. There is no more water in the system (the
remaining 0.02 mol of free water are within the
experimental error of determination of the crossing
composition). As a conclusion, 100 g of 7.6NaOH/
18urea/water solution contains 18 g of urea and
43.56 g of water, i.e. the local concentration of urea-
in-water is 18/(18 + 43.56) 9 100%=29.2% which
corresponds to the composition of the urea eutectic
mixture, as shown above for urea/water binary
solution. At this composition, the solution is com-
posed of only the two eutectic mixtures:
NaOH + water and urea + water.
These results show that both NaOH and urea
eutectic mixtures are formed independently and thus
are competing for water.
Conclusion on the 7.6NaOH/urea/water ternary
phase diagram
A part of the ternary phase diagram of the 7.6NaOH/
urea/water system is given on Fig. 4. NaOH and urea
are forming both their normal eutectic mixture with
water, NaOH
5H2O + 4H2O and urea + 8H2O,
respectively. This means that they are not interacting,
but they are competing for water. In 100 g of
solution, at Z \ 18, there is enough water for both
compounds to be independent and peaks of NaOH/
water eutectic, urea/water eutectic and water are
present. At Z = 18, there is no anymore free water in
solution (the peak n°4 corresponding to the melting
of water disappears) and all water molecules are
linked either to the NaOH + water eutectic mixture
or to the urea + water eutectic mixture. At Z [ 18,
there is not enough water for all NaOH and urea to
form eutectics. Since the enthalpy of the NaOH
eutectic is constant at all urea concentration (see
Table 3), it implies that the lack of water is supported
367
by urea. At Z [ 18, not all urea present in the mixture
can join water to form a eutectic compounds. It
means that there is free urea in the system. Since no
peak of crystallisation of other than the two NaOH
and urea eutectics is present, it implies that the free
urea is in a liquid form at all the studied temperatures.
In general, NaOH, urea and water behave as in
their binary systems.
Solutions of cellulose in NaOH/urea/water
Avicel cellulose solutions in 7.6NaOH/6urea/water
are investigated with cellulose concentrations varying
from 0 to 5 g in 100 g solution. In other words, 100 g
of solution contain X g of cellulose (X varying from 0
to 5), 7.6 g of NaOH, 6 g of urea and the rest being
water. An example of DSC melting thermograms is
represented on Fig. 5. The melting temperatures and
enthalpies of the peaks are reported in Table 4. The
main features of these DSC melting curves are similar
to the ones reported in literature (Cai and Zhang
2005). The addition of cellulose does not modify or
change the position of the peaks as compared to the
case without cellulose. The DSC melting curves has
three peaks. The peak at the lowest temperature, at
about -35 °C, corresponds to the melting of the
NaOH + water eutectic mixture. The next one, at
about -25 °C, corresponds to the melting of the
Heat Flow
0.6
0.4
0.2
2
1
0
-40 -30 -20 -10 0 T°C
Fig. 5 DSC melting thermograms of XAvicel/7.6NaOH/6
urea/water solutions for X = 3 g (1) and 5 g (2). Curves are
shifted vertically for clarity
123
368 Cellulose (2008) 15:361–370

Table 4 Melting
Cellulose content, NaOH eutectic Urea eutectic Free ice
temperatures and enthalpies
X g in 100 g
of the peaks for different TNaOH, eut DH T urea, eut DH, T free ice, DH,
of solution
content of cellulose in (onset) (°C) (J/g) (peak) (°C) (J/g) (end) (°C) (J/g)
7.6NaOH/6urea/water
0 -35.9 72 -25.7 30 -8.6 160
1 -35.8 41 -24.8 34 -7.2 176
3 -35.7 35 -24.0 29 -6.5 175
5 -35.6 22 -23.7 26 -6.4 172

urea + water eutectic mixture. The peak at the 1.2

highest temperature, at about -7 °C, corresponds to
the melting of free ice. As far as the melting peaks are 1.0
not well separated, the PeakFit software was used to
determine the melting enthalpy of each of the

reduced enthalpy
0.8
compound melting in this system, as reported in
Table 4.
0.6

Peak of NaOH eutectic mixture 0.4

Whatever the concentration of cellulose is, the 0.2

melting temperature of the NaOH + water eutectic
mixture is the same to the one obtained for a pure
7.6NaOH/6urea/water (without cellulose). In the case
of cellulose in NaOH aqueous solutions without urea,
there is a decrease of the eutectic melting enthalpy
with cellulose concentration (Egal et al. 2007).
During the dissolution process, cellulose is trapping
some NaOH molecules that cannot participate any-
more to the formation of the eutectic mixture. It is
interesting to investigate if the addition of urea is
influencing this trapping of NaOH molecules by the
cellulose chains. Figure 6 gives the reduced melting
enthalpy versus reduced cellulose concentration for
cellulose/7.6NaOH/water (taken from Egal et al.
2007) and for cellulose/7.6NaOH/6urea/water solu-
tions. It is remarkable to see that the addition of
cellulose is trapping the same amount of NaOH with
or without urea. The addition of urea does not change
the interactions between cellulose and NaOH. This is
a very important and rather puzzling result.
0.0
0 0.5 1
mcell/mNaOH
Fig. 6 Reduced melting enthalpy of the NaOH + water
eutectic versus reduced cellulose/NaOH mass ratio. Dark
points are for cellulose/7.6NaOH/water without urea and open
points are for cellulose/7.6NaOH/6urea/water. The full line is
given to guide the eyes
increasing with cellulose content. An explanation of
this increase of melting temperature is a change in the
molecular environment of urea and water due to the
addition of cellulose. The values of the melting
enthalpy of the urea eutectic are scattered, but we can
assume that there is no influence of the cellulose
content on the melting enthalpy of the urea eutectic
peak. The enthalpy of the urea eutectic does not
depend on cellulose concentration. The addition of
cellulose does not change the urea-water interactions.

Peak of urea eutectic Peak of free ice

Whatever the concentration of cellulose is, the peak The melting temperatures of ice are increasing with
of the urea + water eutectic mixture is seen. We can cellulose content. An explanation of this increase of
note that the melting temperature of urea eutectic is melting temperatures is a change in the molecular

123
Cellulose (2008) 15:361–370
environment of water due to the addition of cellulose.
Since the melting enthalpy of free ice is approxi-
mately constant for all cellulose concentrations (the
same was observed for cellulose/7.6NaOH/water
without urea, see Egal 2006; Egal et al. 2007), we
conclude that the amount of free ice remains the same
with and without cellulose.
Three main facts are obtained from these series of
experiments and their interpretations.
(i) NaOH and urea do not interact when mixed
together with water. Their eutectic mixtures are
formed independently,
(ii) urea and cellulose do not interact when mixed
with NaOH and water since the urea + water
eutectic is not changed,
(iii) the interactions between NaOH hydrates and
cellulose are not changed by the presence of
urea (the decrease of the eutectic peak enthalpy
of NaOH + water with cellulose content is the
same with or without urea).
This is clearly bringing a question about the role of
urea as a promoter for cellulose dissolution and a
retardation agent for solution gelation. A point to note
is that the dissolution limit of micro-crystalline
cellulose in NaOH-water is not changed when adding
urea, since it remains four NaOH molecules per one
anhydroglucose unit, as shown in (Egal et al. 2007).
Discussion
Micro-crystalline cellulose can be dissolved in
NaOH/water with 7–10% of NaOH below 0 °C.
DSC experiments reveal that the addition of Avicel
cellulose does not change either the temperature of
the NaOH eutectic mixture or the temperature of
melting ice. This means that cellulose does not
disrupt the formation of the NaOH eutectic and does
not directly interact with water. Nevertheless, the
intensity of the eutectic peak decreases when cellu-
lose concentration increases. This shows that at least
four NaOH should be bound to one AGU (4NaOH/
AGU) to provide dissolution (expressed in weight
ratio, it gives mcell/mNaOH B 1 as a limit of cellulose
dissolution). In these limiting conditions, about 36
water molecules are bound to these four NaOH linked
to one AGU.
369
The present DSC investigations show that the
addition of urea is not changing the interactions
between NaOH and cellulose. Urea + water form a
simple eutectic phase diagram. The results also show
that urea and NaOH do not interact when mixed with
water. These two components behave each as if they
were alone, when enough water is present in the
system: both NaOH and urea form their eutectics with
water, NaOH
5H2O + 4H2O and urea + 8H2O,
respectively. When cellulose is added to NaOH/
urea/water, the interaction between NaOH and cellu-
lose is the same as if urea were not present. This
means that urea is interacting neither with NaOH nor
with cellulose, and is not changing the NaOH-
cellulose interactions. The two questions are rising:
(i) why urea is efficient for helping the dissolution
and delaying gelation and (ii) why this seems to be
different from the NMR results reported in (Zhou
et al. 2004; Cai and Zhang 2005). NMR experiments
performed by Cai and Zhang 2005 and Zhou et al.
2004 show that there is a difference in the chemical
shift of + (0.7–0.8) ppm in the C=O vibration of
urea/D2O when it is in the presence of NaOH,
indicating some interaction of urea with NaOH. This
is a rather small shift that might indicate a special
interaction, but could also be due to small changes in
temperature or concentration. DCS experiments seem
to indicate that no interaction is taking place.
A possible origin of the role of urea as a
dissolution promoter can be that it strongly interacts
with water. Cellulose chains have the tendency to
aggregate as soon as the proportion 4NaOH/AGU
does not hold any more for any reason (temperature
increase, cellulose concentration increase). The addi-
tion of urea is decreasing the amount of free water,
thus helping cellulose chains to stay in solution.
Conclusions
Using DSC technique we showed that urea is not
directly interacting with NaOH or with cellulose.
This implies that the way urea is acting in cellulose/
NaOH/water solutions is not by making new com-
pounds with NaOH or cellulose, but by another
indirect way. It can be that the role of urea is to trap
the free water that is present in solution, preventing
cellulose chain to interact with other cellulose chains
and associate via hydrogen bond formation. It is
123
370
expected that the role of thiourea is similar than the
one of urea. More detailed studies focusing on the
water-urea interactions in the presence of cellulose
and NaOH are clearly needed to understand in depth
the role of urea.
Acknowledgements We are grateful to Spontex, France and
Innovia Films, UK, for the financial support of this work and
authorization to publish it. We thank Thomas Rosenau (BOKU,
Vienna, Austria) for his comments.
References
Cai J, Zhang L (2005) Rapid dissolution of cellulose in LiOH/
urea and NaOH/urea aqueous solutions. Macromol Biosci
5:539–548
Cohen-Adad R, Tranquard A, Peronne R, Negri P, Rollet A-P
(1960) Comptes Rendus de l’Académie des Sciences,
Paris, France, Novembre–Décembre 251(3):2035–2037
Cuissinat C, Navard P (2006) Swelling and dissolution of cellu-
lose Part II: free floating cotton and wood fibres in NaOH-
water-additives systems. Macromol Symp 244:19–30
Egal M (2006) Structure and properties of cellulose/NaOH
aqueous solutions, gels and regenerated objects, Thèse de
doctorat, Ecole Nationale Supérieure des Mines de Paris,
Sophia-Antipolis
Egal M, Budtova T, Navard P (2007) Structure of aqueous
solutions of microcrystalline cellulose-sodium hydroxide
below 0 °C and the limit of cellulose dissolution. Bio-
macromolecules 8:2282–2287
Isogai A, Atalla RH (1998) Dissolution of cellulose in aqueous
NaOH solutions. Cellulose 5:309–319
Kunze J, Fink H-P (2005) Structural changes and activation of
cellulose by caustic soda solution with urea. Macromol
Symp 223:175–188
Kuo Y-N, Hong J (2005) Investigation of solubility of micro-
crystalline cellulose in aqueous NaOH. Polym Adv
Technol 16:425–428
Laszkiewicz B (1998) Solubility of bacterial cellulose and its
structural properties. J Appl Polym Sci 67:1871–1876
Pickering SU (1893) The hydrates of sodium, potassium and
lithium hydroxides. J Chem Soc 63:890–909
123
Cellulose (2008) 15:361–370
Rabinovich VA, Khavin ZYa (1978) Handbook on chemistry
(in Russian), 2nd edn. ‘‘Khimiya’’, Leningrad division
Roy C Etude de mélanges de cellulose dans des solutions
aqueuses de soude (2002) Thèse de doctorat, Ecole Na-
tionale Supérieure des Mines de Paris, Sophia-Antipolis
Roy C, Budtova T, Navard P, Bedue O (2001) Structure of
cellulose-soda solutions at low temperatures. Biomacro-
molecules 2:687–694
Roy C, Budtova T., Navard P (2003) Rheological properties
and gelation of aqueous cellulose-NaOH solutions. Bio-
macromolecules 4:259–264
Sobue H, Kiesslig H, Hess K (1939) The cellulose-sodium
hydroxide-water system as a function of the temperature.
Z Phys Chem B 43:309–328
Weast RC, Astle MJ, Beyer WH (1983) Handbook of chem-
istry and physics, 64th edn., 1983–1984. CRC Press Inc.,
Boca Raton
Weng L, Zhang L, Ruan D, Shi L, Xu J (2004) Thermal
gelation of cellulose in a NaOH/thiourea aqueous solu-
tion. Langmuir 20(6):2086–2093
Yamane C, Saito M, Okajima K 1996a) Specification of alkali
soluble pulp suitable for new cellulosic filament produc-
tion. Sen’I Gakkaishi 52:318–324
Yamane C, Saito M, Okajima K 1996b) Industrial preparation
method of cellulose-alkali dope with high solubility. Sen’I
Gakkaishi 52:310–317
Yamane C, Saito M, Okajima K (1996c) New spinning process
of cellulose filament production from alkli soluble cellu-
lose dope-net process. Sen’I Gakkaishi 52:378–384
Yamashiki T, Kamide K, Okajima K, Kowsaka K, Matsui T,
Fukase H (1988) Some characteristic features of dilute
aqueous alkali solutions of specific alkali concentration
(2.5 mol/l) which possess maximum solubility power
against cellulose. Polym J 20:447–457
Zhang L, Ruan D, Gao S (2002) Dissolution and regeneration
of cellulose inNaOH/Thiourea aqueous solution. J Polym
Sci: Part B 40:1521–1529
Zhou J, Zhang L (2000) Solubility of cellulose in NaOH/Urea
aqueous solution. Polym J 32(10):866–870
Zhou J, Zhang L, Cai J, Shu H (2002) Cellulose microporous
membranes prepared from NaOH/urea aqueous solution. J
Membr Sci 210:77–90
Zhou J, Zhang L, Cai J (2004) Behavior of cellulose in NaOH/
Urea aqueous solution characterized by light scattering
and viscometry. J Polym Sci: Part B 42:347–353